silane cross-linked polyolefin elastomer blend, and method for making an elastomeric article.

专利摘要:
An elastomeric article is envisaged which includes a composition having a silane crosslinked polyolefin elastomer with a density of less than 0.90 g / cm3. the elastomeric article may exhibit a deformation after compression of from about 5.0% to about 35.0% as measured according to astm d 395 (22 hours at 70 ° c). the silane crosslinked polyolefin elastomer may include a first polyolefin having a density of less than 0.86 g / cm3, a second polyolefin having a crystallinity less than 40%, a silane crosslinker, a graft initiator, and a condensation.
公开号:BR112019011570A2
申请号:R112019011570
申请日:2017-12-08
公开日:2019-10-22
发明作者:Ji Gending；Gopalan Krishnamachari；j lenhart Robert；Herd-Smith Roland
申请人:Cooper Standard Automotive Inc；
IPC主号:

专利说明:

BLEND OF POLYOLEFIN ELASTOMER cross-linked by a silane, and, a method for manufacturing an elastomeric article
FIELD OF DESCRIPTION [001] The description generally refers to silane-grafted polyolefin elastomer compositions that can be used to form many different end products and, more particularly, to compositions and methods for manufacturing these compositions used to form gasket seals. tightness, membranes, hoses, and other elastic materials.
BACKGROUND OF THE DESCRIPTION [002] Vulcanized thermoplastics (TPV) are part of the thermoplastic elastomer (TPE) family of polymers, but are the closest in elastomeric properties of thermofixed rubber of ethylene propylene diene monomer (EPDM). TPVs are relatively easy to process, but their properties may be limited in terms of elastomeric performance and durability over time. Similarly, EPDM rubber formulations often require many ingredients (for example, carbon black, petroleum based oil, zinc oxide, various fillers, such as calcium carbonate or talc, processing aids, dressings, blowing agents, and many other materials to meet performance requirements), which tend to decrease their elastic performance over time and increase their material cost.
[003] EPDM-based materials are also expensive from a process point of view. The constituent ingredients of EPDM are typically mixed together in a one or two step process before dispatch to an extrusion facility. In the extrusion facility, the ingredients and rubber compound (s) are extruded together to form a final material, which is subsequently formed into a variety of elastomeric materials. Thus, the extrusion process used to manufacture joints
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2/81 tightness can include many stages, depending on the type of EPDM or other types of resins, and may additionally require long lengths of curing wafers. For example, extrusion lines up to 73.15 meters (80 yards) in length that are powered by natural gas and / or electricity may be required. Most natural gas and / or electricity are used to heat hot air, microwaves, infrared, or other types of equipment used to vulcanize EPDM rubber compounds. The vulcanization process also produces fumes that must be exhausted and monitored to meet environmental requirements. Overall, the processes used to make traditional EPDM-based products can be very time-consuming, expensive and environmentally aggressive.
[004] Aware of the drawbacks associated with current polymeric compositions based on TPV and EPDM, the industry has a need for the development of new compositions and methods for manufacturing polyolefin elastomeric materials that are simpler, of lower weight, less cost , have superior long-term head loss (LLS) and are more environmentally friendly.
SUMMARY OF DESCRIPTION [005] In accordance with an aspect of the present description, a blend of polyolefin elastomer crosslinked by a silane is described. A blend of polyolefin elastomer crosslinked by a silane includes a first polyolefin having a density of less than 0.86 g / cm ³ , a second polyolefin having a crystallinity of less than 40%, and a silane crosslinker. The silane-crosslinked polyolefin elastomer blend has a deformation after compression of about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 h at 70 ° C). The silane-crosslinked polyolefin elastomer blend has a density of less than 0.90 g / cm ^3.
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3/81 [006] In accordance with another aspect of the present description, a blend of polyolefin elastomer crosslinked by a silane is described. The silane crosslinked polyolefin elastomer blend includes a first polyolefin having a density less than 0.6 g / cm ³ , a second polyolefin having a crystallinity of less than 40%, a silane crosslinker, and a microencapsulating foaming agent. The silane-crosslinked polyolefin elastomer blend has a deformation after compression of about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 h at 70 ° C). The silane crosslinked polyolefin elastomer blend has a density less than 0.70 g / cm ^3, [007] In accordance with a further aspect of the present description, a silane crosslinked polyolefin elastomer blend is described. The silane crosslinked polyolefin elastomer blend includes a first polyolefin having a density less than 0.86 g / cm ³ , a second polyolefin having a crystallinity of less than 40%, a silane crosslinker, and a foaming agent. The polyolefin elastomer blend crosslinked by a silane shows a deformation after compression of about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 h at 7 ° C). The silane-crosslinked polyolefin elastomer blend has a density of less than 0.60 g / cm ^3, [008] In accordance with an additional aspect of the present description, an elastomeric article having a crosslinked polyolefin elastomer blend is described. a silane including a first polyolefin having a density less than 0.86 g / cm ³ , a second polyolefin having a crystallinity of less than 40%, and a silane crosslinker. The elastomeric article presents a deformation after compression of about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 h at 70 ° C). The elastomeric article additionally has a density of less than 0.60 g / cm ^3, [009] According to a further aspect of this
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4/81 description, a method for making an elastomeric article is described. The method includes the steps of: extruding a first polyolefin having a density less than 0.86 g / cm ³ , a second polyolefin having less than 40% crystallinity, a silane crosslinker and a graft initiator together to form a blend of polyolefin grafted with silane; extruding the silane-grafted polyolefin blend and a condensation catalyst together to form a silane crosslinkable polyolefin blend; molding the silane crosslinkable polyolefin blend into an uncured elastomeric article; and cross-link the crosslinkable polyolefin blend at room temperature and room humidity to form the elastomeric article having a density of less than 0.90 g / cm ^3. The elastomeric article shows a compression strain of about 5.0% at about 35.0%, as measured according to ASTM D 395 (22 h at 70 ° C).
[0010] These and other aspects, objects, and characteristics of the present description will be understood and appreciated by those skilled in the art by studying the following specification, claims and attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
Figure 1 is a schematic reaction path used to produce a silane crosslinked polyolefin elastomer according to some aspects of the present description.
Figure 2 is a flow chart of a method for fabricating a static seal with a silane crosslinked polyolefin elastomer using a two-stage Sioplas approach in accordance with some aspects of the present description;
Figure 3A is a schematic cross-sectional view of a reactive twin screw extruder according to some aspects of the present description;
Figure 3B is a schematic cross-sectional view of
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5/81 a single screw extruder according to some aspects of the present description;
Figure 4 is a flow chart of a method for fabricating a static seal with a silane crosslinked polyolefin elastomer using a one-step Monosil approach according to some aspects of the present description;
Figure 5 is a schematic cross-sectional view of a reactive single screw extruder according to some aspects of the present description;
Figure 6 is a graph illustrating the stress / strain behavior of a silane crosslinked polyolefin elastomer compared to EPDM compounds;
Figure 7 is a graph illustrating the edge deformation after compression of inventive silane crosslinked polyolefin elastomers and comparative polyolefin elastomers;
Figure 8 is a graph illustrating the edge deformation recovery of inventive silane crosslinked polyolefin elastomers and comparative polyolefin elastomers;
Figure 9 is a graph illustrating the relaxation rate of various silane-crosslinked polyolefin elastomers and comparative polyolefin elastomers;
Figure 10 is a graph illustrating the stress / strain behavior of a polyolefin elastomer crosslinked by an inventive silane;
Figure 11 is a graph illustrating the deformation after compression of EPDM, TPV, and a silane crosslinked polyolefin elastomer as plotted with respect to various test temperatures and weather conditions;
Figure 12 is a graph illustrating the deformation after
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6/81 compression of EPDM, TPV, and a silane crosslinked polyolefin elastomer as plotted with respect to temperatures ranging from 23 ° C to 175 ° C;
Figure 13 is a graph illustrating the deformation after compression of TPV and several polyolefin elastomers cross-linked by a silane as plotted with respect to temperatures of 23 ° C and 125 ° C;
Figure 14 is a graph illustrating the loading behavior versus position of a dynamic silane crosslinked elastomer compared to the loading behavior versus position of comparative EPDM compounds; and
Figure 15 is a series of micrographs of dynamic silane-crosslinked elastomers, as processed with a gas-injected supercritical fluid or a chemical foaming agent fluid, according to aspects of the description.
DETAILED DESCRIPTION OF THE MODALITIES [0011] For purposes of description here the terms “top”, “bottom”, “right”, “left” “rear”, “front”, “vertical”, “horizontal” and their derivatives must relate to the static seals in the description as oriented on the vehicle shown in Figure 1. However, it should be understood that the device can assume several alternative orientations and step sequences, except where expressly specified otherwise. It should also be understood that the specific devices and processes illustrated in the attached drawings, and described in the specification below are simply exemplary modalities of the inventive concepts defined in the attached claims. Thus, specific dimensions and other physical characteristics relating to the modalities described here should not be considered as limiting, unless the claims expressly state otherwise.
[0012] All ranges described here are inclusive of the extreme point
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7/81 cited and independently combinable (for example, the range “from 2 to 10” is inclusive of the extreme points, 2 and 10, and all intermediate values). The extreme points of the ranges and any values described here are not limited to the precise range or value; they are sufficiently inaccurate to include values that approximate these ranges and / or values.
[0013] A value modified by a term or terms, such as "about" and "substantially", may not be limited to the precise value specified. The approximate language can correspond to the precision of an instrument to measure the value. The “about” modifier should also be considered to describe the range defined by the absolute values of the two extreme points. For example, the expression "from about 2 to about 4" also describes the range "from 2 to 4".
[0014] As used herein, the term “and / or”, when used in a list of two or more items, means that any of the items listed can be used in itself, or any combination of two or more of the items listed can be employed. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A only; B only; C only; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
[0015] With reference to Figures 1-13, a silane crosslinked polyolefin elastomer is provided. In general, the polyolefin elastomer crosslinked by a silane can show a strain after compression of about 5.0% to about 35.0% measured according to ASTM D 395 (22 h at 70 ° C). The silane crosslinked polyolefin elastomer can be produced from a blend including a first polyolefin having a density less than 0.86 g / cm ³ , a second polyolefin having a crystallinity less than 40 ° C, a silane crosslinker, a graft initiator, and a condensation catalyst. In some respects, the silane crosslinked polyolefin elastomer has a density less than 0.90
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8/81 g / cm ³ . In other respects, the silane crosslinked polyolefin elastomer has a density less than 0.70 g / cm ³ . In still other aspects, ο polyolefin elastomer crosslinked by a silane has a density of less than 0.60 g / cm ^3, [0016] Thus, the present description is centered on the composition, the method of making the composition, and the corresponding properties of the material for the silane crosslinked polyolefin elastomer used to manufacture the elastomeric articles. The elastomeric article is formed from a silane-grafted polyolefin where the silane-grafted polyolefin can have a catalyst added to form a silane crosslinkable polyolefin elastomer. This silane crosslinkable polyolefin can then be crosslinked by exposure to moisture and / or heat to form the polyolefin elastomer crosslinked by a final silane or blend. In many respects, the polyolefin elastomer crosslinked by a silane or blend includes a first polyolefin having a density of less than 0.90 g / cm ³ , a second polyolefin having a crystallinity of less than 40%, a silane crosslinker, an initiator of graft, and a condensation catalyst. In other respects, the polyolefin elastomer crosslinked by a silane or blend includes only one polyolefin having a density less than 0.90 g / cm ³ and a crystallinity less than 40%, a silane crosslinker, a graft initiator, and a condensation catalyst.
First Polyolefin [0017] The first polyolefin can be a polyolefin elastomer including an olefin block copolymer, an ethylene / aolefin copolymer, a propylene / a-olefin copolymer, EPDM, EPM, or a mixture of two or more any of these materials. Exemplary block copolymers include those sold under the trade names INFUSE ™, an olefin block copolymer (The Dow Chemical Company) and SEPTON ™ V-SERIES, a styrene block copolymer
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9/81 ethylene-butylene-styrene (Kuraray Co., LTD.). Exemplary ethylene / aolefin copolymers include those sold under the trade names TAFMER ™ (for example, TAFMER DF710) (Mitsui Chemicals, Inc.), and ENGAGE ™ (for example, ENGAGE 8150) (Dow Chemical Company). Exemplary propylene / α-olefin copolymers include those sold under the brand name types VISTAMAXX 6102 (Exxon Mobil Chemical Company), TAFMER ™ XM (Mitsui Chemical Company), and Versify (Dow Chemical Company). EPDM can have a diene content of about 0.5 to about 10% by weight. Ο EPM can have an ethylene content of 45% by weight to 75% by weight.
[0018] The term "comonomer" refers to olefin comonomers that are suitable to be polymerized with olefin monomers, such as ethylene or propylene monomers. Comonomers can comprise, but are not limited to, aliphatic, C2-C20 α-olefins. Examples of suitable aliphatic C2-C20 α-olefins include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1hexadecene, 1-octadecene and 1-eicosene. In some ways, the comonomer is vinyl acetate. The term "copolymer" refers to a polymer, which is produced by attaching more than one type of monomer to the same polymer chain. The term "homopolymer" refers to a polymer that is produced by binding olefin monomers, in the absence of comonomers. The amount of comonomer may, in some embodiments, be greater than 0 to about 12% by weight based on the weight of the polyolefin, including from greater than 0 to about 9% by weight and greater than 0 to about 7% by weight. In some embodiments, the comonomer content is greater than about 2 mol% of the final polymer, including greater than about 3 mol% and greater than about 6 mol%. The comonomer content can be less than or equal to about 30 mol%. A copolymer can be a random or block (heterophasic) copolymer. In
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10/81 some modalities, polyolefin is a random copolymer of propylene and ethylene.
[0019] In some respects, the first polyolefin is selected from the group consisting of: an olefin homopolymer, a blend of homopolymers, a copolymer produced using two or more olefins, a blend of copolymers each produced using two or more olefins, and a combination of olefin homopolymers mixed with copolymers produced using two or more olefins. The olefin can be selected from ethylene, propylene, 1-butene, 1-propene, 1-hexene, 1-octene, and another 1olefin higher. The first polyolefin can be synthesized using many different processes (for example, using solution-based metallocene gas and Ziegler-Natta catalysis) and optionally using a suitable catalyst to polymerize ethylene and / or a-olefins. In some ways, a metallocene catalyst can be used to produce low density ethylene / α-olefin polymers.
[0020] In some respects, the first polyolefin includes an ethylene-octene copolymer, a random ethylene-octene copolymer, an ethylene-octene block copolymer where the ethylene-octene copolymer is produced from about 30% by weight of ethylene, about 35% by weight of ethylene, about 40% by weight of ethylene, about 45% by weight of ethylene, about 50% by weight of ethylene, about 55% by weight of ethylene, about 60% by weight of ethylene, about 65% by weight of ethylene, about 70% by weight of ethylene, about 75% by weight of ethylene, about 80% by weight of ethylene, or about 85% by weight of ethylene. In other respects, the first polyolefin includes an ethylene-1-alkene copolymer, a random ethylene-1-alkene copolymer, an ethylene-1-alkene block copolymer where the ethylene-1-alkene copolymer is produced from about about 30% by weight of ethylene, about 35% by weight of ethylene, about 40% by weight of ethylene, about 45% by weight of ethylene, about 50% by weight of ethylene, about
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11/81
55% by weight of ethylene, about 60% by weight of ethylene, about 65% by weight of ethylene, about 70% by weight of ethylene, about 75% by weight of ethylene, about 80% by weight of ethylene, or about 85% by weight of ethylene.
[0021] In some respects, the polyethylene used for the first polyolefin can be classified into several types including, but not limited to, LDPE (Low Density Polyethylene), LLDPE (Linear Low Density Polyethylene), and HDPE (High Polyethylene) Density). In other respects, polyethylene can be classified as Ultra High Molecular Weight (UHMW), High Molecular Weight (HMW), Average Molecular Weight (MMW) and Low Molecular Weight (LMW). In still other aspects, polyethylene can be an ultra-low density ethylene elastomer.
[0022] In some respects, the first polyolefin may include an LDPE / silane copolymer or blend. In other respects, the first polyolefin can be polyethylene which can be produced using any catalyst known in the art including, but not limited to, chromium catalysts, Ziegler-Natta catalysts, metallocene catalysts or post-metallocene catalysts.
[0023] In some respects, the first polyolefin may have a molecular weight distribution Mw / Mn less than or equal to about 5, less than or equal to about 4, from about 1 to about 3.5 , or from about 1 to about 3. [0024] The first polyolefin can be present in an amount of more than 0 to about 100% by weight of the composition. In some embodiments, the amount of polyolefin elastomer is from about 30 to about 70% by weight. In some aspects, the first polyolefin fed to an extruder can include from about 50% by weight to about 80% by weight of an ethylene / α-olefin copolymer, including from about 60% by weight to about 75% by weight and from about 62% by weight to about 72% by weight
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12/81 weight.
[0025] The first polyolefin may have a melt viscosity in the range of about 2000 cP to about 50,000 cP, as measured using a Brookfield viscometer at a temperature of about 177 ° C. In some embodiments, the melt viscosity is from about 4000 cP to about 40,000 cP, including from about 5000 cP to about 30,000 cP and from about 6000 cP to about 18000 cP.
[0026] The first polyolefin can have a melting index (T2), measured at 190 ° C under a load of 2.16 kg, from about 20.0 g / 10 min to about 3500 g / 10 min, including from about 250 g / 10 min to about 1900 g / 10 min and from about 300 g / 10 min to about 1500 g / 10 min. In some respects, the first polyolefin has a fractional melt index of 0.5 g / 10 min to about 3500 g / 10 min.
[0027] In some respects, the density of the first polyolefin is less than 0.90 g / cm ³ , less than about 0.89 g / cm ³ , less than about 0.88 g / cm ³ , less than about 0.87 g / cm ³ , less than about 0.86 g / cm ³ , less than about 0.85 g / cm ³ , less than about 0.84 g / cm ³ , less than about 0.83 g / cm ³ , less than about 0.82 g / cm ³ , less than about 0.81 g / cm ³ , or less than about 0.80 g / cm ^3. In other respects, the density of the first polyolefin can be from about 0.85 g / cm ³ to about 0.89 g / cm ³ , from about 0.85 g / cm ³ to about 0.88 g / cm ³ , from about 0.84 g / cm ³ to about 0.88 g / cm ³ , or from about 0.83 g / cm ³ to about 0.87 g / cm ^{3 .} in yet other aspects, the density is about 0.84 g / cm ³ to about 0.85 g / cm ³ to about 0.86 g / cm ³ to about 0.87 g / cm ^3, about 0.88 g / cm ³ , or about 0.89 g / cm ^3, [0028] The percent crystallinity of the first polyolefin may be less than about 60%, less or about 50%, less than about 40%, less than about 35%, less than about 30%, less than about 25%, or less than about 20%. The percentage crystallinity
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13/81 can be at least about 10%. In some aspects, crystallinity is in the range of about 2% to about 60%.
Second Polyolefin [0029] The second polyolefin can be a polyolefin elastomer including an olefin block copolymer, an ethylene / aolefin copolymer, a propylene / a-olefin copolymer, EPDM, EPM, or a mixture of two or more of any of these materials. Exemplary olefin block copolymers include those sold under the trade names INFUSE ™ (Dow Chemical Company) and SEPTON ™ V-SERIES (Kuraray Co., LTD.). Exemplary ethylene / α-olefin copolymers include those sold under the trade names TAFMER ™ (for example, TAFMER DF710) (Mitsui Chemicals, Inc.) and ENGAGE ™ (for example, ENGAGE 8150) (Dow Chemical Company). Exemplary propylene / aolefin copolymers include those sold under the brand names TAFMER ™ XM (Mitsui Chemical Company) and VISTAMAXX ™ (for example, VISTAMAXX 6102) (Exxon Mobil Chemical Company). EPDM can have a diene content of about 0.5 to about 10% by weight. EPM can have an ethylene content of 45% by weight to 75% by weight.
[0030] In some respects, the second polyolefin is selected from the group consisting of: an olefin homopolymer, a blend of homopolymers, a copolymer produced using two or more olefins, a blend of copolymers each produced using two or more olefins, and a blend of olefin homopolymers with copolymers produced using two or more olefins. The olefin can be selected from ethylene, propylene, 1-butene, 1-propene, 1-hexene, 1-octene, another higher 1-olefin. The first polyolefin can be synthesized using many different processes (for example, using solution-based metallocene gas and Ziegler-Natta catalysis) and optionally using a suitable catalyst to polymerize ethylene and / or α-olefins. In some respects, a
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14/81 metallocene catalyst can be used to produce low density ethylene / α-olefin polymers.
[0031] In some respects, the second polyolefin includes an ethylene-octene copolymer, a random ethylene-octene copolymer, an ethylene-octene block copolymer where the ethylene-octene copolymer is produced of about 30% by weight ethylene, about 35% by weight ethylene, about 40% by weight ethylene, about 45% by weight ethylene, about 50% by weight ethylene, about 55% by weight ethylene, about 60% by weight of ethylene, about 65% by weight of ethylene, about 70% by weight of ethylene, about 75% by weight of ethylene, about 80% by weight of ethylene, or about 85% by weight of ethylene. In other respects, the first polyolefin includes an ethylene-1-alkene copolymer, a random ethylene-1-alkene copolymer, an ethylene-1-alkene block copolymer where the ethylene-1-alkene copolymer is produced from about about 30% by weight of ethylene, about 35% by weight of ethylene, about 40% by weight of ethylene, about 45% by weight of ethylene, about 50% by weight of ethylene, about 55% by weight ethylene, about 60% by weight ethylene, about 65% by weight ethylene, about 70% by weight ethylene, about 75% by weight ethylene, about 80% by weight ethylene, or about 85% by weight of ethylene.
[0032] In some respects, the second polyolefin may include a polypropylene homopolymer, a polypropylene copolymer, a polyethylene-co-propylene copolymer, or a mixture thereof. Suitable polypropylenes include, but are not limited to, polypropylene obtained by homopolymerization of propylene or copolymerization of propylene and an alpha-olefin comonomer. In some respects, the second polyolefin may have a higher molecular weight and / or a higher density than the first polyolefin.
[0033] In some embodiments, the second polyolefin can have a
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15/81 molecular weight distribution M _w / M _n less than or equal to about 5, less than or equal to about 4, about 1 to about 3.5, or about 1 to about 3. [0034] The second polyolefin can be present in an amount of more than 0% by weight to about 100% by weight of the composition. In some embodiments, the amount of polyolefin elastomer is about 30% by weight to about 70% by weight. In some embodiments, the second polyolefin fed to the extruder may include from about 10% by weight to about 50% by weight of polypropylene, from about 20% by weight to about 40% by weight of polypropylene, or from about 25% by weight to about 35% by weight of polypropylene. The polypropylene can be a homopolymer or a copolymer.
[0035] The second polyolefin may have a melt viscosity in the range of about 2000 cP to about 50,000 cP as measured using a Brookfield viscometer at a temperature of about 177 ° C. In some embodiments, the melt viscosity is from about 4000 cP to about 40,000 cP, including from about 5000 cP to about 30,000 cP and from about 6000 cP to about 18000 cP.
[0036] The second polyolefin can have a melt index (T2), measured at 190 ° C under a load of 2.16 kg, from about 20.0 g / 10 min to about 3500 g / 10 min, including from about 250 g / 10 min to about 1900 g / 10 min and from about 300 g / 10 min to about 1500 g / 10 min. In some embodiments, the polyolefin has a fractional melt index of 0.5 g / 10 min to about 3,500 g / 10 min.
[0037] In some respects, the density of the second polyolefin is less than 0.90 g / cm ³ , less than about 0.89 g / cm ³ , less than about 0.88 g / cm ³ , less than about 0.87 g / cm ³ , less than about 0.86 g / cm ³ , less than about 0.85 g / cm ³ , less than about 0.84 g / cm ³ , less than about 0.83 g / cm ³ , less than about 0.82 g / cm ³ ,
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16/81 less than about 0.81 g / cm ³ , or less than about 0.80 g / cm ^3. In other respects, the density of the first polyolefin may be about 0.85 g / cm ³ to about 0.89 g / cm ³ , from about 0.85 g / cm ³ to about 0.88 g / cm ³ , from about 0.84 g / cm ³ to about 0.88 g / cm ³ , or from about 0.83 g / cm ³ to about 0.87 g / cm ^3. In still other aspects, the density is about 0.84 g / cm ³ , about 0.85 g / cm ³ , about 0.86 g / cm ³ , about 0.87 g / cm ³ , about 0.88 g / cm ³ , or about 0.89 g / cm ^3, [0038] A Percent crystallinity of the second polyolefin can be less than about 60%, less than about 50%, less than about 40%, less than about 35%, less than about 30%, less than about 25%, or less than about 20%. The percentage crystallinity can be at least about 10%. In some aspects, crystallinity is in the range of about 2% to about 60%.
[0039] As noted, the polyolefin elastomer crosslinked by a silane or blend, for example, as used in static sealing members 12 (see Figures 1, 2, 4 and 5), includes both the first polyolefin and the second polyolefin. The second polyolefin is generally used to modify the hardness and / or processability of the first polyolefin having a density less than 0.90 g / cm ³ . In some ways, more than just the first and second polyolefins can be used to form the polyolefin elastomer crosslinked by a silane or blend. For example, in some ways, one, two, three, four, or more different polyolefins having a density less than 0.90 g / cm ³ , less than 0.89 g / cm ³ , less than 0.88 g / cm ³ , less than 0.87 g / cm ³ , less than 0.86 g / cm ³ , or less than 0.85 g / cm ³ can replace and / or be used for the first polyolefin. In some respects, one, two, three, four, or more different polyolefins, polyethylene-co-propylene copolymers can substitute and / or be used for the second polyolefin.
[0040] The blend of the first polyolefin having a lower density
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17/81 that 0.90 g / cm ³ and the second polyolefin having less than 40% crystallinity is used because the subsequent silane grafting and crosslinking of these first and second polyolefin materials together are what form the core resin structure in the polyolefin elastomer structure cross-linked by a final silane. Although additional polyolefins can be added to the blend of silane-grafted polyolefin elastomer, cross-linked with silane, and / or cross-linked with silane as fillers to improve and / or modify the Young's modulus as desired for the final product, any polyolefins added to the blend having a crystallinity equal to or greater than 40% are not chemically or covalently incorporated into the crosslinked structure of the polyolefin elastomer crosslinked by a final silane.
[0041] In some respects, the first and second polyolefins may additionally include one or more TPVs and / or EPDM with or without silane graft units where TPV and / or EPDM polymers are present in an amount of up to 20% by weight of the polyolefin elastomer blend / silane crosslinker.
Graft initiator [0042] A graft initiator (also referred to as "a radical initiator" in the description) can be used in the process of grafting at least the first and second polyolefins by reacting with the respective polyolefins to form a reactive species that can react and / or couple with the silane crosslinker molecule. The graft initiator can include halogen molecules, azo compounds (for example, azobisisobutyl), carboxylic peroxyacids, peroxyesters, peroxicetals, and peroxides (for example, alkyl hydroperoxides, dialkyl peroxides, and diacyl peroxides). In some embodiments, the graft initiator is an organic peroxide selected from di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl-peroxy ) hexine-3, 1,3-bis (t
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18/81 butyl-peroxy-isopropyl) benzene, n-butyl-4,4-bis (t-butyl-peroxy) valerate, benzoyl peroxide, t-butyl peroxybenzoate, isopropyl t-butylperoxy carbonate, and t-perbenzoation -butyl, as well as bis (2-methylbenzoyl) peroxide, bis (4-methylbenzoyl) peroxide, t-butyl peroctoate, cumene hydroperoxides, methyl ethyl ketone peroxide, lauryl peroxide, tert-butyl peracetate, dioxide peroxide -t-amyl, t-amyl peroxybenzoate,
1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, a, a'-bis (t-butylperoxy) -l, 3diisopropillbenzene, a, a'-bis (t-butylpexoxy) -l , 4-diisopropylbenzene, 2,5-bis (tbutylperoxy) -2,5-dimethylhexane, and 2,5-bis (t-butylperoxy) -2,5-dimethyl-3-hexine and 2,4- dichlorobenzoyl, Exemplary peroxides include those sold under the trade name LUPEROX ™ (available from Arkema, Inc.).
[0043] In some respects, the graft initiator is present in an amount of more than 0% by weight to about 2% by weight of the composition, including from about 0.15% by weight to about 1.2 % by weight of the composition. The amount of initiator and silane employed can affect the final structure of the silane-grafted polymer (for example, the degree of grafting in the grafted polymer and the degree of crosslinking in the cured polymer). In some respects, the reactive composition contains at least 100 ppm of initiator, or at least 300 ppm of initiator. The initiator can be present in an amount of 300 ppm to 1500 ppm, or 300 ppm to 2000 ppm. The silane: initiator weight ratio can be about 20: 1 to 400: 1, including about 30: 1 to about 400: 1, about 48: 1 to about 350: 1, and about 55: 1 to about 333: 1, [0044] The graft reaction can be performed under conditions that optimize grafts on the 'backbone' of the interpolymer while minimizing side reactions (for example, homopolymerization of the graft agent). The graft reaction can be performed in a bath, in solution, in a solid state, and / or in a swollen state. Silanation can be
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19/81 carried out in a wide variety of equipment (for example, twin screw extruders, single screw extruders, Brabenders, internal blenders, such as Banbury blenders, and batch reactors). In some embodiments, the polyolefin, silane, and initiator are mixed in the first stage of an extruder. The bath temperature (that is, the temperature at which the polymer starts to melt and starts to flow) can be from about 120 ° C to about 260 ° C, including from about 130 ° C to about 250 ° C .
Silane crosslinker [0045] A silane crosslinker can be used to graft silane units over the first and second polyolefins covalently and the silane crosslinker can include and alkoxysilanes, silazanes, siloxanes, or a combination thereof. The grafting and / or coupling of the various silane crosslinkers or potential silane crosslinker molecules is facilitated by the reactive species formed by the graft initiator reacting with the respective silane crosslinker.
[0046] In some respects, the silane crosslinker is a silazane where the silazane may include, for example, hexamethyldisilazane (HMDS) or bis (trimethylsilyl) amine. In some respects, the silane crosslinker is a siloxane where the siloxane may include, for example, polydimethylsiloxane (PDMS) and octamethylcyclotetrassiloxane.
[0047] In some respects, the silane crosslinker is an alkoxysilane. As used herein, the term "alkoxysilane" refers to a compound comprising a silicon atom, at least one alkoxy group and at least one other organic group, wherein the silicon atom is bonded to the organic group by a bond covalent. Preferably, the alkoxysilane is selected from alkylsilanes; acrylic-based silanes; vinyl-based silanes; aromatic silanes; epoxy-based silanes; amino-based silanes and amines having -NH, -NHCH3 or -N (CH3) 2; ureido-based silanes; mercapto-based silanes; and alkoxysilanes that have a hydroxyl group (i.e., -OH). a
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20/81 acrylic-based silane can be selected from the group comprising betaacryloxyethyl trimethoxysilane; beta-acryloxy propyl trimethoxysilane; gamma acryloxyethyl trimethoxysilane; gamma-acryloxypropyl trimethoxysilane; betaacryloxyethyl triethoxysilane; beta-acryloxypropyl triethoxysilane; gammaacryloxyethyl triethoxysilane; gamma-acryloxypropyl triethoxysilane; betamethacryloxyethyl trimethoxysilane; beta-methacryloxypropyl trimethoxysilane; gamma-methacryloxyethyl trimethoxysilane; gamma-methacryloxypropyl trimethoxysilane; beta-methacryloxyethyl triethoxysilane; beta-methacryloxypropyl triethoxysilane; gamma-methacryloxyethyl triethoxysilane; gamma-methacryloxypropyl triethoxysilane; 3-methacryloxypropylmethyl diethoxysilane. A vinyl-based silane can be selected from the group comprising vinyl trimethoxysilane; vinyl triethoxysilane; p-styryl trimethoxysilane, methylvinldimethoxysilane, vinildimethylmethoxysilane, di vinildimethoxysilane, vinyltris (2methoxyethoxy) silane, and vinylbenzylethylenediaminopropyltrimethoxysilane. An aromatic silane can be selected from phenyltrimethoxysilane and phenyltriethoxysilane. An epoxy-based silane can be selected from the group comprising 3-glycidoxypropyl trimethoxysilane; 3-glycidoxypropylmethyl diethoxysilane; 3-glycidoxypropyl triethoxysilane; 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, and glycidyloxypropylmethyldimethoxysilane. An amino-based silane can be selected from the group comprising 3-aminopropyl triethoxysilane; 3-aminopropyl trimethoxysilane; 3-aminopropyldimethyl ethoxysilane; 3-aminopropylmethyldiethoxysilane; 4-aminobutyltriethoxysilane; 3- aminopropyl diisopropyl ethoxysilane; 1-amino-2- (dimethylethoxysilyl) propane; (aminoethylamino) -3-isobutyldimethyl methoxy silane; N- (2-aminoethyl) -3aminoisobutylmethyl dimethoxysilane; (aminoethylaminomethyl) phenethyl trimethoxysilane; N- (2-aminoethyl) -3-aminopropylmethyl dimethoxysilane; N- (2aminoethyl) -3-aminopropyl trimethoxysilane; N- (2-aminoethyl) -3-aminopropyl triethoxysilane; N- (6-aminohexyl) aminomethyl trimethoxysilane; N- (6aminohexyl) aminomethyl trimethoxysilane; N- (6-amino-hexyl) aminopropyl
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21/81 trimethoxysilane; N- (2-aminoethyl) -1,1-aminoundecyl trimethoxysilane; 1,1aminoundecyl triethoxysilane; 3- (m-aminophenoxy) propyl trimethoxysilane; maminophenyl trimethoxy silane; p-aminophenyl trimethoxysilane; (3-trimethoxysilylpropyl) diethylene triamine; N-methylaminopropylmethyl dimethoxysilane; N-methylaminopropyl trimethoxysilane; dimethylaminomethyl ethoxysilane; (N, N-dimethylaminopropyl) trimethoxysilane; (N-acetylglycysyl) -3aminopropyl trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-
3-aminopropyltriethoxysilane, phenylaminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, and aminoethylaminopropylmethyl dimethoxysilane. A ureido-based silane can be 3-ureidepropyl triethoxysilane. A mercapto-based silane can be selected from the group comprising 3-mercaptopropylmethyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, and 3-mercaptopropyl triethoxysilane. An alkoxysilane having a hydroxyl group can be selected from the group comprising hydroxymethyl triethoxysilane; N- (hydroxyethyl) -N-methylaminopropyl trimethoxysilane; bis (2-hydroxyethyl) -3-aminopropyl triethoxysilane; N- (3-triethoxysilylpropyl) -4-hydroxy butylamide; 1.1 - (triethoxysilyl) undecanol;
triethoxysilyl undecanol; ethylene glycol acetal; and N- (3-ethoxysilylpropyl) gluconamide.
[0048] In some aspects, the alkylsilane can be expressed with a general formula: R _n Si (OR ') _4-n ^wherein: n is 1, 2 or 3; R is C1-20 alkyl or C2-20 alkenyl; and R 'is C1-20 alkyl. The term "alkyl" alone or as part of another substituent, refers to a straight, branched or cyclic saturated hydrocarbon group joined by single carbonocarbon bonds having 1 to 20 carbon atoms, for example 1 to 10 carbon atoms, for example 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. When a subscript is used here following a carbon atom, the subscript refers to the number of carbon atoms that the named group can contain. So, for example, C1-6 alkyl means alkyl
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22/81 of one to six carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, f-butyl, 2-methylbutyl, pentyl, iso-amyl and its isomers, hexyl and its isomers, heptila and its isomers, octyl and its isomer, decila and its isomer, dodecyl and its isomers. The term "C2-20 alkenyl" alone or as part of another substituent, refers to an unsaturated hydrocarbyl group, which can be linear, or branched, comprising one or more double carbon-carbon bonds having 2 to 20 carbon atoms . Examples of C2-6 alkenyl groups are ethylene, 2propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and its isomers, 2,4-pentadienyl and the like.
[0049] In some respects, alkylsilane can be selected from the group comprising methyltrimethoxysilane; methyltriethoxysilane; ethyltrimethoxysilane; ethyltriethoxysilane; propyltrimethoxysilane;
propyltriethoxysilane; hexyltrimethoxysilane; hexyltriethoxysilane;
octyltrimethoxysilane; octyltriethoxysilane; decyltrimethoxysilane;
decyltriethoxysilane; dodecyltrimethoxysilane: dodecyltriethoxis silane;
tridecyltrimethoxysilane; dodecyltriethoxysilane; hexadecyltrimethoxysilane; hexadecyltriethoxysilane; octadecyltrimethoxysilane; octadecyltriethoxysilane, trimethylmethoxysilane, methylhydrodimethoxysilane, dimethyldimethoxysilane, diisopropyl dimethoxysilane,
Itrimetoxissilano, n-butiltrimetoxissilano, diisobutildimetoxissilano, isobutyl n-butilmetildimetoxissilano, silane feniltrimetoxis, silane feniltrimetoxis, fenilmetildimetoxissilano, trifenilsilanol, n-hexiltrimetoxis silane, n-octiltrimetoxissilano, silane isooctiltrimetoxis, deciltrimetoxissilano, hexadeciltrimetoxissilano, cyclohexane hexilmetildimetoxissilano, cyclohexane hexiletildimetoxissilano, silane diciclopentildimetoxis, tert-butylethyldimethoxysilane, tert-butylpropyl dimethoxysilane, dicyclohexyldimethoxysilane, and a combination thereof.
[0050] In some ways, the alkylsilane compound can be
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23/81 selected from trietoxyoctylsilane, trimethoxyoctylsilane, and a combination thereof.
[0051] Additional examples of silanes that can be used as silane crosslinkers include, but are not limited to, the general formula CH2 = CR- (COO) _x (C _n H2n) iSiR'3, where R is a hydrogen atom or methyl group; xéOou 1; i is 0 or 1; n is an integer from 1 to 12; each R 'can be an organic group and can be independently selected from an alkoxy group having 1 to 12 carbon atoms (for example, methoxy, ethoxy, butoxy), aryloxy group (for example, phenoxy), araloxy group (for example , benzyloxy), aliphatic acyloxy group having 1 to 12 carbon atoms (eg, formyloxy, acetyloxy, propanoyloxy), substituted amino or amino groups (eg, alkylamino, arylamino), or a lower alkyl group having 1 to 6 atoms carbon, x and y can both be equal to 1. In some respects, no more than one of the three groups R 'is an alkyl. In other respects, no more than two of the three groups R 'is alkyl.
[0052] Any silane or mixture of silanes, as known in the art, that can effectively graft and cross-link an olefin polymer, can be used in the practice of the present description. In some respects, the silane crosslinker may include, but is not limited to, unsaturated silanes that include an ethylenically unsaturated hydrocarbyl group (for example, a vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or gamma (meth) acryloxy allyl group ) and a hydrolyzable group (for example, a hydrocarbiloxy, hydrocarbonyloxy, or hydrocarbilamino group). Non-limiting examples of hydrolyzable groups include, but are not limited to, methoxy, ethoxy, formyloxy, acetoxy, proprionyloxy, and alkyl, or arylamino groups. In other respects, silane crosslinkers are unsaturated alkoxysilanes that can be grafted onto the polymer. In yet other exemplary additional silane crosslinking aspects include vinyltrimethoxysilane, vinyltriethoxysilane, 3- (trimethoxysilyl) propyl methacrylate
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24/81 gamma- (meth) acryloxypropyl trimethoxysilane), and mixtures thereof.
[0053] The silane crosslinker may be present in the polyolefin elastomer grafted with silane in an amount of more than 0% by weight to about 10% by weight, including from about 0.5% by weight to about 5 % by weight. The amount of silane crosslinker can be varied based on the nature of the olefin polymer, the silane itself, processing conditions, graft efficiency, application, and other factors. The amount of silane crosslinker can be at least 2% by weight, including at least 4% by weight or at least 5% by weight, based on the weight of the reactive composition. In other respects, the amount of silane crosslinker can be at least 10% by weight, based on the weight of the reactive composition. In still other aspects, the silane crosslinker content is at least 1% based on the weight of the reactive composition. In some embodiments, the silane crosslinker fed to the extruder may include from about 0.5% by weight to about 10% by weight of silane monomer, from about 1% by weight to about 5% by weight monomer. silane, or from about 2% by weight to about 4% by weight silane monomer.
Condensation catalyst [0054] A condensation catalyst can facilitate both hydrolysis and subsequent condensation of the silane graft onto the silane-grafted polyolefin elastomer to form crosslinking. In some respects, crosslinking can be aided by the use of electron beam radiation. In some aspects, the condensation catalyst may include, for example, organic bases, carboxylic acids, and organometallic compounds (for example, complex and organic titanates or lead, cobalt, iron, nickel, zinc and tin carboxylates). In other respects, the condensation catalyst may include acidic fatty acids and metal complex compounds, such as metal carboxylates; aluminum triacetyl acetonate, iron triacetyl acetonate, tetraacetyl acetonate
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25/81 manganese, tetraacetyl nickel acetonate, hexaacetyl chromium acetonate, titanium tetraacetyl acetonate and cobalt tetraacetyl acetonate; metal alkoxides, such as aluminum ethoxide, aluminum propoxide, aluminum butoxide, titanium ethoxide, titanium propoxide and titanium butoxide; metal salt compounds such as sodium acetate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate and dibutyltin di (2-ethylhexanoate); acidic compounds, such as formic acid, acetic acid, propionic acid, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, p-hydroxyethyl (meth) acrylate, monoalkylphosphorous acid and dialkyl acid; acids, such as p-toluenesulfonic acid, phthalic anhydride, benzoic acid, benzenesulfonic acid, dodecybenzenesulfonic acid, formic acid, acetic acid, itaconic acid, oxalic acid and maleic acid, ammonium salts, lower amine salts or polyvalent metal salts of these acids , sodium hydroxide, lithium chloride; organometallic compounds, such as diethyl zinc and tetra (n-butoxy) titanium; and amines, such as dicyclohexylamine, triethylamine, Ν, Ν-dimethylbenzylamine, N, N, N ', N'-tetramethyl-1,3, butanediamine, diethanolamine, triethanolamine and cyclohexylethylamine. In still other aspects, the condensation catalyst may include dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate, and cobalt naphthenate. Depending on the desired final properties of the polyolefin elastomer material crosslinked by a silane or blend, a single condensation catalyst or a mixture of condensation catalysts can be used. The condensation catalyst (s) can be present in an amount of about 0.01% by weight to about 1.0% by weight, including about
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0.25% by weight to about 8% by weight, based on the total weight of the silane-grafted polyolefin blend elastomer / blend composition.
[0055] In some respects, a crosslinking system may include and use one or all of a combination of radiation, heat, humidity, and additional condensation catalyst. In some aspects, the condensation catalyst can be present in an amount of 0.25% by weight to 8% by weight. In other aspects, the condensation catalyst can be included in an amount of about 1% by weight to about 10% by weight, or from about 2% by weight to about 5% by weight.
Foaming agent [0056] The foaming agent can be a chemical foaming agent (for example, organic or inorganic foaming agent) and / or a physical foaming agent (for example, volatile low-weight gases and molecules) that is added to the elastomer blend of polyolefin grafted with silane and condensation catalyst during the extrusion and / or molding process to produce the polyolefin elastomer crosslinked by a foamed silane. [0057] In some aspects, the foaming agent may be a physical foaming agent including a microencapsulated foaming agent, otherwise referred to in the art as a microencapsulated blowing agent (MEBA). MEBAs include a family of physical foaming agents that are defined as a thermoexpansible microsphere that is formed by encapsulating a volatile hydrocarbon in an acrylic copolymer wrap. When the acrylic copolymer wrap expands, the volatile hydrocarbon (e.g., butane) positioned inside the wrap further expands within the wrap to create a cell or balls in the silane crosslinkable polyolefin elastomer to reduce its weight. The MEBA wrap is designed not to break, so that the blowing agent does not lose its ability to expand and reduce the density of the silane crosslinkable polyolefin elastomer. In some
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27/81 aspects, MEBAs have an average particle size of about 20 pm to about 30 pm. Exemplary MEBAs include those sold under the trade name MATSUMOTO F-AC170D. In some ways, MEBA’s can be used in combination with other foaming agents including organic and inorganic foaming agents.
[0058] Organic foaming agents that can be used may include, for example, azo compounds, such as azodicarbonamide (ADCA), barium azodicarboxylate, azobisisobutyronitrile (AIBN), azocyclohexylnitrile, and azodiaminobenzene, N-nitrous compounds, such as N, N 'dinitrosopentamethylenetetramine (DPT), N, N'-dimethyl-N, N dinitrosoterephthalamide, and trinitrosotrimethyltriamine, hydrazide compounds, such as 4,4'-oxybis (benzenesulfonyl-hydrazide) (OBSH), paratolylsulfonyl-sulfonyl -hydrazide, 2,4-toluenedisulfonylhydrazide, p, p-bis ether (benzenesulfonylhydrazide), benzene-1,3-disulfonylhydrazide, and allybis (sulfonylhydrazide), semicarbazide compounds, such as ptoluenesulfonylsemicarbazide, and 4,4 oxybis (benzenesulfonyl semicarbazide), alkane fluorides, such as trichloromonofluoromethane, and dichloromonofluoromethane, and triazole compounds, such as 5-morphol-1, 2,3,4thiatriazole, and other known organic foaming agents. Preferably, azo compounds and N-nitrous compounds are used. Still preferably, azodicarbonamide (ADCA) and N, N'-dinitrosopenta methylenetetramine (DPT) are used. The organic foaming agents listed above can be used alone or in any combination of two or more.
[0059] The decomposition temperature and the amount of organic foaming agent used can have important consequences on the density and material properties of the polyolefin elastomer with foamed silane crosslinker. In some respects, the organic foaming agent has a decomposition temperature of about 150 ° C to about
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210 ° C. The organic foaming agent can be used in an amount of about 0.1% by weight to about 40% by weight, from about 5% by weight to about 30% by weight, from about 5% by weight to about 20% by weight, from about 10% by weight to about 30% by weight, or from about 1% by weight to about 10% by weight based on the total weight of the polymer blend. If the organic foaming agent has a decomposition temperature lower than 150 ° C, premature foaming may occur during the formation of the compound. Meanwhile, if the organic foaming agent has a decomposition temperature higher than 210 ° C, it may take longer, for example, more than 15 minutes, to mold the foam, resulting in low productivity. Additional foaming agents can include any compound whose decomposition temperature is within the range defined above.
[0060] The inorganic foaming agents that can be used include, for example, hydrogen carbonate, as sodium hydrogen carbonate, and ammonium hydrogen carbonate, as sodium carbonate, and ammonium carbonate, nitrite, as sodium nitrite , and ammonium nitrite, borohydride, such as sodium borohydride, and other known inorganic foaming agents, such as azides. In some respect, hydrogen carbonate can be used. In other respects, sodium hydrogen carbonate can be used. The inorganic foaming agents listed above can be used alone or in any combination of two or more. The inorganic foaming agent can be used in an amount of about 0.1% by weight to about 40% by weight, from about 5% by weight to about 30% by weight, from about 5% by weight to about 20% by weight, from about 10% by weight to about 30% by weight, or from about 1% by weight to about 10% by weight based on the total weight of the polymer blend.
[0061] Physical expansion agents that can be used include, for example, supercritical carbon dioxide, supercritical nitrogen, butane,
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29/81 pentane, isopentane, cyclopentane. The physical foaming agent can be used in an amount of about 0.1% by weight to about 40% by weight, from about 5% by weight to about 30% by weight, from about 5% by weight to about 20% by weight, from about 10% by weight to about 30% by weight, or from about 1% by weight to about 10% by weight based on the total weight of the polymer blend.
[0062] In some respects, an endothermic (foaming) blowing agent can be used which may include, for example, sodium bicarbonate and / or citric acid and its salts or derivatives. Exemplary citric acid foaming agents include those sold under the trade name HYDROCEROL® which include a mixture of zinc stearate, polyethylene glycol, and a citric acid or citric acid derivative. The desired decomposition temperature for the endothermic blowing agent can be about 160 ° C to about 200 ° C, or about 175 ° C, about 180 ° C, about 185 ° C, about 190 ° C, or about 195 ° C.
Optional additional components [0063] The silane crosslinked polyolefin elastomer can optionally include one or more fillers. The filler (s) may be extruded with the silane-grafted polyolefin and in some respects may include additional polyolefins having a crystallinity greater than 20%, greater than 30%, greater than 40%, or greater than 50%. In some respects, the filler (s) may include metal oxides, metal hydroxides, metal carbonates, metal sulfates, metal silicates, clays, talc, carbon black, and silicas. Depending on the application and / or the desired properties, these materials can be smoked or calcined.
[0064] Metal from metal oxide, metal hydroxide, metal carbonate, metal sulfate, or metal silicate can be selected from metals
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30/81 alkali (for example, lithium, sodium, potassium, rubidium, cesium, and francium); alkaline earth metals (eg, beryllium, magnesium, calcium, strontium, barium and radium); transition metals (eg zinc, molybdenum, cadmium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum , tungsten, rhenium, osmium, indium, platinum, gold, mercury, ruterophorium, dubium, seaborium, boron, haassium and copemium); post-transition metals (for example, aluminum, gallium, indium, tin, thallium, lead, bismuth and polonium); lanthanides (for example, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium); actinides (for example, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, california, einsteinium, fermium, mendelium, nobium and laurence); germanium; arsenic; antimony; and astatine.
[0065] The filling (s) of the polyolefin elastomer crosslinked by a silane or blend may be present in an amount of more than 0% by weight to about 50% by weight, including from about 1% by weight to about 20% by weight and from about 3% by weight to about 10% by weight.
[0066] The polyolefin elastomer crosslinked by a silane and / or the related articles formed (e.g., static sealing members 12) may also include waxes (e.g., paraffin waxes, microcrystalline waxes, HDPE waxes, LDPE waxes, waxes thermally degraded, by-product polyethylene waxes, optionally oxidized Fischer-Tropsch waxes, and functionalized waxes). In some embodiments, the wax (s) is present in an amount from about 0% by weight to about 10% by weight.
[0067] Stickiness resins (for example, aliphatic hydrocarbons, aromatic hydrocarbons, modified hydrocarbons, terpenes, modified terpenes, hydrogenated terpenes, rosin, rosin derivatives, hydrogenated rosin, and mixtures thereof) can also be
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31/81 included in the polyolefin elastomer crosslinked by a silane / blend. Stickiness resins can have a ball and ring softening point in the range of 70 ° C to about 150 ° C and a viscosity of less than about 3000 cP at 177 ° C. In some respects, the tackiness resin (s) is present in an amount from about 0% by weight to about 10% by weight.
[0068] In some respects, the polyolefin elastomer crosslinked by a silane may include one or more oils. Non-limiting types of oils include white mineral oils and naphthenic oils. In some embodiments, the oil (s) is present in an amount from about 0% by weight to about 10% by weight.
[0069] In some respects, the silane crosslinked polyolefin elastomer may include one or more filler polyolefins having a crystallinity greater than 20%, greater than 30%, greater than 40%, or greater than 50% . The filler polyolefin can include polypropylene, poly (ethylene-co-propylene), and / or other ethylene / α-olefin copolymers. In some aspects, the use of the filler polyolefin may be present in an amount of about 5% by weight to about 60% by weight, from about 10% by weight to about 50% by weight, from about 20 % by weight to about 40% by weight, or from about 5% by weight to about 20% by weight. The addition of the filler polyolefin can increase the Young's modulus by at least 10%, at least 25%, or at least 50% for the polyolefin elastomer crosslinked by a final silane.
[0070] In some respects, the silane crosslinked polyolefin elastomer of the present description may include one or more stabilizers (for example, antioxidants). The silane crosslinked polyolefin elastomer can be treated before grafting, after grafting, before crosslinking, and / or after crosslinking. Other additives can also be included. Non-limiting examples of additives include antistatic agents, colorants,
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32/81 pigments, UV light absorbers, nucleating agents, fillers, gliding agents, plasticizers, flame retardants, lubricants, processing aids, smoke inhibitors, anti-block agents, and viscosity control agents. The antioxidant (s) may be present in an amount less than 0.5% by weight, including less than 0.2% by weight of the composition.
[0071] In some respects, a coloring agent may be added to the silane crosslinked polyolefin elastomer during its production as the silane crosslinkable polyolefin elastomer or the silane grafted polyolefin elastomer. In some respects, the coloring agent can be added in combination with the condensation catalyst (eg LE4423 / AMBICAT ™) and can include colors that include, for example, black (PPM1200 / 2), blue (PPM1201 / 2), brown (PPM1202 / 2), green (PPM1203 / 2), gray (PPM1204 / 2), orange (PPM1205 / 2), red (PPM 1206/2), violet (PPM 1207/2), white (PPM 1208/2 ), and / or yellow (PPM 1200/2) as provided by commercial suppliers.
Method for making the silane-grafted polyolefin elastomer [0072] The synthesis / production of the cross-linked polyolefin elastomer by a silane can be carried out by combining the respective components in an extruder using a single-stage Monosil process or in two extruders using one Sioplas process in two stages that eliminates the need for additional blending and shipping of rubber compounds before extrusion.
[0073] Referring now to Figure 1, the general chemical process used during both the Monosil single-step process and the Sioplas two-step process used to synthesize the polyolefin elastomer crosslinked by a silane is provided. The process begins with a grafting step that includes initiation of a graft initiator followed by propagation and chain transfer with the first and second polyolefins. The initiator
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33/81 graft, in some aspects a peroxide or azo compound, homolytically olive to form two radical initiator fragments that transfer one of the first and second polyolefin chains through a propagation step. The free radical, now positioned on the first or second polyolefin chain, can then transfer to a silane molecule and / or another polyolefin chain. Once the initiator and free radicals are consumed, the silanation reaction graft for the first and second polyolefins is complete.
[0074] Still with reference to Figure 1, once the silanation reaction graft is complete, a mixture of first and second stable silane-grafted polyolefins is produced. A crosslinking catalyst can then be added to the first and second silane-grafted polyolefins to form the silane-grafted polyolefin elastomer. The crosslinking catalyst can first facilitate the hydrolysis of the grafted silyl group on the polyolefin backbones to form reactive silanol groups. The silanol groups can then react with other silanol groups on other polyolefin molecules to form a cross-linked network of chains of elastomeric polyolefin molecules linked together through siloxane bonds. The density of silane crosslinks across the entire polyolefin elastomer grafted with silane can influence the material properties shown by the elastomer.
[0075] With reference now to Figures 2 and 3A, a method 10 for manufacturing the elastomeric article, using the Sioplas process in two stages is shown. Method 10 can start with a step 14 which includes extruding (for example, with a twin screw extruder 66) the first polyolefin 54 having a density less than 0.86 g / cm ³ , the second polyolefin 58 having a crystallinity less than 40%, a silane cocktail 62, including the silane crosslinker (for example, vinyltrimethoxy silane, VTMO) and the graft initiator (for example, dicumyl peroxide)
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34/81 together to form a blend of polyolefin grafted with silane 90. The first polyolefin 54 and the second polyolefin 58 can be added to the twin screw reactive extruder 66 using an addition hopper 70. Silane cocktail 62 can be added to twin screws 74 further down the extrusion line below to help promote better blending with the first and second polyolefin blend 54, 58. A forced volatile organic compound (VOC) vacuum 78 can be used over the twin screw reactive extruder 66 to help maintain a desired reaction pressure. Twin screw extruder 66 is considered to be reactive because the radical initiator and silane crosslinker are reacting and forming new covalent bonds with both the first and the second polyolefins 54, 58. A blend of fused silane-grafted polyolefin may come out of the extruder twin screw reactor 66 using a gear pump 82 that injects the fused silane-grafted polyolefin blend into a water granulator 86 that can form a silane-grafted polyolefin granular blend 90. In some respects, the grafted polyolefin blend with fused silane it can be extruded into granules, pads, or any other configuration before the incorporation of condensation catalyst 94 (see Figure 3B) and formation of the final elastomeric article.
[0076] The twin screw reactive extruder 66 can be configured to have a plurality of different temperature zones (for example, Z0-Z12 as shown in Figure 3A) that span multiple lengths of the twin screw extruder 66, In some aspects, the respective temperature zones can have temperatures ranging from about room temperature to about 180 ° C, from about 120 ° C to about 170 ° C, from about 120 ° C to about 160 ° C, from about 120 ° C to about 150 ° C, about 120 ° C to about 140 ° C, about 120 ° C to about 130 ° C, about 130 ° C to about 170 ° C , from about 130 ° C to about 160 ° C, from
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35/81 about 130 ° C to about 150 ° C, from about 130 ° C to about 140 ° C, from about 140 ° C to about 170 ° C, from about 140 ° C to about 160 ° C, from about 140 ° C to about 150 ° C, from about 150 ° C to about 170 ° C, and from about 150 ° C to about 160 ° C. In some ways, ZO can have a temperature of about 60 ° C to about 110 ° C or no cooling; Z1 can have a temperature of about 120 ° C to about 130 ° C; Z2 can have a temperature of about 140 ° C to about 150 ° C; Z3 can have a temperature of about 150 ° C to about 160 ° C; Z4 can have a temperature of about 150 ° C to about 160 ° C; Z5 can have a temperature of about 150 ° C to about 160 ° C; Z6 can have a temperature of about 150 ° C to about 160 ° C; and Z7-Z12 can have a temperature of about 150 ° C to about 160 ° C.
[0077] In some ways, the average molecular weight in number of polyolefin elastomers grafted with silane can be in the range of about 4000 g / mol to about 30,000 g / mol, including from about 5000 g / mol to about 25000 g / mol, from about 6000 g / mol to about 14000 g / mol, and greater than 25000 g / mol. The average molecular weight by weight of the grafted polymers can be from about 8000 g / mol to about 60,000 g / mol, including from about 10,000 g / mol to about 30,000 g / mol.
[0078] Referring now to Figures 2 and 3B, method 10 then includes a step 18 of extruding the silane-grafted polyolefin blend 90 and the condensation catalyst 94 together to form a silane 114 crosslinkable polyolefin blend. In some aspects, one or more optional additives 98 can be added with the silane-grafted polyolefin blend 90 and the condensation catalyst 94 to adjust the properties of the final material in the silane cross-linked polyolefin blend. In step 18, the silane-grafted polyolefin blend 90 is mixed with a silanol-forming condensation catalyst 94 to form reactive silanol groups on the silane grafts that can
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36/81 subsequently cross-linked when exposed to moisture and / or heat. In some respects, the condensation catalyst is AMBICAT ™ LE4472 which may include a mixture of sulfonic acid, antioxidant, process aid, and carbon black for coloring where ambient humidity is sufficient for the condensation catalyst 94 to crosslink the polyolefin blend crosslinkable by silane 114 for a longer period of time (for example, about 48 hours). A silane-grafted polyolefin blend 90 and condensation catalyst 94 can be added to a reactive single-screw extruder 102 using an addition hopper and an addition gear pump 110. The combination of the silane-grafted polyolefin blend 90 and condensation catalyst 94, and in some respects one or more optional additives 98, can be added to a single screw 106 of the single screw reactive extruder 102. The single screw extruder 102 is considered reactive because crosslinking can begin as soon as the blend of polyolefin grafted with silane 90 and condensation catalyst 94 are fused and combined to blend the condensation catalyst 94 completely and regularly through the entire melt of polyolefin grafted with silane 90. The molten blend of crosslinkable polyolefin with silane 114 can exit the single screw reactive extruder 102 through a die that can inject the blend of polyolefin crosslinkable by a silane melting into an uncured static sealing element.
[0079] During step 18, as the polyolefin blend grafted with silane 90 is extruded along with the condensation catalyst 94 to form the silane 114 crosslinkable polyolefin blend, a certain amount of crosslinking may occur. In some respects, the silane 114 crosslinkable polyolefin blend can be about 25% cured, about 30% cured, about 35% cured, about 40% cured, about 45% cured, about 50% cured , about 55% cured, about 60% cured, about 65% cured, or about 70% cured where gel test (ASTM
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D2765) can be used to determine the amount of crosslinking in the polyolefin elastomer crosslinked by a final silane.
[0080] Still with reference to Figures 2 and 3B, method 10 additionally includes a step 22 of molding the silane-crosslinkable polyolefin blend 114 on the uncured elastomeric article. The single screw extruder 102 fuses and extrudes the crosslinkable polyolefin with silane 114 through a matrix that can extrude the blend of crosslinkable polyolefin by a melting silane 114 into the uncured elastomeric element.
[0081] Referring again to Figure 2, method 10 may additionally include a step 26 of crosslinking the polyolefin blend crosslinkable by silane 114 or the uncured elastomeric article at an ambient or elevated temperature and / or an ambient or elevated humidity to form the elastomeric article having a density of about 0.80 g / cm ³ to about 0.89 g / cm ³ , 0.60 g / cm ³ to 0.69 g / cm ³ , or 0.50 g / cm ³ at 0.59 g / cm ^3. More particularly, in this crosslinking process, water hydrolyzes the silane of the silane crosslinkable polyolefin elastomer to produce a silanol. The silanol groups on various silane grafts can then be condensed to form intermolecular, irreversible Si-O-Si crosslinking sites. The amount of cross-linked silane groups, and thus the properties of the final polymer, can be regulated by controlling the production process, including the amount of catalyst used.
[0082] The crosslinking / curing of step 26 of method 10 can occur for a period of time of more than about 20 seconds to about 200 seconds or 0 to about 20 hours. In some respects, healing takes place over a period of about 20 seconds to about 200 seconds, about 1 hour to about 20 hours, about 10 hours to about 20 hours, about 15 hours to about 20 hours, about 5 hours to about 15 hours, about 1 hour to about 8 hours, or about 3 hours to about 6 hours. The temperature during crosslinking / curing can be around the temperature
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38/81 environment, from about 20 ° C to about 25 ° C, from about 20 ° C to about 150 ° C, from about 25 ° C to about 100 ° C, from about 20 ° C about 75 ° C, about 50 ° C to about 200 ° C, about 100 ° C to about 400 ° C, about 100 ° C to about 300 ° C, or about 100 ° C to about 200 ° C. The humidity during curing can be from about 30% to about 100%, from about 40% to about 100%, or from about 50% to about 100%.
[0083] In some respects, an extruder grade is used that is capable of extruding thermoplastic, with long L / D, 30 to 1, in an extruder heat gradation close to the TPV processing conditions in which the extrudate reticulates in ambient conditions becoming a thermoset in properties. In other aspects, this process can be accelerated by exposure to water vapor. Immediately after the extrusion step, the gel content (also called the crosslink density) can be about 40%, about 50%, or about 60%, but after 96 h at ambient conditions, the gel content it can reach more than about 80%, about 85%, about 90%, or about 95%.
[0084] In some respects, one or more reactive single screw extruders 102 can be used to form the uncured sealing element and the corresponding static sealing member that have one or more types of polyolefin elastomers cross-linked by a silane. For example, in some respects, a single screw reactive extruder 102 can be used to produce and extrude the silane crosslinked polyolefin elastomer while a second single screw reactive extruder 102 can be used to produce and extrude a second elastomer from polyolefin cross-linked by a silane. The complexity and architecture of the article or final product will determine the number and types of single screw reactive extruder 102.
[0085] It should be understood that the description outlining and teaching the various elastomeric articles and their respective components / composition
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39/81 previously discussed, which can be used in any combination, applies equally well to method 10 to manufacture the elastomeric article using the two-stage Sioplas process as shown.
[0086] With reference now to Figures 4 and 5, a method 200 for manufacturing the elastomeric article, using the Monosil process in one step is shown. Method 200 can start with a step 204 which includes extruding (for example, with a single screw extruder 216) the first polyolefin 54 having a density less than 0.86 g / cm ³ , the second polyolefin 58 having a crystallinity less than 40%, the silane cocktail 62 including the silane crosslinker (eg vinyltrimethoxy silane, VTMO) and graft initiator (eg dicumyl peroxide), and condensation catalyst 94 together to form the polyolefin blend grafted with crosslinkable silane 114, The first polyolefin 54, the second polyolefin 58, and the silane cocktail 62 can be added to the single screw reactive extruder 216 using an addition hopper 70. In some respects, the silane cocktail 62 can be added to a single screw 220 over the extrusion line below to help promote a better blend with the blend of the first and second polyolefins 54, 58. In some respects, one or more optional additives 98 can be used were added with the first polyolefin 54, the second polyolefin 58, and the silane cocktail 62 to modify the properties of the final material of the silane 114 crosslinkable polyolefin blend. The single screw extruder 216 is considered reactive because the radical initiator and silane crosslinker of silane cocktail 62 are reacting with and forming new covalent bonds with both the first and the second polyolefin blends 54, 58. In addition, the single screw reactive extruder 216 blends the condensation catalyst 94 along with the polyolefin blend grafted with fused silane 90. The fused silane crosslinkable polyolefin blend 114 can come out of the single screw reactive extruder 216 using a
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40/81 gear (not shown) and / or matrix that can inject, eject, and / or extrude the polyolefin blend crosslinkable by a silane melting into the uncured static sealing element.
[0087] During step 204, as the first polyolefin 54, second polyolefin 58, silane cocktail 62, and condensation catalyst 94 are extruded together, a certain amount of crosslinking can occur in the single screw reactive extruder 216 (see Figures 4 and 5). In some respects, the silane 114 crosslinkable polyolefin blend can be about 25% cured, about 30% cured, about 35% cured, about 40% cured, about 45% cured, about 50% cured , about 55% cured, about 60% cured, about 65% cured, or about 70% as it leaves the 216 single screw reactive extruder, The gel test (ASTM D2765) can be used to determine the amount of crosslinking in the polyolefin elastomer crosslinked by a final silane.
[0088] The single screw reactive extruder 216 can be configured to have a plurality of different temperature zones (for example, Z0-Z7 as shown in Figure 5) that span several lengths along the extruder. In some respects, the respective temperature zones can have temperatures ranging from about room temperature to about 180 ° C, from about 120 ° C to about 170 ° C, from about 120 ° C to about 160 ° C , from about 120 ° C to about 150 ° C, around
120 ° C to about 140 ° C, from about 120 ° C to about 130 ° C, about
130 ° C to about 170 ° C, about 130 ° C to about 160 ° C, about
130 ° C to about 150 ° C, about 130 ° C to about 140 ° C, about
140 ° C to about 170 ° C, from about 140 ° C to about 160 ° C, about
140 ° C to about 150 ° C, from about 150 ° C to about 170 ° C, and about
150 ° C to about 160 ° C. In some ways, Z0 can have a temperature of about 60 ° C to about 110 ° C or in cooling; Z1 can have a temperature of about 120 ° C to about 130 ° C; Z2 can have a
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temperature in fence in 140 ° C The fence in 150 ° C; Z3 can Tue an temperature in fence in 150 ° C The fence in 160 ° C; Z4 can Tue an temperature in fence in 150 ° C The fence in 160 ° C; Z5 can Tue an temperature in fence in 150 ° C The fence in 160 ° C; Z6 can Tue an temperature in fence in 150 ° C The fence i in 160 ° C; and Z7 can Tue an
temperature from about 150 ° C to about 160 ° C.
[0089] In some respects, the average molecular weight in number of polyolefin elastomers grafted with silane can be in the range of about 4000 g / mol to about 30,000 g / mol, including from about 5000 g / mol to about 25,000 g / mol, from about 6000 g / mol to about 14000 g / mol, and greater than 25000 g / mol. The average molecular weight by weight of the grafted polymers can be from about 8000 g / mol to about 60,000 g / mol, including from about 10,000 g / mol to about 30,000 g / mol.
[0090] Still referring to Figures 4 and 5, method 200 additionally includes a step 208 of molding the silane crosslinkable polyolefin blend into the elastomeric element. The single screw reactive extruder 216 can melt and extrude the silane-crosslinkable polyolefin blend 114 through the matrix which can extrude the polyolefin blend crosslinkable by a melting silane 114 into the uncured elastomeric article.
[0091] Still referring to Figure 4, method 200 may additionally include a step 212 of crosslinking the polyolefin blend crosslinkable by a silane 114 of the uncured elastomeric article at an ambient or elevated temperature and an ambient or elevated humidity to form the elastomeric article having a density of about 0.80 g / cm ³ to about 0.89 g / cm ³ , 0.60 g / cm ³ to 0.69 g / cm ³ , or 0.50 g / cm ³ at 0.59 g / cm ^3, The amount of cross-linked silane groups, and thus the properties of the final polymer, can be regulated by controlling the production process, including the amount of catalyst used.
[0092] Step 212 of crosslinking of the crosslinkable polyolefin blend
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42/81 by a silane 114 can occur over a period of more than about 40 seconds to about 200 seconds, 0 hours to about 10 hours, or 0 to about 20 hours. In some ways, healing takes place over a period of about 10 seconds to about 200 seconds, about 40 seconds to about 400 seconds, about 1 hour to about 20 hours, 10 hours to about 20 hours, about 15 hours to about 20 hours, about 5 hours to about 15 hours, about 1 hour to about 8 hours, or about 3 hours to about 6 hours. The temperature during crosslinking and curing can be about room temperature, from about 20 ° C to about 425 ° C, from about 20 ° C to about 250 ° C, from about 25 ° C to about 200 ° C, or from about 20 ° C to about 75 ° C. The humidity during curing can be from about 30% to about 100%, from about 40% to about 100%, or from about 50% to about 100%.
[0093] In some respects, an extruder gradation is used that is capable of extruding thermoplastic, with long L / D, 30 to 1, to an extruder heat gradation close to the TPV processing conditions in which the extrudate can crosslink at room temperature or higher by taking a thermoset in properties. In other aspects, this process can be accelerated by exposure to water vapor. Immediately after extrusion, the gel content (also called crosslink density) can be about 40%, about 50%, or about 60%, but after 96 h at ambient conditions, the gel content can reach more than that about 80%, about 85%, about 90%, or about 95%.
[0094] In some respects, one or more reactive single screw extruders 216 (see Figure 5) can be used to form the uncured sealing element and the corresponding static sealing member that have one or more types of crosslinked polyolefin elastomers by a silane. For example, in some respects, a 216 single screw reactive extruder can be used to produce and extrude the crosslinked polyolefin elastomer
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43/81 by a silane while a second reactive single screw extruder 216 can be used to produce and extrude the second silane crosslinked polyolefin elastomer. The complexity and architecture of the article or final product will determine the number and types of single screw reactive extruder 216,
It should be understood that the description outlining and teaching the various polyolefin elastomers crosslinked by a silane and their respective components / composition previously discussed, which can be in any combination, applies equally well to method 200 to manufacture the elastomeric article using the Monosil process in one step as shown.
[0095] Non-limiting examples of elastomeric articles that the silane-crosslinked polyolefin elastomer of the description can be used for manufacture include static seals such as weather seals (e.g. glass runners including molded details / corners), seals sunroof, convertible top seals, top mirror seals, bodywork interface seals, stationary window molded parts, glass encapsulations, cut line seals, greenhouse molded parts, occupancy detector system sensor switches, rocker, external and internal belts, auxiliary and margin seals, edge / clamp protector seals, and belt clamps and grooves; automotive hoses, such as refrigerant hoses, air conditioning hoses, and vacuum hoses; anti-vibration system components (AVS), such as supports (for example, engine, body, accessory, component), shock absorbers, bushes, stirrup supports, and insulators; coatings, such as coatings for brake lines, fuel lines, transmission oil cooler lines, clamps, crosspieces, chassis components, panels and body components,
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44/81 suspension components, wheels, hubs, springs, and fasteners, air deflectors, spoilers, strips, and linings; building, window, and door fences; cabins, bellows, and eyelets; gaskets (for example, pneumatic and / or hydraulic gaskets); sheathing of wires and cables; tires; windshield and squeegee cleaners; floor mats; pedal covers; automotive belts; conveyor belts; shoe components; marine bumpers; O-ring type; valves and seals; and springs (for example, as substitutes for mechanical metal springs).
Molding techniques [0096] Injection or addition of the polyolefin elastomer blend crosslinkable with silanol 14 into a mold can be performed using one of several different approaches. Depending on the molding approach selected, different material properties can be obtained for the elastomeric article. Molding can be performed using one of the following four processes: Compression Molding, Injection Molding, Injection Molding and Compression, and Supercritical Injection Molding.
[0097] According to the compression molding process, the silane 114 crosslinkable polyolefin elastomer is pressurized in a compression mold or press under predetermined conditions of temperature, pressure, and time to obtain a silane crosslinked polyolefin elastomer foamed in the form of a plate-type sponge. As the silane 114 crosslinkable polyolefin elastomer is heated and pressed into the mold by compression, the chemical and / or physical foaming agents are activated to form the polyolefin elastomer crosslinked by a foamed silane. Portions and / or edges of the plate-type sponge can then be scraped, cut, and / or ground into a shape for the desired elastomeric article. Subsequently, the elastomeric article is again molded into a final mold with elastomeric article and other related components under heat and pressure and the assembly is then pressurized during cooling in
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45/81 a closed state of the mold.
[0098] According to the injection molding process, the single screw reactive extruder 102, 216 used in the process or Sioplas or Monosil prepares and injects the silane-crosslinkable polyolefin elastomer 114 into a mold having a top mold and a mold bottom. Upon initial injection of the silane 114 crosslinkable polyolefin elastomer into the mold, an uncured elastomeric article is formed. As the uncured elastomeric article is heated and cured, chemical and / or physical foaming agents are activated to form the polyolefin elastomer crosslinked by a foamed silane. The mold used in these aspects is designed to be smaller than the size of the final cured elastomeric article (polyolefin elastomer crosslinked by a foamed silane). After foaming and expansion of the silane crosslinkable polyolefin elastomer, the uncured elastomeric article is expanded to the desired size of the elastomeric article and the mold releases the final article.
[0099] The injection compression mold provides a hybrid approach to form the elastomeric article using aspects of both the compression mold and the injection mold. According to the compression and injection process, the single screw reactive extruder 102, 216 used in the process or Sioplas or Monosil prepares and injects a mass of the crosslinkable polyolefin elastomer with silane 90 in a mold having an upper mold and a lower mold . The silane 114 crosslinkable polyolefin elastomer mass is then heated and pressed in the mold to form the uncured elastomeric article while chemical and / or physical foaming agents are activated to form the polyolefin elastomer crosslinked by a foamed silane constituting the article. final cured elastomeric. The mold used in these injection and compression processes is designed to be smaller than the size of the final cured elastomeric article (polyolefin elastomer crosslinked by a foamed silane). After
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46/81 of the defoaming and expansion of the silane crosslinked polyolefin elastomer, the mold is released to eject the final cured elastomeric article. [00100] According to the supercritical fluid defoaming approach, a supercritical fluid injector is coupled to an extruder. The process begins (for example, with the single screw reactive extruder 216 as provided in Figure 5) the first polyolefin having a density less than 0.86 g / cm ³ 54, the second polyolefin 58, the silane cocktail 62 including the silane crosslinker (eg vinyltrimethoxy silane, VTMO), graft initiator (eg dicumyl peroxide), and condensation catalyst 94 together to form the polyolefin blend grafted with crosslinkable silane 114, The first polyolefin 54, the second polyolefin 58, and silane cocktail 62 can be added to the single screw reactive extruder 216 using the addition hopper 70 and a gear pump. In some respects, the silane cocktail 62 can be added to single screw 220 plus by the extrusion line below to help promote a better blend with the first and second polyolefin blend 54, 58. In some respects, one or more optional additives 98 can be added with the first polyolefin 54, the second polyolefin 58, and the silane cocktail 62 to adjust the final material properties of the silane 114 crosslinkable polyolefin blend.
[00101] A supercritical fluid injector can be coupled to the single screw extruder 216 to add a supercritical fluid such as carbon dioxide or nitrogen to the silane-crosslinkable polyolefin blend 114 before it is injected through the die into a mold. The reactive single screw extruder 216 then injects the silane-crosslinkable polyolefin elastomer 114 into the mold. Upon initial injection of the silane crosslinkable polyolefin elastomer 11 into the mold, an uncured elastomeric article is formed. As the uncured elastomeric article is heated and cured, the supercritical fluid foaming agent expands to form the
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47/81 polyolefin elastomer crosslinked by foamed silane. The mold used in these aspects is designed to be smaller than the size of the final cured elastomeric article (polyolefin elastomer crosslinked by a foamed silane). After defoaming, the polyolefin elastomer crosslinked by a foamed silane is expanded to the desired size of the elastomeric article using pulling the core back to accommodate the expansion, and the mold releases.
Physical properties of the silane crosslinked polyolefin elastomer [00102] A "thermoplastic", as used herein, is defined as meaning a polymer that softens when exposed to heat and returns to its original condition when cooled at room temperature. A “thermoset”, as used here, is defined as meaning a polymer that solidifies and “fixes” or “reticulates” irreversibly when cured. In any of the Monosil or Sioplas processes described above, it is important to understand the careful balance of thermoplastic and thermoset properties of the various different materials used to produce the final thermosetted silane crosslinked polyolefin article. Each of the intermediate polymer materials mixed and reacted using a twin screw reactive extruder, a single screw reactive extruder, and / or a single screw reactive extruder is thermoset. Consequently, the silane-grafted polyolefin blend and the silane crosslinkable polyolefin blend are thermoplastic and can be softened by heating so that the respective materials can flow. Once the silane crosslinkable polyolefin blend is extruded, molded, pressed, and / or shaped into the uncured elastomeric article, the silane crosslinkable polyolefin blend can begin to crosslink or cure at room or elevated temperature and a ambient or elevated humidity to form the elastomeric article and the silane crosslinked polyolefin blend or a silane crosslinked polyolefin elastomer blend.
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48/81 [00103] The thermoplastic / thermosetting behavior of the silane crosslinkable polyolefin blend and corresponding silane crosslinked polyolefin blend is important for the various compositions and articles described here because of the potential energy savings provided using these materials. For example, a manufacturer can save considerable amounts of energy by being able to cure the silane crosslinkable polyolefin blend at room or reduced temperature and room or reduced humidity. This curing process is typically carried out in the industry by applying significant amounts of energy to heat or treat crosslinkable polyolefins with water vapor. The ability to cure the inventive silane crosslinkable polyolefin blend at room temperature and / or ambient humidity is not necessarily an intrinsic property of crosslinkable polyolefins, but, on the contrary, it is a specifically low density dependent property (ie compared to EPDM and / or TPV) of the silane crosslinkable polyolefin blend. In some respects, no curing furnace, heating furnace, additional water steam furnace, or other forms of heat-producing machinery other than that provided in the extruders is used to form the polyolefin elastomers cross-linked by a silane.
[00104] The specific density of the silane crosslinked polyolefin elastomer of the present description may be lower than the relative densities of existing TPV and EPDM formulations used in the art. The reduced specific density of these materials can lead to lower weight parts, thus helping car manufacturers to meet increasing demands for better fuel economy. For example, the specific density of the silane crosslinked polyolefin elastomer of the present description can be from about 0.80 g / cm ³ to about 0.89 g / cm ³ , from about 0.85 g / cm ³ to about 0.89 g / cm ³ , from about 0.60 g / cm ³ to about 0.69 g / cm ³ , from about 0.50 g / cm ³ to about 0.59 g / cm cm ³ , less than 0.90
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49/81 g / cm ³ , less than 0.89 g / cm ³ , less than 0.88 g / cm ³ , less than 0.87 g / cm ³ , less than 0.86 g / cm ³ , or less than 0.85 g / cm ³ compared to existing TPV materials that can have a specific density of 0.95 to 1.2 g / cm ³ and EPDM TPV that can have a specific density of 1, 0 to 1.35 g / cm ^3, The low specific density or density of the silane crosslinked polyolefin elastomer is attributable to the low crystallinity of that found in Examples 1-7 described below. In some respects, the percentage crystallinity of the silane crosslinked polyolefin elastomer is less than 10%, less than 20%, or less than 30%.
[00105] Referring now to Figure 6, the stress / strain behavior of a silane crosslinked polyolefin elastomer exemplifying the present description (ie, the “silane crosslinked polyolefin elastomer” in the legend) relative to the two EPDM materials existing ones is provided. In particular, Figure 12 shows a smaller area between the stress / strain curves for the silane crosslinked polyolefin of the description, versus the areas between the stress / strain curves for EPDM A compound and EPDM B compound. This smaller area between the curves stress / strain for the silane crosslinked polyolefin elastomer may be desirable for the application of elastomeric articles. Elastomeric materials typically have nonlinear stress-strain curves with a significant loss of energy when stressed repeatedly. The polyolefin elastomers crosslinked by a silane of the present description can have greater elasticity and less viscoelasticity (for example, have linear curves and have very low energy loss). Modalities of the silane-crosslinked polyolefin elastomers described here do not have any fillers or plasticizers incorporated in these materials so that their corresponding stress / strain curves have or do not exhibit any Mullins effect and / or Payne effect. The lack of Mullins effect
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50/81 for these silane crosslinked polyolefin elastomers is due to the lack of any conventional reinforcement fillers (e.g. carbon black) or plasticizer added to the silane crosslinked polyolefin blend so that the stress-strain curve does not depend the maximum load previously found where there is no instantaneous and irreversible softening. The lack of Payne effect for these silane-crosslinked polyolefin elastomers is due to the lack of any filler or plasticizer added to the silane-crosslinked polyolefin blend so that the stress-strain curve does not depend on the small strain ranges previously encountered where there is no change of the viscoelastic storage module based on the amplitude of the deformation.
[00106] The polyolefin elastomer crosslinked by a silane or elastomeric article may show a deformation after compression of about 5.0% to about 30.0%, from about 5.0% to about 25.0%, from about 5.0% to about 20.0%, from about 5.0% to about 15.0%, from about 5.0% to about 10.0%, from about 10, 0% to about 20.0%, from about 10.0% to about 30.0%, from about 15.0% to about 25.0%, from about 10.0% to about 15.0%, from about 15.0% to about 25.0%, from about 15.0% to about 20.0%, from about 20.0% to about 30.0%, or from about 20.0% to about 25.0%, as measured according to ASTM D 395 (22 h to 23 ° C, 70 ° C, 80 ° C, 90 ° C, 125 ° C, and / or 175 ° C).
[00107] In other implementations, the polyolefin elastomer crosslinked by a silane or elastomeric article may show a compression strain of about 5.0% to about 20.0%, from about 5.0% to about 15 , 0%, from about 5.0% to about 10.0%, from about 7.0% to about 20.0%, from about 7.0% to about 15.0%, from about 7.0% to about 10.0%, from about 9.0% to about 20.0%, from about 9.0% to about 15.0%, from about 9.0 % to about 10.0%, from about 10.0% to about
20.0%, from about 10.0% to about 15.0%, from about 12.0% to about
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20.0%, or from about 12.0% to about 15.0%, as measured according to ASTM D 395 (22 h to 23 ° C, 70 ° C, 80 ° C, 90 ° C, 125 ° C, and / or 175 ° C).
[00108] The polyolefin elastomers crosslinked by a silane and elastomeric articles of the description can have a crystallinity of about 5% to about 40%, from about 5% to about 25%, from about 5% to about 15%, from about 10% to about 20%, from about 10% to about 15%, or from about 11% to about 14% as determined using density, differential scanning calorimetry (DSC) measurements , X-ray diffraction, infrared spectroscopy, and / or nuclear magnetic spectroscopy in solid state. As described here, DSC was used to measure the melting enthalpy in order to calculate the crystallinity of the respective samples.
[00109] Polyolefin elastomers crosslinked by silane and elastomer articles can have a glass transition temperature of about -75 ° C to about -25 ° C, from about -65 ° C to about -40 ° C, about -60 ° C to about -50 ° C, about -50 ° C to about -25 ° C, about -50 ° C to about -30 ° C, or about from -45 ° C to about -25 ° C as measured according to differential scanning calorimetry (DSC) using a second heating test at a rate of 5 ° C / min or 10 ° C / min.
[00110] Polyolefin elastomers crosslinked by a silane and elastomeric articles may have a weather color difference of about 0.25 ΔΕ to about 2.0 ΔΕ, from about 0.25 ΔΕ to about 1.5 ΔΕ, from about 0.25 ΔΕ to about 1.0 ΔΕ, or from 0.25 ΔΕ to about 0.5 ΔΕ, as measured according to ASTM D2244 after 3000 h of exposure to weather conditions outside.
[00111] Polyolefin elastomers crosslinked by a silane and elastomeric articles may have exceptional stain resistance properties compared to EPDM samples. Example 3, as described below, showed no crack, wrinkle, crack, iridescence, flowering, milkyness, separation, loss of adhesion, or loss of relief,
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52/81 as measures according to ASTM D1566. In addition, Example 3, which is representative of all the silane crosslinked polyolefin elastomers produced, showed no staining or discoloration in NaOH solutions at pH 11, pH 12.5, and pH 13, as measured according to SunSimulation and Spotting Test (PR231-2.2.15).
EXAMPLES [00112] The following examples represent certain non-limiting examples of elastomeric articles, compositions and methods of making them, according to the description.
Materials [00113] All chemicals, precursors and other constituents were obtained from commercial suppliers and used as supplied without further purification.
Example 1 [00114] Example 1 or ED4 was produced by extruding 77.36% by weight of ENGAGE ™ 8150 and 19.34% by weight of VISTAMAX ™ 6102 together with 3.3% by weight of SILFIN 13 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 1 was then extruded with 3 wt.% AMBICAT ™ LE4472 condensation catalyst to form a silane crosslinkable polyolefin elastomer, which was then extruded into an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 1 was cured at room temperature and humidity to form a silane crosslinked polyolefin elastomer, consistent with the elastomers of the description. The composition of Example 1 is given in Table 1 below.
Example 2 [00115] Example 2 or ED76-4A was produced by extruding 82.55% by weight of ENGAGE ™ 8842 and 14.45% by weight of MOSTEN ™ TB 003
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53/81 together with 3.0% by weight of SILAN RHS 14/032 or SILFIN 29 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer from Example 2 was then extruded with 3 wt.% AMBICAT ™ LE4472 condensation catalyst to form a silane crosslinkable polyolefin elastomer, which was then extruded into an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 2 was cured at room temperature and humidity to form a silane crosslinked polyolefin elastomer, consistent with the elastomers of the description. The composition of Example 2 is given in Table 1 below and some of its material properties are provided in Figures 13-18.
Example 3 [00116] Example 3 or ED76-4E was produced by extruding 19.00% by weight of ENGAGE ™ 8150, 58.00% by weight of ENGAGE ™ 8842, and 20.00% by weight of MOSTEN ™ TB 003 together with 3.0% by weight of SILAN RHS 14/032 or SILFIN 29 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 3 was then extruded with 3 wt.% AMBICAT ™ LE4472 condensation catalyst to form the silane crosslinkable polyolefin elastomer, which was then extruded into an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 3 was cured at ambient temperature and humidity to form a silane crosslinked polyolefin elastomer, consistent with the elastomers of the description. The composition of Example 3 is given in Table 1 below.
Example 4 [00117] Example 4 or ED76-5 was produced by extruding 19.00% by weight of ENGAGE ™ 8150, 53.00% by weight of ENGAGE ™ 8842, and 25.00% by weight of MOSTEN TB 003 along with 3 , 0% by weight of SILAN RHS
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14/032 or SILFIN 29 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 4 was then extruded with 3 wt.% AMBICAT ™ LE4472 condensation catalyst to form the silane crosslinkable polyolefin elastomer, which was then extruded into an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 4 was cured at room temperature and humidity to form a silane crosslinked polyolefin elastomer, consistent with the elastomers of the description. The composition of Example 4 is given in Table 1 below.
Example 5 [00118] Example 5 or ED76-6 was produced by extruding 16.36% by weight of ENGAGE ™ 8150, 45.64% by weight of ENGAGE ™ 8842, and 35.00% by weight of MOSTEN ™ TB 003 together with 3.0% by weight of SILAN RHS 14/032 or SILFIN 29 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 5 was then extruded with 3 wt.% AMBICAT ™ LE4472 condensation catalyst to form the silane crosslinkable polyolefin elastomer, which was then extruded into an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 5 was cured at room temperature and humidity to form a silane crosslinked polyolefin elastomer, consistent with the elastomers of the description. The composition of Example 5 is given in Table 1 below.
[00119] Table 1 below shows the compositions of the silane-grafted polyolefin elastomers of Examples 1-5,
TABLE 1
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 ENGAGE 8150 77.36 - 19.00 19.00 16.36 ENGAGE 8842 - 82.55 58.00 53.00 45.64 MOSTEN TB 003 - 14.45 20.00 25.00 35.00
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VISTAMAXX 6102 19.34 - - - - SILAN RHS 14/032 orSILFIN 293.00 3.00 3.00 3.00 SILFIN 13 3.30 - - - - TOTAL 100 100 100 100 100
Example 6 [00120] Example 6 or ED108-2A was produced by extruding 48.7% by weight of ENGAGE ™ XLT8677 or XUS 38677.15 and 48.7% by weight of ENGAGE ™ 8842 along with 2.6% by weight of SILAN RHS 14/032 or SILFIN 29 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 6 was then extruded with about 360 ppm of dioctyltin dilaurate (DOTL) condensation catalyst to form a silane crosslinkable polyolefin elastomer as an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 6 was cured at room temperature and humidity to form a silane crosslinked polyolefin elastomer, consistent with the elastomers of the description. The composition of Example 6 is given in Table 2 below and some of its material properties are given in Figures 13-18, Example 7 [00121] Example 7 or ED92 was produced by extruding 41.4% by weight of ENGAGE ™ XLT8677 or XUS 38677 , 15 and 41.4 wt% ENGAGE ™ 8842, and 14.4 wt% MOSTEN ™ TB 003 along with 2.8 wt% SILAN RHS 14/032 or SILFIN 29 to form the grafted polyolefin elastomer with silane. The silane-grafted polyolefin elastomer of Example 7 was then extruded with about 360 ppm of dioctyltin dilaurate (DOTL) condensation catalyst to form a silane crosslinkable polyolefin elastomer as an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the uncured elastomeric article as an article was cured at room temperature and humidity to form a crosslinked polyolefin elastomer by
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56/81 a silane, consistent with the elastomers of the description. The composition of Example 7 is given in Table 2 below and some of its material properties are provided in Figures 13-18, [00122] Table 2 below shows the compositions of the silane-grafted polyolefin elastomers of Examples 6-7,
TABLE 2
Ingredients Ex. 6 Ex. 7 ENGAGE XLT8677 / XUS 38677.15 48.7 41.4 ENGAGE 8842 48.7 41.4 SILAN RHS 14/032 or SILFIN 29 2.6 2.8 MOSTEN TB 003 - 14.4 TOTAL 100 100
[00123] Table 3 below shows several of the material properties of Example 1, In particular, percentages of bend strain after compression are provided using ASTM D 395, method B for 22 h at 23 ° C, 70 ° C, 80 ° C, 90 ° C, 125 ° C, and 175 ° C. Example 1 is representative of the polyolefin elastomers crosslinked by a silane described here in which the percentage of deformation after compression does not vary as much as the standard EPDM or TPV oi materials do over a range of different temperatures. In some respects, the percentage difference in percentage values of doubled strain after compression for the silane crosslinked polyolefin elastomer is less than 400%, less than 300%, less than 275%, less than 250%, less than 225%, or less than 210%.
TABLE 3
test Ex. 1 Durometer (type A by ASTM D 2240) 75 MPa traction (ASTM D 412, matrix C) 9.8 Elongation% (ASTM D 412, matrix C) 291 Tear resistance (ASTM D624, matrix C) 19 22 h / 23 ° C Bent deformation after compression% 20.0 22 h / 70 ° C Bent deformation after compression% 12.6 22 h / 80 ° C Bent deformation after compression 16.5 22 h / 90 ° C Bent deformation after compression% 10.9 22 h / 125 ° C Bent deformation after compression% 7.6 22 h / 175 ° C Bent deformation after compression% 9.6 Gel% 90
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57/81 [00124] Table 4 below shows density, hardness, low and high temperature performance, deformation after compression, and weathering material properties for Examples 2-4,
TABLE 4
Property test Method Units / Output Ex. 2 Ex. 3 Ex. 4 Originals Density ASTM D297 g / cm ³ 0.88 0.89 0.89 Toughness ASTM D412 matrix C Shore A 76 84 88 Traction ASTM D412 matrix C MPa 10.4 13.2 14.5 Stretching ASTM D412 matrix C % 300 306 314 Tear C ASTM D624 matrix C N / mm 24 37 48 Toughness JIS K 6253 IRHD 72 82 87 Traction JIS K6251 MPa 8.3 13.3 16.1 Stretching JIS K6251 % 260 255 334 Tear C JIS K 6252 N / cm 249 401 564 Low and high temperature performance Hardness Thermal aging (70h / 100 ° C) ASTM D573 Variation (Shore A) -2 -2 1 TractionThermal aging (70h / 100 ° C) ASTM D573 % Change -3.1 -6 9.1 Elongation Thermal aging (70h / 100 ° C) ASTM D573 % Change -10.4 -8.7 -2.6 Hardness Thermal aging (168h / 100 ° C) JIS K 6251/7 Variation (IRHD) 0 2 -5 Traction Thermal aging (168h / 100 ° C) JIS K 6251/7 % Change 0 -15.1 -9.9 Elongation Thermal aging (168h / 100 ° C) JIS K 6251/7 % Change -18 -22.7 -21 Tearing Thermal aging (168h / 100 ° C) JIS K 6251/7 % Change -11.2 -8.7 -10 Traction Thermal aging (1000h / 125 ° C) ASTM D573 Variation (Shore A) -2 -1 0 Elongation Thermal aging (1000h / 125 ° C) ASTM D573 % Change -4.4 18.7 1.4 Tearing Thermal aging (1000h / 125 ° C) ASTM D573 % Change -6.1 -11 -8.8
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-40 ° C Traction ASTM D412 matrix C % Change 38.5 -40 ° C Elongation ASTM D412 matrix C % Change 17.6 Low temperature (-40 ° C) ASTM D2137 Method ADo not break Do not break Do not break 80 ° C Traction ASTM D412 matrix C % Change -10.8 80 ° C Elongation ASTM D412 matrix C % Change -1.5 Deformation byCompression Folded C / S(22h / 70 ° C) ASTM D395 Method B % 20.7 25 30 Folded C / S(22h / 80 ° C) ASTM D395 Method B % 20.2 30.5Folded C / S(72h / 80 ° C) ASTM D395 Method B % 22.5 32.6Folded C / S (100h / 80 ° C) ASTM D395 Method B % 39.2 44.3 54.7 Folded C / S (168h / 80 ° C) ASTM D395 Method B % 29 39Folded C / S (500h / 80 ° C) ASTM D395 Method B % 41.2 53.8Folded C / S (1000h / 80 ° C) ASTM D395 Method B % 43.8 55.4Folded C / S(22h / 90 ° C) ASTM D395 Method B % 22.5 32.8Folded C / S (22h / 100 ° C) ASTM D395 Method B % 25.4 35 42.5 Folded C / S (70h / 125 ° C) ASTM D395 Method B % 29 37.9 46.6 Folded C / S (2211/135 ° C) ASTM D395 Method B % 38.5 46.6Folded C / S (22h / 150 ° C) ASTM D395 Method B % 44.3 61Folded C / S (22h / 175 ° C) ASTM D395 Method B % 23.3 38.1Permanent Compressive Distortion (22h / 100 ° C) JIS K 6257 % 30 41 43 Miscellaneous Volume Resistivity IEC 60093 Ω cm 2.1 x 10 ¹⁶ 2.2 x 10 ¹⁶ 2.2 x 10 ¹⁶ Weather (3000 h.) SAE J2527 AATCC 4-5 4-5 4-5 Natural Weather in Arizona (2 years) SAEJ1976, ProcedureTHE ΔΕ 1.6 1.2 1.7 Natural storms in Florida (2 years) SAEJ1976, Procedure A ΔΕ 1.6 1.0 1.2 Mist SAEJ1756 % 97 96 97
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Ozone resistance ASTM Dl 171 Method B Retention Rating (%) 100 100 100Flammability ISO 3795 Rate ofBurning (mm / min) 19 22 17Odor SAEJ1351 No shy or dry unpleasant odor Approved Approved ApprovedPaint staining (24h / 70 ° C) ASTM D925 Method ANo spots No spots No spots
[00125] Table 5 below shows the chemical resistance material properties for Example 2, which is representative of all the silane-crosslinked polyolefin elastomers described. Method B includes reporting any evidence of softening, staining, blistering, flake formation, splintering, checking, calcination, cracking, spillage, sinking, bulging, adherence, flaking or delamination. The degree of equity is 5 for a CELAB difference of 0 and a Tolerance of 0.2 and the degree of equity is 4 for a CELAB difference of 1.7 and a Tolerance of ± 0.3.
TABLE 5
test Chemical product Method Units/Production Ex. 2 Resist, solvent (72h / RT) 7: 3 (kerosene: mineral alcohol) TSM1720G % Change in volume 170 Resist, fluid Gasoline Oct. 87, unleaded, 20% Ethanol FLTM BI 168-01, Method B Classif. (see above) Approved,4 Diesel, type 2, 20% Biodiesel FLTM BI 168-01, Method B Classif. (see above) Approved,4 Soda, Ethylene Glycol / Water 50/50 FLTM BI 168-01, Method B Classif. (see above) Approved,5 engine oil, meets APIILSAC requirements FLTM BI 168-01, Method B Classif. (see above) Approved,5 Deionized water FLTM BI 168-01, Method B Classif. (see above) Approved,5 Multiple use cleaner (Formula 409, Fantastic, or Armor All) FLTM BI 168-01, Method B Classif. (see above) Approved,5 Ethanol-based windshield washer fluid, 1 part Motorcraft fluid for 1.5 pairs of water FLTM BI 168-01, Method B Classif. (see above) Approved,5 Product Motor craft Bug and tar remover FLTM BI 168-01, Method B Classif. (see above) Approved,5 Glass cleaner FLTM BI 168-01, Method B Classif. (see above) Approved,5 Isopropyl alcohol 1: 1 with water FLTM BI 168-01, Method B Classif. (see above) Approved,5
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60/81 [00126] Referring now to Figure 13, the percentage of deformation after compression is given by CB = [(Ho-Ho ') / (Ho-H _{C (} > _mp ) x 100% where Ho is the original thickness of the specimen before compression, Ho 'is the thickness of the specimen after the test, and H _CO mp is the thickness of the specimen during the test. As shown in Figure 13, each of Examples 2, 6, and 7 (“Exs. 2, 6 and 7” in Figure 13) made of silane-crosslinked polyolefin elastomers showed a lower strain after compression after one hour and a higher strain recovery rate compared to TOSE 539 70 (“TPS” in Figure 13), a styrenic TPV or TPS, and SANTOPRENE 12167W175 (“EPDM / PP” in Figure 13), an EPDM / PP copolymer. As a deformation after compression provided by each of the polyolefin elastomers cross-linked by a silane (Exs. 2, 6 and 7) compared to the comparative materials TPV and EPDM demonstrate the best pro high elastic properties presented by these materials.
[00127] Referring now to Figure 14, the edge deformation recovery percentage is given by LSR = [(Lo ') / (Lo) x 100% where Lo is the original percentage of the edge before compression and Lo' is the edge thickness after testing. As shown in Figure 14, each of Examples 2, 6, and 7 obtained from the silane-crosslinked polyolefin elastomers showed a higher edge deformation recovery after one hour (97%, 97.5%, and 99.2%, respectively) and a higher speed of edge deformation recovery compared to TPS (93%) or EPDM / PP copolymer (94%). Again, the percentages of edge deformation recovery provided by each of the silane-crosslinked polyolefin elastomers in relation to TPV and EPDM materials demonstrate the best elastic properties presented by these materials.
[00128] With reference now to Figure 15, the percentage of the
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61/81 edge relaxation for 1 h at 23 ° C is given by R (%) = (Fo-F _t ) / (Fo) where Fo is the initial force required for the first compression and F _t is the final force required for compression for the test period. As shown in Figure 15, each of Examples 2, 6, and 7 made of the silane crosslinked polyolefin elastomers had a better relaxation rate compared to TPS or EPDM / PP copolymer.
[00129] With reference now to Figure 16, the stress / strain behavior of a polyolefin elastomer crosslinked by a silane exemplifying the present description is provided. The dashes in Figure 16 demonstrate the particularly small areas that can be obtained between the stress / strain curves for the silane crosslinked polyolefin of the description. Elastomeric materials typically have nonlinear strain curves with a significant loss of energy when repeatedly stretched. The polyolefin elastomers crosslinked by a silane of the present description have greater elasticity and less viscoelasticity (for example, they have linear curves and have very low energy loss). The lack of any filler or plasticizer in these materials leads to no demonstration of any Mullins and / or Payne effect.
[00130] With reference now to Figure 18, deformation performance after compression is provided over a range of elevated temperatures and increasing time periods for Example 1, a comparative TPV, and a comparative EPDM. As shown in the graph, the% deformation after compression of the silane crosslinked polyolefin elastomer (Example 1) increases slightly by the rising temperatures provided (23 ° C175 ° C) for a 22 h test time compared to the comparative materials of TPV and EPDM. The% deformation after compression of the polyolefin elastomer crosslinked by an Ex. 1 silane is surprisingly regular across the temperature range provided compared to the dramatic increase in the% deformation after compression demonstrated for the materials
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[00131] Referring now to Figure 17, deformation performance after compression is provided over a range of elevated temperatures and increasing time periods for Example 1, a comparative TPV, and a comparative EPDM. As shown in the graph, the% deformation after compression of the silane crosslinked polyolefin elastomer (Example 1) increases slightly by the increasing temperatures provided (70 ° C175 ° C) and test time (22 h-1000 h) in relation to comparative materials of TPV and EPDM.
[00132] Figure 19 and Table 6 below provide additional data regarding deformation performance after compression of Examples 2-4 in relation to EPDM 9724 and TPV 121-67, Table 6 provides deformation data after compression performed in triplicate for Examples 2-4 with respect to EPDM 9724 (“EPDM”) and TPV 121-67 (“TPV”). Figure 19 traces the mean values of deformation after compression for these samples performed at 72 h at 23 ° C and 70 h at 125 ° C.
TABLE 6
Compound 72h / 23 ° C 70h / 125 ° Ç Ex. 2 13.8 22.1 Ex. 2 15.7 22.3 Ex. 2 20.4 22.9 Average 16.6 22.4 Ex. 3 19.9 31.0 Ex. 3 21.4 33.6 Ex. 3 23.6 33.6 Average 21.6 32.7 Ex. 4 24.8 41.9 Ex. 4 24.6 40.2 Ex. 4 28.4 40.0 Average 25.9 40.7 EPDM 5.6 75.4 EPDM 8.3 76.3 EPDM 11.5 82.3 Average 8.5 78.0 TPV 21.2 51.2 TPV 21.4 52.4 TPV 21.5 47.8 Average 21.4 50.5
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Example 8 [00133] Example 8 (Example 8) or ED108-2A was produced by extruding 48.70% by weight of ENGAGE ™ 8842 and 48.70% by weight of XUS38677.15 along with 2.6% by weight of SILAN RHS 14/032 or SILFIN 13 to form a polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 8 was then extruded with 1.7 wt% foaming agent Hydrocerol 1170, 2 wt% AMBICAT ™ LE4472 condensation catalyst, and 360 ppm dioctyltin dilaurate condensation catalyst (DOTL) to form a silane crosslinkable polyolefin elastomer, which was then extruded into an uncured elastomeric article. The dynamic sealing member of uncured silane crosslinkable polyolefin elastomer of Example 8 was then cured at ambient temperature and humidity to form a silane crosslinked polyolefin elastomer consistent with the elastomers of the description. The composition of Example 8 is given in Table 7 below and its material properties are given in Table 8 below.
Example 9 [00134] Example 9 (Example 9) or ED108-2B was produced by extruding 48.70% by weight of ENGAGE 8842 and 48.70% by weight of XUS38677.15 and 2.6% by weight of SILAN RHS 14 / 032 or SILFIN 13 together with Exact 9061 / SpectraSyn 10 (70/30) to form the silane-grafted polyolefin elastomer. The silane-grafted polyolefin elastomer of Example 2 was then extruded with 1.7% by weight of Hydrocerol 1170 foaming agent, 2% by weight of AMBICAT ™ LE4472 condensation catalyst, and 360 ppm of dioctyltin dilaurate condensation catalyst (DOTL) to form a silane crosslinkable polyolefin elastomer, which was then extruded into an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 9 was then cured at room temperature and humidity
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64/81 to form a silane crosslinked polyolefin elastomer, consistent with the elastomers of the description. The composition of Example 9 is given in Table 7 below and its material properties are given in Table 8 below. Also provided below in Table 8 are properties associated with a comparative EPDM material (“EPDM”).
TABLE 7
Ingredients Ex. 1 Ex. 2 ENGAGE XLT8677 / XUS 38677.15 48.7 46.25 ENGAGE 8842 48.7 46.25 SILAN RHS 14/032 or SILFIN 29 2.6 2.5 Exact 9061 / SpectraSyn 10 (70/30) - 5 TOTAL 100 100
TABLE 8
Property test Method Units / Production Ex. 1 Ex. 2 EPDM Structural Density ASTM D297 g / cm3 0.52 0.55 0.66 Traction ASTM D412 matrix C MPa 2.6 2.0 2.9 Stretching ASTM D412 matrix C % 230 209 354 100% Module ASTM D412 matrix C MPa 1.5 1.4 0.80 Tear C ASTM D624 matrix C N / mm 8.0 9.6 8.8 Def. After compression (50% compression) Folded C / S (22h / 80 ° C) ASTM D395 Method B % 29.4 35.4 47.4 Folded C / S (96h / 80 ° C) ASTM D395 Method B % 37.6 58.9 56.4 Folded C / S (168h / 80 ° C) ASTM D395 Method B % 67.0 69.6 67.8 Folded C / S (500h / 80 ° C) ASTM D395 Method B % 76.473.5 Folded C / S (1000h / 80 ° C) ASTM D395 Method B % 78.697.3 Miscellaneous Water absorption GM9888P % 0.16 - 0.21
[00135] With reference now to Figure 14, a graph of load versus position is presented for Example 8 Resin ED108-2A (ie, as prepared above in Example 8), as crosslinked with 2% catalyst (“Ex, 8 with 2% cat ”), 3% catalyst (Example 1 with 3% cat”), and 2% catalyst with a sliding coating (“Ex, 8 with 2% cat. and sliding coating”). An example of a load versus position comparison chart is provided for a traditional EPDM sponge material (“EPDM”). Ex. 8 materials (ie dynamic elastomers of
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65/81 silane crosslinked polyolefin according to the description) exhibit a smaller area between the load / position curves compared to the areas between the load / position curves for the comparative EPDM compound. This smaller area between the load / position curves for silane-crosslinked dynamic polyolefin elastomers may be desirable for elastomeric articles, for example, seals, which can be used for various sealing applications. In addition, the polyolefin blends of Example 8 do not contain any fillers or plasticizers incorporated so that each of the corresponding load / position curves for these blends does not have or exhibit any Mullins effect and / or Payne effect.
[00136] The selection of the condensation catalyst can have an influence on the final material properties for a sample. For example, the ED108-2B silane-grafted polyolefin elastomer of Example 9 was produced by extruding 48.70% by weight of ENGAGE 8842 and 48.70% by weight of XUS38677.15 and 2.6% by weight of SILAN RHS 14 / 032 or SILFIN 13 together with Exact 9061 / SpectraSyn 10 (70/30) to form the silane-grafted polyolefin elastomer. These silane-grafted polyolefin elastomers of Example 9 were then extruded with two different condensation catalysts: (a) with 1.7% by weight of Hydrocerol 1170 foaming agent, 2% by weight of AMBICAT ™ LE4472 condensation catalyst, and 360 ppm of dioctyltin dilaurate condensation catalyst (DOTL); and (b) with 1.7% by weight Hydrocerol 1170 foaming agent, 2% by weight of AMBICAT ™ LE4472 condensation catalyst, and 360 ppm of dibutyltin dilaurate (DBTDL) condensation catalyst. Consequently, two silane crosslinkable polyolefin elastomers were formed (identified as “DOTL” and “DBTDL”), which were then extruded into an uncured elastomeric article. The difference in material properties of these crosslinkable elastomers is given in Tables 9 and 10.
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TABLE 9
Elastomer group 22h / 80C Tube C / S (%) 9611 / 80C Tube C / S (%) 168h / 80C Tube C / S DOTL 38.9 42.1 52.3 DBTDL 25.9 27.9 34.0
TABLE 10
Group Hard Traction MPa Stretching (%) 100% Module (Mpa) Auburn density (g / cm ³ ) TC (N / mm) DOTL 43 2.8 294 1.3 0.52 9.3 DBTDL 39 2.9 170 1.9 0.51 7.6
[00137] With reference now to Figure 15, cross-sectional views are provided for a polyolefin elastomer crosslinked by a foamed silane using supercritical gas injection and chemical foaming agents. As provided by the images, the pore size resulting from the chemical foaming agent is from 20 pm to 147 pm while the pore size resulting from the supercritical gas injection is from 46 pm to 274 pm. Depending on the type of foaming agent selected to foam each respective silane crosslinkable polyolefin elastomer described here, a variety of different pore sizes can be obtained that will affect the final density of the polyolefin elastomer crosslinked by a foamed silane. In some ways, the pore size can be from 20 pm to 200 pm, from 25 pm to 400 pm, or from 25 pm to 300 pm.
Example 10 [00138] Example 10 (Example 10) or ED76-4A was produced by extruding 82.55% by weight of ENGAGE ™ 8842 and 14.45% by weight of MOSTEN ™ TB 003 together with 3.0% by weight of SILAN RHS 14/032 or SILFIN 29 to form a silane grafted polyolefin elastomer. The silane-grafted polyolefin elastomer of Example 10 was then extruded with 2.0 wt% microencapsulated blowing agent MBFAC170EVA, 3 wt% AMBICAT ™ LE4472 condensation catalyst, and 0.7 wt% auxiliary AD-2 process to form a
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67/81 polyolefin elastomer crosslinkable with foamed silane, which was then extruded as an uncured elastomeric article. The silane crosslinkable polyolefin elastomer of the foamed uncured elastomeric article of Example 10 was then cured at ambient temperature and humidity to form a polyolefin elastomer crosslinked by a foamed silane, consistent with the elastomers of the description. The composition of Example 10 is given in Table 11 below and the material properties associated with its foamed silane crosslinked polyolefin blend are provided in Table 12 below.
Example 11 [00139] Example 11 (Example 11) or ED76-4E was produced by extruding 19.00% by weight of ENGAGE ™ 8150, 58.00% by weight of ENGAGE ™ 8842, and 20.00% by weight of MOSTEN ™ TB 003 together with 3.0% by weight of SILAN RHS 14/032 or SILFIN 29 to form a polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 2 was then extruded with 2.0 wt% microencapsulated blowing agent MBF-AC170EVA, 3 wt% AMBICAT ™ LE4472 condensation catalyst, and 0.7 wt% process aid AD-2 to form a crosslinkable polyolefin elastomer with foamed silane, which was then extruded into an uncured elastomeric article. The foamed silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 11 was then cured at ambient temperature and humidity to form a crosslinked polyolefin elastomer by a foamed silane, consistent with the elastomers of the description. The composition of Example 11 is given in Table 11 below and the material properties associated with its foamed silane crosslinked polyolefin blend are provided in Table 12 below.
Example 12 [00140] Example 12 (Example 12) or ED76-5 was produced
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68/81 extruding 19.00% by weight of ENGAGE ™ 8150, 53.00% by weight of ENGAGE ™ 8842, and 25.00% by weight of MOSTEN ™ TB 003 together with 3.0% by weight of SILAN RHS 14 / 032 or SILFIN 29 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 3 was then extruded with 2.0% by weight of microencapsulated blowing agent MBF-AC170EVA, 3% by weight of AMBICAT ™ LE4472 condensation catalyst, and 0.7% by weight. process aid weight AD-2 to form a crosslinkable polyolefin elastomer with foamed silane, which was then extruded into an uncured elastomeric article. The foamed silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 12 was then cured at ambient temperature and humidity to form a polyolefin elastomer crosslinked by a foamed silane, consistent with the elastomers of the description. The composition of Example 12 is given in Table 11 below and the material properties associated with its foamed silane crosslinked polyolefin blend are given in Table 12 below.
Example 13 [00141] Example 13 (Example 13) or ED76-6 was produced by extruding 16.36% by weight of ENGAGE ™ 8150, 45.64% by weight of ENGAGE ™ 8842, and 35.00% by weight of MOSTEN ™ TB 003 together with 3.0% by weight of SILAN RHS 14/032 or SILFIN 29 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 13 was then extruded with 2.0 wt% microencapsulated blowing agent MBF-AC170EVA, 3 wt% AMBICAT ™ LE4472 condensation catalyst, and 0.7 wt% process aid AD-2 to form a crosslinkable polyolefin elastomer with foamed silane, which was then extruded into an uncured elastomeric article. The foamed silane crosslinkable polyolefin elastomer of the uncured elastomeric article of Example 4 was then cured
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69/81 at room temperature and humidity to form a polyolefin elastomer crosslinked by a foamed silane, consistent with the elastomers of the description. The composition of Example 13 is given in Table 11 below and the material properties associated with its foamed silane crosslinked polyolefin blend are provided in Table 12 below.
TABLE 11
Ingredients Ex. 1 Ex. 2 Ex. 3 Ex. 4 ENGAGE 8150 - 19.00 19.00 16.36 ENGAGE 8842 82.55 58.00 53.00 45.64 MOSTEN TB 003 14.45 20.00 25.00 35.00 SILAN RHS 14/032 or SILFIN 29 3.00 3.00 3.00 3.00 TOTAL 100 100 100 100
TABLE 12
Property test Method Units / Production Ex. 1 Ex. 2 Ex. 3 Ex. 4 Physical properties Density ASTM D297 g / cm ³ 0.67 0.66 0.67 0.69 Toughness ASTM D412 matrix C Shore A 60 67 69 87 Traction ASTM D412 matrix C MPa 5.0 7.2 8.7 7.6 Stretching ASTM D412 matrix C % 160 174 203 293 Tear C ASTM D624 matrix C N / mm 12.6 22.8 22.5 46.8 PropertiesI have known Hardness Aging thermal cement (70h / 70 ° C) ASTM D573 Variation (Shore A) 2 0 1 1 Traction Aging thermal cement (70h / 70 ° C) ASTM D573 % Change 12.6 5.5 -0.8 7 StretchingThermal aging (70h / 70 ° C) ASTM D573 % Change -0.6 -7.2 -13.5 -12.8 Def. After pres. Folded C / S(22h / 70 ° C) ASTM D395Method B % 40 41 61 78 Misce lânea Water absorption MS-AK-92 % 0.5 0.2 0.7 0.5 Resistance toozone (168h / 40% elongation) ASTM Dl 149No cracks No cracks No cracks No cracks Odor SAEJ1351 No wet or dry odor Approved Approved Approved Approved Paint staining (24h / 70 ° C) ASTM D925Method ANo bad calls No stain No bad chas No bad chas
Example 14
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70/81 [00142] A foamed elastomeric article was prepared using a twin screw reactive extruder 66 (see Figure 3A) to extrude 48.7% by weight of ENGAGE ™ XLT8677 or XUS 38677.15 and 48.7% by weight of ENGAGE ™ 8842 together with 2.6% by weight of SILAN RHS 14/032 or SILFIN 29 to form the polyolefin elastomer grafted with ED 108-2A silane. Then, a single screw reactive extruder 102 (see Figure 3B) equipped with a supercritical fluid injector (not shown) was used to further process the blend, where the supercritical fluid medium was nitrogen (N2) with a gas flow of 0.29 kg / h. The injector open time was 10 s and the pressure was maintained at 140 bar. A gas charge of 0.5% by weight was used with an injection speed of 75 mm / s. The weight of the ED108-2A material used was 153.4 g. The resulting sample has a density of 0.382 g / cm ³ , as measured using a density scale. No condensation catalyst was added and the precision opening was 1.5 mm. The material properties for Example 14 are listed below in Table 13, where the strain values after compression were measured according to ASTM D 395 and the density values were measured by measuring the weight, length, width and thickness of a sample ( approximately 9 cm x 10 cm, and 0.2-0.5 cm thick).
TABLE 13
Deformation 6h / 50 ° C after compression Compression 30 min 24 h 48 h 25% 37.4% 30.6% 26.5% 50% 44.9% 38.2% 35.0% Density % rebound ASKERC ShA 0.46 48.6 43.8 25.6
Example 15 [00143] A foamed elastomeric article was prepared using a twin screw reactive extruder 66 (see Figure 5A) to extrude 82.55% by weight of ENGAGE ™ 8842 and 14.45% by weight of MOSTEN ™ TB 003 together with 3.0% by weight of SILAN RHS 14/032 or SILFIN 29 to form the polyolefin elastomer grafted with ED76-4A silane. In
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71/81 then a single screw reactive extruder 102 was then used to load and extrude silane-grafted polyolefin elastomer with 1.0% by weight of dioctyltin dilaurate condensation catalyst (DOTL), and 10% by weight of MEBA chemical foaming agent. The density of the corresponding polyolefin elastomer crosslinked by a foamed silane was 0.304 g / cm ³ as measured using a density scale. Deformation data after for Example 15 is listed below in Table 14.
TABLE 14
Deformation 6h / 50 ° C after compression Compression 30 min 24 h 48 h 25% 22.1% 17.2% 18.4% 50% 14.6% 12.9% 10.4%
Example 16 [00144] Example 16 or ED76-4A was produced by extruding 82.55% by weight of ENGAGE ™ 8842, 14.45% by weight of MOSTEN ™ TB 003 together with 3.0% by weight of SILAN RHS14 / 032 or SILFIN 29 to form the polyolefin elastomer grafted with silane. The silane-grafted polyolefin elastomer of Example 16 was then extruded with 300 ppm to 400 ppm of dioctyltin dilaurate (DOTL) condensation catalyst to form a silane crosslinkable polyolefin elastomer that can be molded or extruded into an element of hose not cured. The silane crosslinkable polyolefin elastomer of Example 16 was then cured at room temperature and humidity to form the corresponding silane crosslinked polyolefin elastomer. The composition of Example 16 and acceptable composition ranges for the various components thereof are given in Table 15 below.
TABLE 15
Component Relative quantity (% by weight) First range (% by weight) Second range (% by weight) ENGAGE 8842 82.55 60-90 75-85 RHS 14/032 3.00 1-5 2-4 MOSTEN TB 003 14.45 5-25 10-20 Total 100 100 100
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Example 17 [00145] Example 17 (Example 17) or ED 92-GF was produced by extruding 34.20% by weight of ENGAGE ™ 8842, 41.20% by weight of ENGAGE ™ XLT8677 or XUS 38677.15, 14.50% by weight and 19.34% by weight of MOSTEN ™ TB 003, and 7.50% by weight of RHS14 / 033 (35% GF) with 2.6% by weight of SILAN RHS14 / 032 or SILFIN 29 to form the elastomer of polyolefin grafted with silane. The silane-grafted polyolefin elastomer of Example 17 was then extruded with dioctyltin dilaurate (DOTL) condensation catalyst to form a silane crosslinkable polyolefin elastomer that can be molded or extruded into an uncured hose element. The silane crosslinkable polyolefin elastomer of Example 17 was cured at room temperature and humidity to form the corresponding silane crosslinked polyolefin elastomer. The composition of Example 17 and acceptable composition ranges for the various elements thereof are provided in Table 16 below. The material properties of Example 17 are provided in Table 17 below, the material properties provided are representative of those shared by each of the silane crosslinked polyolefin elastomers described here.
[00146] The composition of Example 17 can be cured using 200 ppm to about 500 ppm dioctyltin dilaurate (DOTL) catalyst system. ENGAGE ™ Polyolefin elastomer 8842 is an ultra-low density ethylene-octene copolymer. ENGAGE ™ XLT8677 polyolefin elastomer is an ethylene-octene copolymer that is added to function as an impact modifier. MOSTEN ™ TB 003 is a polypropylene homopolymer. RHS 14/033 is a copolymer of ethyleneoctene having 35% by weight of glass fibers. SILAN RHS 14/032 and SILFIN 29 are both blends of a vinyltrimethoxysilane monomer and a peroxide molecule for grafting and crosslinking the various polyolefins
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73/81 added to the blend.
TABLE 16
Component Relative quantity (% by weight) First range (% by weight) Second range (% by weight) ENGAGE 8842 34.20 20-50 30-40 ENGAGE XLT8677(XUS 38677.15) 41.20 20-60 35-45 MOSTEN TB 003 14.50 5-25 10-20 RHS 14/033 (35% GF) 7.50 2-20 5-10 SILAN RHS 14/032 orSILFIN 29 2.60 1-10 2-3 Total 100 100 100
TABLE 17
Property test Method Units/Production Ex. 1 Originals Toughness ASTM D412 matrix C Shore A 74 Traction ASTM D412 matrix C Mpa 9.3 Stretching ASTM D412 matrix C % 301 Tear C ASTM D624 matrix C N / mm 33.4 Tearing Delft Environment Tearing Delft ISO 34-2 N 44.3 100 ° C Delft tear ISO 34-2 N 14.8 125 ° C Delft tear ISO 34-2 N 9.4 135 ° C Delft tear ISO 34-2 N 8.5 Thermal aging Hardness Thermal Env (1000h / 120 ° C) ASTM D573 Variation (Shore A) -1 Traction Env. Thermal (1000h / 120 ° C) ASTM D573 % Change 9.1 Elongation Thermal Env (1000h / 120 ° C) ASTM D573 % Change -28.2 Thermal Env. Hardness (168h / 135 ° C) ASTM D573 Variation (Shore A) -1 Traction Env. Thermal (168h / 135 ° C) ASTM D573 % Change 6.5 Elongation Thermal Env (168h / 135 ° C) ASTM D573 % Change -17 Thermal Env. Hardness (1000h / 135 ° C) ASTM D573 Variation (Shore A) -3 Traction Env. Thermal (1000h / 135 ° C) ASTM D573 % Change 20.8 Elongation Thermal Env (1000h / 135 ° C) ASTM D573 % Change -25.5 Thermal Env. Hardness (168h / 150 ° C) ASTM D573 Variation (Shore A) 0 Traction Env. Thermal (168h / 150 ° C) ASTM D573 % Change -1.3 Elongation Thermal Env (168h / 150 ° C) ASTM D573 % Change -33 Def. After compression Folded C / S (22h / 80 ° C) ASTM D395 Method B % 28 Misc. Weather (3000 h.) SAE J2527 AATCC 4-5(approved)
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74/81 [00147] Abrasion test results were obtained for Examples 16 and 17 using a TeWilliam abrasion test method (JIS K6242). The test conditions included a rotation speed of 37 + 3 rpm, a load of 35.5 N, and a test time of 6 minutes. The results are provided below in Table 18,
TABLE 18
Material SGDecrease in mass (g) Abrasion volume ΔΝ JV1000(g / cm ³ )1 2 3 Average (mm ³ ) (mm ³ ) Ex. 16 0.8800.0036 0.0062 0.0045 0.0044 5.0 21.80.0029 0.0033 0.0057 Ex. 17 0.9110.0450 0.0424 0.0271 0.0296 32.5 142.3
Silane effect [00148] Blends of polyolefin elastomers (Engage 8842), polypropylene (PP 4.0), and silane (silfin 13) were mixed in a high temperature twin screw extruder to graft the silane onto the polyolefin. The amount of silane was varied. The results are shown in Table 19 below. For this blend, traction, stretching, and Tearing C (TC) were good at 2.6% by weight of silane cocktail, but C / S results were less than 2.8% by weight.
TABLE 19
Component ED76 ED76-2.4 ED76-2.6 ED76-2.8 Engage 8842 0.8245 0.8296 0.8279 0.8262 PP4.0 0.1455 0.1464 0.1461 0.1458 silfin 13 0.03 0.024 0.026 0.028 test Property ED76 ED76-2.4 ED 76-2.6 ED76-2.8 Orig. Traction (D412 matrix) Lrg matrix Durometer (ShA) 67 67 72 68 Peak voltage (MPa) 7.7 7.7 8.7 8.4 Stretching (%) 223 246 271 263 100%Module (MPa) 3.3 3.2 3.2 3.1 TC Tear C (N / mm) 20.8 20.3 21.4 19.3 VWC / S (def. After compression) 2211 / 90C (%) 76.5 78.2 - 75 VWC / S 2211 / 70C (%)Daimler 76 74.7 78.4 75 Folded C / S 2211 / 80C (%) 22.6 19.5 21.6 17.6
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Polypropylene effect [00149] The polypropylene effect was also tested. Variable amounts of TAMPER ™ PN 3560 and PP 4.0 were used. The results are shown in Table 20 below. Comparing ED76 to ED87, a slight improvement in elongation was observed, but on the whole, no significant improvement was seen from the addition of PN-3560 (propylene-based polymer, a special olefinic resin designed to improve transparency, flexibility, softness, and strength impact). Without wishing to be bound by theory, PN3560 is believed to improve doubled C / S due to the higher melting point in the crystalline region.
TABLE 20
Component ED76 ED86 ED87 Engage 8842 0.8245 0.8279 0.8279PN 3560 0.1461 0.0487 PP 4.0 0.1455 - 0.0974 silfin 13 0.03 0.026 0.026- - test Property ED76 ED86 ED87 Orig. Traction (D412 die) Lrg die Durometer (ShA) 67 60 66 Peak voltage (MPa) 7.7 6.1 8 Stretching (%) 223 299 284 100% Module (MPa) 3.3 2.1 2.9 TC Tear C (N / mm) 20.8 14.6 19.2 VWC / S 22h / 90C (%) 76.5 78.8 76.7 VWC / S 2211 / 70C (%) Daimler 76 76.6 74.7 Folded C / S 22h / 80C (%) 22.6 16.1 20.7
Effect of the XUS Polymer [00150] The effect of the XUS polymer has also been studied. The results are shown in Table 21 below. ENGAGE ™ 8842 and XUS 38677.15 are both ethylene-octene copolymers. ENGAGE ™ 8842 has about 55% ethylene and XUS 38677.15 has about 52% ethylene. However, XUS 38677.15 is a block olefin copolymer where the soft segment is amorphous (to have low deformation after compression). The hard segment has a melting point well above 70 ° C. Excellent traction and CT results were seen for ED89, but C / S was high. Lower C / S resulted from ED92,
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TABLE 21
Component ED 88 ED89 ED 92 XUS 38677 (XUS) 0.828 0.414 0.414 Engage 8003 - 0.414Engage 8842 - - 0.414 PP4.0 0.146 0.146 0.146 silfin 13 0.026 0.026 0.026 test Property ED88 ED89 ED92 Orig. Durometer 75 84 74 Traction (ShA) (matrixD412) Peak voltage (MPa) 9.7 12.2 8.6 Lrg die Stretching (%) 254 310 257 100% Module (MPa) 4.7 5.3 3.7 TC Tear C (N / mm) 26 33.3 25.7 VW c / s 2211 / 90C (%) 66 85.6 60.2 VW c / s 2211 / 70C (%)Daimler 58.4 83.5 53.1 TripeC / S 2211 / 80C (%) 21.8 29.5 16.5
[00151] For the purposes of this description, the term “coupled” in all its forms, coupling, coupling, coupled, etc.) generally means the union of two components directly or indirectly to each other. Such a connection may be of a stationary nature or of a mobile nature. Such a union can be achieved with the two components and any additional intermediate members being formed integrally as a single unitary body with each other or with the two components. Such a union may be of a permanent nature or it may be of a removable or detachable nature, unless stated otherwise.
[00152] It is also important to note that the construction and arrangement of the device elements as shown in the exemplary modalities are illustrative only. Although only a few modalities of the present innovations have been described in detail in this
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77/81 description, those skilled in the art who review this description will readily appreciate that many modifications are possible (for example, variations in sizes, dimensions, structures, shapes and proportions of the various elements, parameter values, mounting arrangements, use of materials, colors, orientations, etc.) without deviating materially from the new teachings and advantages of the mentioned material. For example, elements shown as integrally formed can be constructed of multiple parts or elements shown as multiple parts can be integrally formed, the operation of the interfaces can be reversed or varied in another way, the length or width of the structures and / or members or connector or other elements of the system can be varied, the nature or number of predicted adjustment positions between the elements can be varied. It should be noted that the system elements and / or assemblies can be constructed from any of a wide variety of materials that provide sufficient strength or durability, in any of a wide variety of colors, textures and combinations. Consequently, all these modifications are intended to be included within the scope of the present innovations. Other substitutions, modifications, changes, and omissions can be made in the design, operating conditions and arrangement of the desired modalities and other examples without departing from the spirit of the present innovations.
[00153] It should be understood that any processes or steps described within the described processes can be combined with other processes or steps described to form structures within the scope of the present device. The exemplary structures and processes described here are for illustrative purposes and should not be construed as limiting.
[00154] The description above is considered that of the modalities illustrated only. Modifications to the device will occur to those skilled in the art and to those who produce or use the device. Therefore, it is understood that the modalities shown in the drawings and described above are intended
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78/81 for illustrative purposes only and not to limit the scope of articles, processes and compositions, which are defined by the following claims as interpreted in accordance with the principles of patent law, including the Doctrine of Equivalents.
LIST OF NON-LIMIT ACTIVE MODALITIES [00155] Mode A is a blend of polyolefin elastomer crosslinked by a silane comprising: a first polyolefin having a density less than 0.86 g / cm ³ ; a second polyolefin having a percentage crystallinity of less than 40%; a silane crosslinker, in which the silane crosslinked polyolefin elastomer blend has a deformation after compression of about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 h at 70 ° C) and in which the polyolefin elastomer blend crosslinked by a silane has a density less than 0.90 g / cm ^3, [00156] The polyolefin elastomer blend crosslinked by a modality A silane additionally comprising a microencapsulating foaming agent .
[00157] The blend of polyolefin elastomer crosslinked by a modality A or modality A silane with any of the intervening characteristics in which the density is less than 0.70 g / cm ^3, [00158] The polyolefin elastomer blend crosslinked by a Modality A or Modality A silane with any of the intervening characteristics additionally comprising a foaming agent.
[00159] The polyolefin elastomer blend crosslinked by a Modality A or Modality A silane with any of the intervening characteristics in which the density is less than 0.60 g / cm ^3, [00160] The polyolefin elastomer blend crosslinked by Modality A or Modality A silane with any of the intervening characteristics in which the deformation after compression is about 15.0% at
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79/81 about 35.0%, as measured according to ASTM D 395 (22 h at 70 ° C). [00161] The blend of polyolefin elastomer crosslinked by a modality A or modality A silane with any of the intervening characteristics in which the first polyolefin comprises an ethylene-octene copolymer of about 60% by weight at about 97% by weight Weight.
[00162] The blend of polyolefin elastomer crosslinked by a Modality A or Modality A silane with any of the intervening characteristics in which the second polyolefin comprises a polypropylene homopolymer of about 10% by weight to about 35% by weight and / or a poly (ethylene-co-propylene).
[00163] The blend of polyolefin elastomer crosslinked by a Modality A or Modality A silane with any of the intervening characteristics in which the silane crosslinker comprises a vinyltrimethoxy silane of about 1% by weight to about 4% by weight.
[00164] Mode B is a blend of polyolefin elastomer crosslinked by a silane comprising: a first polyolefin having a density less than 0.86 g / cm ³ ; a second polyolefin having a percentage crystallinity of less than 40%; a silane crosslinker; a foaming agent; where the silane-crosslinked polyolefin elastomer blend has a strain after compression of about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 h at 70 ° C) and where the blend of polyolefin elastomer crosslinked by a silane has a density less than 0.70 g / cm ^3, [00165] The blend of polyolefin elastomer crosslinked by a modality B silane in which the first polyolefin comprises an ethylene-copolymer octene from about 60% by weight to about 97% by weight.
[00166] The blend of polyolefin elastomer crosslinked by a modality B or modality B silane with any of the intervening characteristics in which the second polyolefin comprises a homopolymer
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80/81 polypropylene of about 10% by weight to about 35% by weight and / or a poly (ethylene-co-propylene).
[00167] The blend of polyolefin elastomer crosslinked by a modality B or modality B silane with any of the intervening characteristics in which the silane crosslinker comprises a vinyltrimethoxy silane of about 1% by weight to about 4% by weight.
[00168] The blend of polyolefin elastomer crosslinked by a Modality B or Modality B silane with any of the intervening characteristics further comprising a condensation catalyst comprising a sulfonic ester of about 1% by weight to about 4% by weight .
[00169] The blend of polyolefin elastomer crosslinked by a modality B or modality B silane with any of the intervening characteristics in which the density is less than 0.60 g / cm ^3, [00170] The polyolefin elastomer blend crosslinked by a modality B or modality B silane with any of the intervening characteristics in which the foaming agent includes a microencapsulating foaming agent.
[00171] The blend of polyolefin elastomer crosslinked by a modality B or modality B silane with any of the intervening characteristics in which the deformation after compression is from 15.0% to about 35.0%, as a measure of according to ASTM D 395 (22 h at 70 ° C).
[00172] Mode C is a method for making an elastomeric article, the method comprising: extruding a first polyolefin having a density less than 0.86 g / cm ³ , a second polyolefin having a crystallinity less than 40%, a silane crosslinker and a graft initiator together to form a silane-grafted polyolefin blend; extrude the silane-grafted polyolefin blend and a condensation catalyst together to form a crosslinkable polyolefin blend
Petition 870190058681, of 06/25/2019, p. 86/107
81/81 silane; molding the silane crosslinkable polyolefin blend into an uncured elastomeric article; and crosslinking the crosslinkable polyolefin blend of the uncured elastomeric article at room temperature and ambient humidity to form the elastomeric article having a density less than 0.70 g / cm ³ , in which the elastomeric article shows a deformation after compression of fence from 5.0% to about 35.0%, as measured according to ASTM D 395 (22 h at 70 ° C).
[00173] The Method C method in which the polyolefin blend grafted with silane and the crosslinkable polyolefin blend are thermoplastics and the crosslinked polyolefin blend is a thermoset.
[00174] Method C or Mode C with any of the intervening characteristics in which the first polyolefin is a copolymer of ethylene / a-olefin and the second polyolefin is a homopolymer and polypropylene and / or a poly (ethylene-co- propylene).

权利要求:
Claims (20)
[1]
1. Blend of silane-crosslinked polyolefin elastomer, characterized by the fact that it comprises:
a first polyolefin having a density less than 0.86 g / cm ³ ;
a second polyolefin having a percentage crystallinity of less than 40%;
a silane crosslinker, in which the silane crosslinked polyolefin elastomer blend exhibits a strain after compression of about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 hours at 70 ° C) and where the silane-crosslinked polyolefin elastomer blend has a density of less than 0.90 g / cm ³ .
[2]
2. Blend of silane-crosslinked polyolefin elastomer according to claim 1, characterized in that it additionally comprises a microencapsulating foaming agent.
[3]
3. Blend of silane-crosslinked polyolefin elastomer according to claim 1 or 2, characterized in that the density is less than 0.70 g / cm ³ .
[4]
Blend of silane-crosslinked polyolefin elastomer according to any one of claims 1 to 3, characterized in that it additionally comprises a foaming agent.
[5]
A blend of silane-crosslinked polyolefin elastomer according to any one of claims 1 to 4, characterized in that the density is less than 0.60 g / cm ³ .
[6]
6. Blend of silane-crosslinked polyolefin elastomer according to any one of claims 1 to 5, characterized by the fact that the deformation after compression is from 15.0% to about 35.0%, as a measure of according to ASTM D 395 (22 hours at 70 ° C).
Petition 870190058681, of 06/25/2019, p. 88/107
2/4
[7]
A blend of silane crosslinked polyolefin elastomer according to any one of claims 1 to 6, characterized in that the first polyolefin comprises an ethyleneoctene copolymer of about 60% by weight to about 97% by weight.
[8]
8. Blend of silane crosslinked polyolefin elastomer according to any one of claims 1 to 7, characterized in that the second polyolefin comprises a polypropylene homopolymer of about 10% by weight to about 35% by weight and / or a poly (ethylene-co-propylene).
[9]
Blend of silane crosslinked polyolefin elastomer according to any one of claims 1 to 8, characterized in that the silane crosslinker comprises a vinyltrimethoxy silane of about 1% by weight to about 4% by weight.
[10]
10. Blend of silane-crosslinked polyolefin elastomer, characterized by the fact that it comprises:
a first polyolefin having a density less than 0.86 g / cm ³ ;
a second polyolefin having a percentage crystallinity of less than 40%;
a silane crosslinker;
a foaming agent;
wherein the silane-crosslinked polyolefin elastomer blend exhibits a strain after compression of about 5.0% to about 35.0%, as measured according to ASTM D 395 (22 hours at 70 ° C) and in that the silane-crosslinked polyolefin elastomer blend has a density less than 0.70 g / cm ³ .
[11]
11. Blend of silane-crosslinked polyolefin elastomer according to claim 10, characterized in that the first polyolefin comprises an ethylene-octene copolymer of about
Petition 870190058681, of 06/25/2019, p. 89/107
3/4
60% by weight to about 97% by weight.
[12]
12. Blend of silane-crosslinked polyolefin elastomer according to claim 10 or 11, characterized in that the second polyolefin comprises a polypropylene homopolymer of about 10% by weight to about 35% by weight and / or a poly (ethylene-copropylene).
[13]
13. Blend of a silane crosslinked polyolefin elastomer according to any one of claims 10 to 12, characterized in that the silane crosslinker comprises a vinyltrimethoxy silane of about 1% by weight to about 4% by weight.
[14]
14. Blend of silane-crosslinked polyolefin elastomer according to any one of claims 10 to 13, characterized in that it additionally comprises a condensation catalyst comprising a sulfonic ester of about 1% by weight to about 4% in weight.
[15]
15. Blend of silane-crosslinked polyolefin elastomer according to any one of claims 10 to 14, characterized in that the density is less than 0.60 g / cm ³ .
[16]
16. Blend of silane-crosslinked polyolefin elastomer according to any one of claims 10 to 15, characterized in that the foaming agent includes a microencapsulating foaming agent.
[17]
17. Blend of silane-crosslinked polyolefin elastomer according to any one of claims 10 to 16, characterized in that the deformation after compression is from 15.0% to about 35.0%, as a measure of according to ASTM D 395 (22 hours at 70 ° C).
[18]
18. Method for making an elastomeric article, the method characterized by the fact that it comprises:
extrude a first polyolefin having a lower density
Petition 870190058681, of 06/25/2019, p. 90/107
4/4 than 0.86 g / cm ³ , a second polyolefin having less than 40% crystallinity, a silane crosslinker and a graft initiator together to form a silane-grafted polyolefin blend;
extruding the silane-grafted polyolefin blend and a condensation catalyst together to form a silane crosslinkable polyolefin blend;
molding the silane crosslinkable polyolefin blend into an uncured elastomeric article; and crosslinking the crosslinkable polyolefin blend of the uncured elastomeric article at room temperature and ambient humidity to form the elastomeric article having a density less than 0.70 g / cm ³ , where the elastomeric article exhibits a deformation after compression of fence from 5.0% to about 35.0%, as measured according to ASTM D 395 (22 hours at 70 ° C).
[19]
19. Method according to claim 18, characterized in that the silane-grafted polyolefin blend and the cross-linkable polyolefin blend are thermoplastics and the cross-linked polyolefin blend is a thermoset.
[20]
20. Method according to claim 18 or 19, characterized in that the first polyolefin is an ethylene / a-olefin copolymer and the second polyolefin is a polypropylene homopolymer and / or a poly (ethylene-co-propylene) .

类似技术:

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法律状态:
2021-08-31| B06W| Patent application suspended after preliminary examination (for patents with searches from other patent authorities) chapter 6.23 patent gazette]|

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2021-10-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-12-28| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

优先权:

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申请号 | 申请日 | 专利标题

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US201662497954P| true| 2016-12-10|2016-12-10|

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US201662497959P| true| 2016-12-10|2016-12-10|

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PCT/US2017/065459|WO2018107118A1|2016-12-10|2017-12-08|Polyolefin elastomer compositions and methods of making the same|

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