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    • 专利摘要:
    composition, article and method for forming a composition the invention provides a composition comprising a first ethylene based polymer formed by a high pressure free radical polymerization process and comprising the following properties: a) a ratio of mw(abs) ) for i2: mw(abs)<ax [(i2)b], where a=5.00 x 10 2 (kg/mol)/(dg/min)b, eb= -0.40; and b) a ratio of ms to i2: ms>c x [(i2)d], where c=13.5 cn/dg/min)d, and d=-0.55.
    公开号:BR112015010787B1
    申请号:R112015010787-7
    申请日:2013-03-12
    公开日:2022-01-18
    发明作者:Otto J. Berbee；Cornelis F. J. Den Doelder；Teresa P. Karjala；Karl Zuercher；Jian Wang；Stefan Hinrichs
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    prior art
    [0001] Low density polyethylene (LDPE) resins for extrusion coating or extrusion lamination on paper, cardboard, aluminum, etc., are calculated with wide MWD (molecular weight distribution) and low extractables. In extrusion coating applications, the polymer is processed under high temperature conditions, typically above 260oC and below 350oC. Wide Molecular Weight Distribution (MWD) resins with a very high molecular weight fraction are used for good processability during coating (extruded side shrinkage balance (“neck-in) and draw down”). Low extractables are necessary to reduce undesirable taste and odor problems in the final product. Low extractables are also needed to reduce smoke formation during resin processing, especially during high temperature coating processes.
    [0002] Typically, LDPE resins with wide MWD are made using autoclave reactors or a combination of autoclave and tubular reactors. Resins with wide MWD can be obtained in autoclave reactors promoting long chain branching, and through the distribution of an inherent residence time, by which the molecules will undergo longer growth paths (high molecular weight).
    [0003] Autoclave and tubular reactor systems differ with respect to the residence time distribution, which is typically more uniform in tubular reactors and dispersed in zones of autoclave reactors. Polymerization conditions such as temperature, pressure and polymer concentration vary widely in tubular reactor systems, and are uniform or less differentiated in tubular reactor systems.
    [0004] The uniform residence time in tubular reactors leads to a narrower MWD, hence a very wide MWD can only be obtained in tubular reactors applying extremely different polymerization conditions, for example, as described in the international patent application PCT/ US 12/064284 (filed November 9, 2012), and/or by applying a branching/crosslinking agent, for example, as described in US Patent No. 7,820,776. Use of extreme process conditions and/or branching/crosslinking agents may lead to low density, high melt strength tubular polyethylene suitable for extrusion coating applications. These tubular polyethylenes will have a specific composition (eg, density), and functionality as determined by the applied process conditions, type and level of branching agent and/or comonomer. Unwanted gels in the polymer can be a problem, resulting from the use of branching or crosslinking agents.
    [0005] In extrusion coating applications, the following product and application properties are, among others, of importance: coating performance at varying processing speeds, substrate adhesion, barrier properties, and seal formation. Coating performance at varying processing speeds will depend primarily on the viscoelastic properties of the polymer, while adhesion, barrier and sealing properties will also depend, in addition to the viscoelastic properties, on the density and functionality of the polymer.
    [0006] EP0792318A1, EP1777238A1, EP2123707A1, and EP2123707A1 describe polymer compositions suitable for use in extrusion coating applications, in which the viscoelastic performance is contributed by autoclave-based LDPE as a minor blending component, and in which the density Overall and application performance is determined by the major (non-LDPE) blending component.
    [0007] The autoclave blend components used in such compositions have melt strength properties superior to those of normal autoclave products in unblended extrusion coating applications and hence are even more difficult to combine in a tubular LDPE process . This favorable viscoelastic performance of these autoclave mixing components is achieved through an extremely broad, and in some cases bimodal, MWD. However, the presence of an ultra-high molecular weight fraction in these resins has a negative impact on the optical appearance in the final extrusion coating application. Furthermore, an autoclave process typically operates at lower conversion levels, and is more capital/energy intensive than a tubular process.
    [0008] Therefore, there is a need for new ethylene-based polymers with a wide MWD, which are suitable for use in extrusion coating applications (sufficient melt strength), but lacking in the ultra-high molecular weight fraction of resins. MWD autoclave, and that can be made in a tubular process.
    [0009] EP0792318A1 discloses an ethylene polymer composition comprising from about 75 to 95 weight percent of at least one ethylene/α-olefin interpolymer, and from about 5 to 25 weight percent of at least one high pressure ethylene polymer. The ethylene/α-olefin interpolymer is selected from the group consisting of a substantially linear ethylene polymer, a homogeneously branched linear ethylene polymer and a heterogeneously branched linear ethylene polymer, wherein the ethylene/α-olefin polymer is characterized by have a density in the range of 0.85 g/cm3 to 0.940 g/cm3. The high pressure ethylene polymer is characterized by having a melt index, I2, of less than 6 g/10 minutes, a density of at least 0.916 g/cm3, a melt strength of at least 9 cN, a ratio of Mw/Mn of at least 7.0, and a bimodal molecular weight distribution as determined by gel permeation chromatography. The ethylene polymer extrusion composition has a melt index, I2 , of at least 1.0 g/10 minutes.
    [0010] US7776987 discloses a composition based on low melt flow rate LDPE (typically in the range of 0.2 to 1.0 g/10 min), in the amount of 10 to 25%, together with a linear polyethylene of high melt index, where the melt flow index of linear polyethylene is in the range of 20 to 100, preferably 30 to 40, and is suitable for use in extrusion coating. The composition comprises polymeric material having certain rheological and gel permeation chromatography (GPC) properties, and exhibits reduced extrudate lateral shrinkage when used in extrusion coatings. This lateral shrinkage of extrudate is independent of melt strength, thus facilitating improved extrusion processes.
    [0011] EP 1777238A1 claims the use of an autoclave-based LDPE with a melt flow index within the range of 2.5 to 10.0 g/10 minutes, with certain rheological properties by dynamic mechanical spectroscopy, as a component mixing into compositions suitable for extrusion coating applications. A related patent EP2123707A1 discloses 2-30% w/w of the above autoclave LDPE in blends with a tubular LDPE having a melt flow index of 2 to 8.
    [0012] US2007/0225445 discloses polymer blends composed of 25 to 75% w/w of homopolymer LDPE, produced in a tubular reactor, and 75 to 25% w/w of ethylene homopolymer LDPE produced in a high pressure autoclave reactor, and provided that each homopolymer is removed from the reaction zone before they are mixed with each other. The blends thus formed have a good combination of extrudate side shrinkage and adhesion properties. When the tubular product is mixed with the autoclave product at mixing ratios ranging from 0.7:0.3 to 0.3:0.7, the lateral shrinkage of polymer extrudate varied between 165 and 95% compared to the extruded side of the autoclave reference. The extrudate lateral shrinkage of the pure tubular (100%) was 305% times the extrudate lateral shrinkage of the autoclave reference.
    [0013] J. Bosch's presentation (“The Introduction of Tubular LDPE to the Extrusion Market and Specifics of the Product”) at the 12th TAPPI European Place Conference, in 2009, discloses the differences between autoclave-based and tubular-based resins, and the consequences on the performance of the extrusion coating. Additionally, this reference explains the need to develop unblended tubular resins for extrusion coating applications.
    [0014] Conventional high melt strength ethylene based polymers used in compositions suitable for extrusion coating are made in the autoclave process with very wide MWD and with the presence of an ultra-high molecular weight fraction, which has a negative impact in optical appearance in the final application. Furthermore, an autoclave process typically operates at lower conversion levels, and is more capital/energy intensive than a tubular process. Conventional tubular products lack melt strength to provide the desired viscoelastic properties for extrusion coating compositions made from these low melt strength resins.
    [0015] Therefore, there is a need for new ethylene-based polymers with high melt strength, which are suitable as a blending component in compositions to be used in extrusion coating applications, but lacking the ultra-high molecular weight fraction of MWD-wide autoclave resins, and whose new polymers can be made in a tubular process. These needs and others have been met by the invention below. summary
    [0016] The invention provides a composition comprising a first polymer of ethylene, formed by a high pressure free radical polymerization process, and comprising the following properties: a) a ratio of Mw(abs) to I2: Mw(abs )<A x [(I2)B], where A=5.00 x 102 (g/mol)/(dg/min)B, and B=0.40; and b) a ratio of MS to I2: MS>C x [(I2)D], where C=13.5 cN/dg/min)D, and D=-0.55. Description of drawings
    [0017] Figure 1 is a schematic of a polymerization flow scheme;
    [0018] Figure 2 shows the GPC chromatograms of the inventive LDPE (IE3, IE5) and comparative LDPE (770G, 662I, LD450E) polymers;
    [0019] Figure 3 shows “weight average molecular weight (Mw) versus melt index (I2)” for the inventive and comparative polymers. The lines for series 1, 2 and 3 show the limits belonging to the following selected values for A, namely 5.00 x 102, 4.25 x 102 and 3.50 x 102, respectively. Figure 3 is a double logarithmic plot;
    [0020] Figure 4 shows “melt strength” (MS) versus melt index (I2) for inventive and comparative polymers. The lines for series 1, 2 and 3 show the limits belonging to the following selected values for C, namely 13.5, 14.5 and 15.5 respectively. Figure 4 is a double logarithmic plot;
    [0021] Figure 5 shows "molecular weight fraction greater than 106 g/mol (w) versus pour index melt index (I2)" for inventive and comparative polymers. The lines for series 1, 2 and 3 show the limits belonging to the following selected values for E, namely 0.110, 0.090 and 0.075 respectively. Figure 5 is a double logarithmic plot; and
    [0022] Figure 6 is a double profile showing “Extrude lateral shrinkage versus weight percent of high melt strength (MS) polymer component” for inventive compositions and “Stretch against polymer component with high percentage of high melt strength ( MS)” comparatives. Detailed Description
    [0023] As discussed above, the invention provides a composition comprising a first ethylene-based polymer, formed by a high-pressure, free-radical polymerization process, and comprising the following properties: c) a ratio of Mw(abs) to I2: Mw(abs)<A x [(I2)B], where A=5.00 x 10 2 (g/mol)/(dg/min)B, and B= -0.40; and d) a ratio of melt strength (MS) to I2: MS>C x [(I2)D], where C=13.5 cN/dg/min)D , and D=-0.55.
    [0024] The composition may comprise a combination of two or more embodiments described herein;
    [0025] In characteristic (a) above, Mw(abs) is determined by GPC Method A as described here.
    [0026] In characteristic (b) above, the melt strength (MS) is determined at 190oC; see test method described here.
    [0027] In one embodiment, the first ethylene-based polymer has a melt index (I2) of 0.1 g/10 min to 6.0 g/10 min (ASTM 2.16 kg/190°C).
    [0028] In one embodiment, the first ethylene-based polymer has a melt index (I2) of 0.2 g/10 min to 6.0 g/10 min, additionally from 0.3 g/10 min to 6.0 g/10 min (ASTM 2.16 kg/190°C).
    [0029] In one embodiment, the first ethylene-based polymer has a melt index (I2) of 0.4 g/10 min to 6.0 g/10 min, additionally from 0.5 g/10 min to 6, 0 g/10 min (ASTM 2.16 kg/190°C).
    [0030] In one embodiment, the first ethylene-based polymer has a melt index (I2) of 0.1 g/10 min to less than 4.0 g/10 min.
    [0031] In one embodiment, the first ethylene-based polymer has a melt index (I2) of 0.3 g/10 min to 6.0 g/10 min.
    [0032] In one embodiment, the first ethylene-based polymer has a melt index (I2) of 0.3 g/10 min to 4.0 g/10 min.
    [0033] In one embodiment, the first ethylene-based polymer has (b) a ratio of Mw(abs) to I2: Mw(abs)<A x [(I2)B], where A= 4.25 x 102 ( g/mol)/(dg/min)B, and B= -0.40 Mw(abs) by GPC method A).
    [0034] In one embodiment, the first ethylene-based polymer has (b) a ratio of Mw(abs) to I2: Mw(abs)<A x [(I2)B], where A= 3.50 x 102 ( g/mol)/(dg/min)B, and B= -0.40 Mw(abs) by GPC method A).
    [0035] In one embodiment, the first ethylene-based polymer has (c) a ratio of melt strength (MS) to melt index (I2): MS>C x [(I2)D], where C=14, 5 cN/(dg/min)D and D= -0.55(melt strength=MS, 190oC).
    [0036] In one embodiment, the first ethylene-based polymer has (c) a ratio of MS to I2: MS>C x [(I2)D], where C= 15.5 cN/(dg/min)D and D= -0.55(melt strength=MS, 190oC).
    [0037] In one embodiment, the first ethylene-based polymer has a G' value greater than or equal to 140 Pa at 170oC, additionally greater than or equal to 150 Pa at 170oC, additionally greater than, or equal to 160 Pa at 170oC.
    [0038] In one embodiment, the first ethylene-based polymer has a melt strength greater than or equal to 9.0 cN at 190oC additionally greater than or equal to 12.0 cN at 190oC additionally greater than or equal to 15.0 cN at 190°C.
    [0039] In one embodiment, the first ethylene-based polymer has a weight fraction (w) of molecular weight greater than 106 g/mol, based on the total weight of polymer, as determined by GPC(abs), which meets the following relationship: w<E x [(I2)F], where E= 0.110 (dg/min)F, and F= -0.38 (GPC Method A).
    [0040] In one embodiment, the first ethylene-based polymer has a weight fraction (w) of molecular weight greater than 106 g/mol, based on the total weight of polymer, as determined by GPC(abs), which meets the following relationship: w<E x [(I2)F], where E= 0.090 (dg/min)-F, and F= -0.38 (GPC Method A).
    [0041] In one embodiment, the first ethylene-based polymer has a weight fraction (w) of molecular weight greater than 106 g/mol, based on the total weight of polymer, as determined by GPC(abs), which meets the following relationship: w<E x [(I2)F], where E= 0.075 (dg/min)-F, and F= -0.38 (GPC Method A).
    [0042] In one embodiment, the first ethylene-based polymer is polymerized in at least one tubular reactor. In a further embodiment, the first ethylene-based polymer is polymerized in a tubular reactor system that does not comprise an autoclave reactor.
    [0043] In one embodiment, the composition additionally comprises a second ethylene-based polymer. In a further embodiment, the composition has a melt index (I 2 ) of 2 to 50 g/10 min, additionally 3 to 35 g/10 min, and additionally 4 to 20 g/10 min. In one embodiment, the composition has a density of 0.900 to 0.955 g/cm 3 . In one embodiment, the composition has a MS value greater than or equal to 2.5 cN (at 190°C).
    [0044] In one embodiment, the second ethylene-based polymer has a density of 0.860 to 0.960 g/cm 3 , additionally 0.870 to 0.955 g/cm 3 , additionally 0.880 to 0.950 g/cm 3 .
    [0045] In one embodiment, the second ethylene-based polymer has a melt index of from 2 to 80 g/10 min, additionally from 4 to 50 g/10 min, and additionally from 6 to 35 g/10 min.
    [0046] In one embodiment, the second ethylene-based polymer has a density of 0.915 to 0.935 g/cm 3 , additionally 0.915 to 0.932 g/cm 3 , additionally 0.915 to 0.930 g/cm 3 .
    [0047] In one embodiment, the second ethylene-based polymer is a LDPE homopolymer with a density greater than or equal to 0.924 g/cm3.
    [0048] The second ethylene-based polymer may comprise a combination of two or more embodiments as described herein.
    [0049] In one embodiment, the second ethylene-based polymer comprises at least one comonomer selected from a C3-C20 alpha-olefin, an acrylate, an acetate, a carboxylic acid, carbon monoxide, or an ionomer.
    [0050] In one embodiment, the second ethylene-based polymer comprises at least one comonomer selected from a C3-C10 alpha-olefin, an acrylate, an acetate, a carboxylic acid, or carbon monoxide.
    [0051] In one embodiment, the second ethylene-based polymer is selected from an ethylene/alpha-olefin copolymer, a low density polyethylene (LDPE), a high density polyethylene (HDPE), or a combination thereof.
    [0052] Suitable second ethylene based polymers include DOWLEX Polyethylene Resins, ELITE Enhanced Polyethylenes (e.g. ELITE 5815 Enhanced Polyethylene), AFFINITY Polyolefin Plastomers, ENGAGE Polyolefin Elastomers, ASPUN Polyethylene, AFFINITY Functional Polymers, and Olefin INFUSE.
    [0053] Linear low density polyethylenes (LDPEs) include copolymers of ethylene with one or more alpha-olefins, such as, but not limited to, propylene, butene-1, pentene-1,4-methylpentene-1, pentene-1 , hexene-1, and octene-1.
    [0054] In one embodiment, the composition additionally comprises a functionalized ethylene-based polymer. Suitable functionalized ethylene based polymers include maleic anhydride grafted ethylene based polymers, for example AMPLIFY TY Functional Polymers.
    [0055] In one embodiment, the composition additionally comprises a propylene-based polymer. Suitable propylene based polymers include VERSIFY Plastomers and Elastomers.
    [0056] In one embodiment, the composition has a density of from 0.900 to 0.955 g/cm3, additionally from 0.900 to 0.950 g/cm3.
    [0057] In one embodiment, the composition has a melt flow index (I2) of from 2 to 50 g/10 min, additionally from 3 to 35 g/10 min, and additionally from 4 to 20 g/10 min.
    [0058] In one embodiment, the composition has a G' value greater than or equal to 80 Pa at 170oC, additionally greater than or equal to 90 Pa at 170oC, additionally greater than or equal to 100 Pa, at 170oC.
    [0059] In one embodiment, the composition has a MS value greater than or equal to 2.5 cN at 190oC, additionally greater than or equal to 3.0 cN at 190oC, additionally greater than, or equal to 3.5 cN at 190°C.
    [0060] In one embodiment, the composition comprises "greater than 0% w/w", but less than 15% w/w, of the first ethylene-based polymer, based on the sum of the weights of the first and second polymers, and being that the composition has a G' value greater than or equal to 80 Pa (at 170oC).
    [0061] In one embodiment, the composition comprises "greater than 0% w/w", but less than 40% w/w, of the first ethylene-based polymer, based on the sum of the weights of the first and second polymers, and being that the composition has a G' value greater than or equal to 80 Pa (at 170oC).
    [0062] The composition may comprise a combination of two or more embodiments as described herein.
    [0063] The first ethylene-based polymer may comprise a combination of two or more embodiments as described herein.
    [0064] In one embodiment, the first ethylene-based polymer is selected from a polyethylene homopolymer or an ethylene-based interpolymer.
    [0065] In one embodiment, the first ethylene-based polymer is selected from a polyethylene homopolymer or an ethylene-based polymer; and wherein the ethylene-based copolymer comonomer is selected from a vinyl acetate, an alkyl acrylate, carbon monoxide, an acrylic acid, a carboxylic acid-containing comonomer, an ionomer, a monoolefin, or selected from an acetate vinyl, an alkyl acrylate, or a mono olefin. In a further embodiment, the comonomer will be present in an amount of 0.5 to 30% w/w comonomer, based on the weight of copolymer.
    [0066] In one embodiment, the first ethylene-based polymer comprises less than 30 molar ppm of a cross-linking agent (capable of forming a covalent bond or bond between two polymer molecules), based on the total moles of monomer units in the polymer. ethylene based. In a further embodiment, the first ethylene-based polymer comprises less than 30 ppm of a comonomer containing multiple unsaturations or containing an acetylenic functionality.
    [0067] It is understood that trace amounts of impurities may be incorporated into the polymer structure; for example, low trace acetylene components (less than 20 molar ppm in the polymer) may be present in the ethylene feed according to typical ethylene specifications (e.g. acetylene at a maximum of 5 molar ppm in the ethylene feed).
    [0068] In one embodiment, the first ethylene-based polymer comprises less than 10 molar ppm of incorporated propylene, based on the total moles of monomer units in the ethylene-based polymer.
    [0069] Desirably, the ethylene-based polymer has low contents of gels. Therefore, the direct addition of cross-linking agents or comonomers with cross-linking capability is not desired in the polymerizations of the first ethylene-based polymers described herein.
    [0070] In one embodiment, the first ethylene-based polymer has an I2 of > 0.5 g/10 min.
    [0071] In one embodiment, the first ethylene-based polymer has an I2 of > 1 g/10min.
    [0072] In one embodiment, the first ethylene-based polymer has an I2 of < 10 g/10 min.
    [0073] In one embodiment, the first ethylene-based polymer has an I2 of < 6 g/10 min.
    [0074] In one embodiment, the first ethylene-based polymer has an I2 of < 5 g/10 min.
    [0075] In one embodiment, the first ethylene-based polymer has an I2 of < 4 g/10 min.
    [0076] In one embodiment, the first ethylene-based polymer has a G' > 120 Pa (at 170°C), additionally a G' > 130 Pa (at 170°C), additionally a G' > 140 Pa (at 170°C), additionally a G' > 150 Pa (at 170°C).
    [0077] In one embodiment, the first ethylene-based polymer has a density of 0.910 to 0.940 g/cm3.
    [0078] In one embodiment, the first ethylene-based polymer has a density greater than or equal to 0.915 g/cm3 , or greater than or equal to 0.918 g/cm3 .
    [0079] A first inventive ethylene-based polymer may comprise a combination of two or more embodiments as described herein.
    [0080] In one embodiment, the composition has an "extrude lateral shrinkage" value < 120 mm, at a set temperature = 290°C, a coating weight = 25 g/m2, and a line speed of 300 m/min .
    [0081] In one embodiment, the composition has a "stretchability" value > 400 m/min at a set temperature of 290°C. Stretchability is defined as the maximum line speed obtainable before the web breaks or web defects/edge inconsistencies occur when accelerating the line speed to constant polymer production. The constant polymer production level is set to a coating weight of 15 g/m2, operating at a line speed of 100 m/min. Lateral shrinkage of extrudate is the difference between the final web width and the die width at a fixed line speed.
    [0082] An inventive composition may comprise a combination of two or more embodiments as described herein.
    [0083] The first ethylene-based polymer may comprise a combination of two or more embodiments as described herein.
    [0084] The invention also provides an article comprising at least one component formed from the inventive composition.
    [0085] In one embodiment, the article is selected from coatings, films, foams, laminates, fibers or tapes.
    [0086] In one embodiment, the article is an extrusion coating. In another embodiment, the article is a film.
    [0087] An inventive article may comprise a combination of two or more embodiments as described herein.
    [0088] The invention also provides a method for forming an inventive composition, said method comprising polymerizing ethylene in a reactor configuration comprising at least one tubular reactor. In a further embodiment, the tubular reactor comprises at least two reaction zones. In a further embodiment, the tubular reactor comprises at least three reaction zones.
    [0089] An inventive method may comprise a combination of two or more embodiments as described herein. polymerizations
    [0090] For a high-pressure, free-radical-initiated polymerization process, two basic types of reactors are known. The first type is a stirred autoclave vessel having one or more reaction zones (the autoclave reactor). The second type is a jacketed tube that has one or more reaction zones (the tubular reactor).
    [0091] The pressure in each process tube and autoclave reactor zone is typically 100 to 400, more typically 120 to 360, and even more typically 150 to 320 MPa.
    [0092] The polymerization temperature in each tubular reactor zone of the process is typically from 100 to 400oC, more typically from 130 to 360oC, and even more typically from 140 to 330oC.
    [0093] The polymerization temperature in each process autoclave reactor zone is typically from 150 to 300oC, more typically from 165 to 290oC, and even more typically from 180 to 280oC. Those skilled in the art understand that temperatures in the autoclave are considerably lower and less differentiated than those in the tubular reactor, and thus more favorable extractables levels are typically observed in polymers produced in autoclave-based reactor systems.
    [0094] The high pressure process of the present invention for producing polyethylene homo or interpolymers having advantageous properties as found in accordance with the present invention is preferably conducted in a tubular reactor having at least three reaction zones. initiators
    [0095] The process of the present invention is a free radical polymerization process. The type of free radical initiator to be used in the present process is not critical, but preferably one of the initiators applied should allow high temperature operation in the range of 300oC to 350oC. Free radical initiators that are commonly used include organic peroxides, such as peresters, perceptals, peroxyketones, peroxycarbonates, and cyclic multifunctional peroxides. These organic peroxy-initiators are used in conventional amounts, typically from 0.005 to 0.2% w/w, based on the weight of polymerizable monomers.
    [0096] Other suitable initiators include azodicarboxylic esters, azodicarboxylic dinitriles and 1,1,2,2-tetramethylethane derivatives, and other components capable of forming free radicals at the desired operating temperature.
    [0097] Peroxides are typically injected as dilute solutions in a suitable solvent, for example a hydrocarbon solvent.
    [0098] In one embodiment, an initiator is added to at least one reaction zone of the polymerization reactor, and wherein the initiator has a "half-life temperature of one second" greater than 255oC, preferably greater than 260oC. In a further embodiment, such initiators are used at a peak polymerization temperature of 320°C to 350°C. In a further embodiment, the initiator comprises at least one peroxide group incorporated in a ring structure.
    [0099] Examples of such primers include, but are not limited to, TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxoneane) and TRIGONOX 311 (3,3, 5,7,7-pentamethyl-1,2,4-trioxepane), both commercially available from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4 ,5-tetroxane) commercially available from United Initiators. See also international publications in WO 02/14379 and WO 01/68723.Chain Transfer Agents (CTA)
    [0100] Chain transfer agents or telogens are used to control the flow rate in a polymerization process. Chain transfer involves terminating growing polymeric chains, thus limiting the final molecular weight of the polymeric material. Chain transfer agents are typically hydrogen atom donors that will react with a growing polymer chain and stop the chain polymerization reaction. These agents can be of many different types, from saturated or unsaturated hydrocarbons to aldehydes, ketones or alcohols. By controlling the concentration of the selected chain transfer agent, one can control the length of the polymeric chains, and hence the molecular weight, for example the number average molecular weight, Mn. The melt flow index (MFI or I2) of a polymer, which is related to Mn, is controlled in the same way.
    [0101] Chain transfer agents used in the process of this invention include, but are not limited to, aliphatic and olefinic hydrocarbons such as pentane, hexane, cyclohexane, propene, pentene or hexene; ketones, such as acetone, diethyl ketone, or diamyl ketone; aldehydes such as formaldehyde or acetic aldehyde; and saturated aliphatic aldehyde alcohols such as methanol, ethanol, propanol or butanol. The chain transfer agent may also be a monomeric chain transfer agent. For example, WO 2012/057975, US 61/579067 (see international patent application no PCT/US12/068727, filed December 10, 2012) and US 61/664956 (filed June 27, 2012).
    [0102] A further way to influence the melt flow rate includes the accumulation and control, in the ethylene recycle streams, of incoming ethylene impurities such as methane and ethane, peroxide dissociation products such as tert-butanol, acetone , etc., and or solvent components used to dilute the initiators. Such ethylene impurities, dissociation products and/or solvent components may function as chain transfer agents. polymers
    [0103] In one embodiment, the first ethylene-based polymers of this invention have a density of from 0.912 to 0.935, more typically from 0.914 to 0.930 and even more typically from 0.916 to 0.926 grams per cubic centimeter (g/cm 3 ). In one embodiment, the ethylene-based polymers of this invention have a melt index (I 2 ) of 0.3 to 6 grams for 10 minutes (g/10 min) at 190°C/2.16 kg, additionally from 0.5 to 5 grams for 10 minutes (g/10 min) at 190°C/2.16 kg.
    [0104] Ethylene-based polymers include LDPE homopolymer, and high pressure copolymers including ethylene/vinyl acetate (EVA), ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), ethylene methacrylic acid (EMAA) , and ethylene carbon monoxide (ECO). Other suitable comonomers are described in Ehrlich, P.; Mortimer, G.A.; Adv. Polymer Science: Fundamentals of Freeradical Polymerization of Ethylene; Vol. 7, pgs. 386-448 (1970). In one embodiment, comonomers exclude comonomers capable of crosslinking polymeric chains, for example, containing multiple unsaturations or an acetylenic functionality. Monomer and Comonomers
    [0105] The term ethylene interpolymer as used in the present description and the claims refers to polymers of ethylene and one or more comonomers. Suitable comonomers for use in the ethylene polymers of the present invention include, but are not limited to, ethylenically unsaturated monomers, and especially C3-20 alpha-olefins, carbon monoxide, vinyl acetate, and C2-6 alkyl acrylates. In one embodiment, the ethylene-based polymer does not contain comonomers capable of crosslinking polymer chains, for example, comonomers containing multiple unsaturations or containing acetylenic functionality. mixtures
    [0106] The inventive polymers may be blended with one or more other polymers, such as, but not limited to, high pressure copolymers and terpolymers, including graft copolymers and graft terpolymers; linear low density polyethylene (LDPE); copolymers of ethylene with one or more alpha-olefins, such as, but not limited to, propylene, butene-1, pentene-1,4-methylpentene-1, pentene-1, hexene-1, and octene-1; high density polyethylene (HDPE), such as HDPE grades HD 940-970, commercially available from The Dow Chemical Company. The amount of inventive polymer in the blend will vary widely, but is typically 5 to 90, or 10 to 85, or 15 to 80 percent by weight, based on the weight of the polymers in the blend. Additions
    [0107] One or more additives may be added to a composition comprising an inventive polymer. Suitable additives include stabilizers; fillers, such as organic and inorganic particles, including clays, talc, titanium dioxide, zeolites, pulverized metals, organic and inorganic fibers, including carbon fibers, silicon nitride fibers, steel wires or wefts, nylon or polyester cord , nano-sized particles, clays, and so on; dryers; and oil extenders, including paraffinic or naphthenic oils. applications
    [0108] An inventive composition may be employed in a variety of conventional thermoplastics manufacturing processes to produce useful articles, including extrusion coatings; films; and molded articles, such as blow molded, injection molded, or rotational molded articles; foams; yarns and cables, fibers and woven and non-woven fabrics. Definitions
    [0109] Unless otherwise noted, implied by context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.
    [0110] The term "composition", as used herein, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.
    [0111] The terms "blend" or "blend of polymers", as used, mean an intimate physical mixture (ie, no reaction) of two or more polymers. A mixture may or may not be miscible (not separated into phases at the molecular level). A mixture may or may not be separated into phases. A mixture may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. The mixing may be physically effected by mixing the two or more polymers at the macro level (eg blending or formulating under melt) or at the micro level (eg simultaneous formation within the same reactor).
    [0112] The term "polymer" refers to a compound prepared by polymerizing monomers of the same or different types. The generic term polymer, therefore, encompasses the term homopolymer (which refers to polymers prepared from only one type of monomer with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and the term “interpolymer”, as defined below. Trace amounts of impurities may be incorporated into and/or within the polymer.
    [0113] The term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers (which refers to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
    [0114] The term "ethylene-based polymer" or "ethylene polymer" refers to a polymer that comprises a major amount of polymerized ethylene, based on the weight of the polymer, and optionally, may comprise at least one comonomer.
    [0115] The term "ethylene-based interpolymer" or "ethylene interpolymer" refers to an interpolymer that comprises a major amount of polymerized ethylene based on the weight of the interpolymer, and comprises at least one comonomer.
    [0116] The term “ethylene-based copolymer” or “ethylene copolymer” refers to a copolymer that comprises a majority amount of polymerized ethylene based on the weight of the copolymer, and comprises only one comonomer (hence, only two types of monomers).
    [0117] The terms "autoclave based products" and "autoclaved based products", as used herein, refer to polymers prepared in a reactor system comprising at least one autoclave reactor.
    [0118] The phrase “high pressure free radical polymerization process” as used herein refers to a free radical initiated polymerization conducted at an elevated pressure of at least 100 MPa (1000 bar).
    [0119] The terms “comprising”, “including”, “having” and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not disclosed. For the avoidance of doubt, all compositions claimed by the use of the term "comprising" may include any additive, adjuvant, or additional compound, whether polymeric or not, unless otherwise noted. In contrast, the term “consisting essentially of” excludes from the scope of any further presentation any other component, step or procedure, except those that are not essential for operability. The term “consisting of” excludes any further presentation of any other component, step or procedure not specifically outlined or listed. test methods
    [0120] Density: Samples for density are prepared in accordance with ASTM D 1928. Polymer samples are pressed at 190oC and 207 MPa (30,000 psi) for three minutes, then at 21oC and 207 MPa for one minute. Measurements are made within one hour of pressing the sample using ASTM D792, Method B.
    [0121] Melt Index: The melt index, or I2, (grams/10 minutes or dg/min) is measured in accordance with ASTM D 1238, Condition 190oC/2.16 kg. I10 is measured in accordance with ASTM D 1238, Condition 190oC/10 kg.
    [0122] GPC Method A: Triple Detector Gel Permeation Chromatography (TDGPC): High temperature analysis of GPC-3Det was conducted on an ALLIANCE GPCV2000 instrument (Waters Corp.) set at 145oC. The flow rate for the GPC was 1 mL/min. The injection volume was 218.5 μ L. The column set consists of four Mixed-A columns (20 μ particles; 7.4 x 300 mm; Polymer Laboratories Ltd.).
    [0123] Detection was achieved using a PolymerChAR IR-4 detector, equipped with a CH sensor; a Dawn DSP MALS detector from Wyatt Technology Corp. Santa Barbara, CA, USA), equipped with a 30 mW argon ion laser operating at Δ = 488 nm; and a Waters three capillary viscosity detector. The MALS detector was calibrated by measuring the dispersion intensity of the TCB solvent. The normalization of the photodiodes was carried out by injecting STM 1483, a high density polyethylene with a weight average molecular weight (Mw) of 32,100 g/mol and a polydispersity (MWD) of 1.11. HDPE SRM 1483 was obtained from the U.S. National Institute of Standards and Technology (Gaithersburg, MD, USA). A specific refractive increment (dn/dc) of -0.104 mL/mg was used for polyethylene in TCB.
    [0124] Conventional GPC calibration was performed with 20 PS standards (Polymer Laboratories) with narrow molecular weight distribution with molecular weights ranging from 580 to 7,500,000 g/mol. The peak molecular weights of polystyrene standards are converted to polyethylene molecular weights using the following equation: Mpolyethylene = A X (Mpolystyrene),
    [0125] with A = 0.39, B = 1. The Value of A was determined using a high density polyethylene homopolymer (HDPE) with an Mw = 115,000 g/mol. HDPE reference material was used to calibrate the IR detector and viscometer assuming 100% mass recovery and an intrinsic viscosity of 1.873 dL/g.
    [0126] Distilled 1,2,4-Trichlorobenzene grade “Analyzed by Baker” (JT Baker, Deventer, The Netherlands), containing 200 ppm of 2,6-di-tert-butyl-4-methylphenol (Merck, Hohenbrunn, Germany ) was used as a solvent for sample preparation as well as for the GPC-3Det experiment.
    [0127] LDPE solutions were prepared by dissolving the samples under gentle agitation for three hours at 160oC. PS standards were dissolved under the same conditions for 30 minutes. The sample concentration for the GPC-3Det experiment was 1.5 mg/mL, and the polystyrene concentrations were 0.2 mg/mL.
    [0128] A MALS detector measures the stray signal of polymers or particles in a sample under different scattering angles θ. The basic light scattering equation (from M. Anderson, B. Wittgren, K.-G. Wahlund, Anal. Chem. 75, 4279 can be written as follows:
    where Rθ is the excess Rayleigh ratio, K is an optical constant, which is, among other things, dependent on the increment of the specific refractive index (dn/dc), c is the solute concentration, M is the molecular weight, Rg is the radius of gyration, and À the wavelength of the incident light. Calculation of molecular weight and gyrus radius from light scattering data requires extrapolation to zero angle (see also PJ Wyatt, Anal. Chim. Acta 272, 1 (1993)). This is done by plotting (Kc/Rθ)1/2 as a function of sin2 (θ/2) in a so-called Debye plot. The molecular weight can be calculated from the intersection with the ordinate, and the radius of gyration from the initial slope of the curve. The second virial coefficient is assumed to be negligible. Intrinsic viscosity numbers are calculated from both the viscosity and concentration signal detectors by taking the ratio of the specific viscosity to the concentration in each elution slice.
    [0129] ASTRA 4.72 software (Wyatt Technology Corp.) was used to collect the signals from the IR detector, viscometer, and MALS detector, and to process the calculations.
    [0130] Calculated molecular weights, e.g., Mw(abs), and molecular weight distributions (e.g., Mw(abs)/Mn(abs)) were obtained using a dispersion constant derived from a or more of the mentioned polyethylene standards and the refractive index concentration coefficient, dn/dc, of 0.104. Generally the mass detector response and light scattering constant should be determined from a linear pattern with a molecular weight in excess of about 50,000 Daltons. Calibration of the viscometer may be obtained using methods described by the manufacturer or, alternatively, using published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a, 1482a, 1483, or 1584a. Chromatographic concentrations are assumed to be low enough to avoid resorting to virial 2nd coefficient effects (concentration effects on molecular weight).
    [0131] The MWD(abs) curve obtained by TD-GPC was summarized with three characteristic parameters: Mw(abs), Mn(abs), and w, where w is defined as “fraction by weight of molecular weight greater than 106 g /mol, based on total polymer weight, and as determined by GPC(abs)”.
    [0132] Figure 2 shows the MWD(abs) for several comparative examples and inventive examples 3 and 4. Additionally, a vertical line, as shown in this figure, indicates the lower limit of integration to determine “w”. So “w” is effectively the area under the curve to the right of this vertical line.
    [0133] In equation form, the parameters are determined as follows. Numerical integration of the “logM” and “dw/dlogM” table is typically done using the trapezoidal rule:

    [0134] The parameter g' is defined as the weight of the intrinsic viscosity of the LDPE to the intrinsic viscosity of the linear HDPE reference material discussed above (Mw of 115,000 g/mol).GPC Method A: Gel Permeation Chromatography with Detector Triple (TDGPC) - Conventional GPC Data
    [0135] A Triple Detector Gel Permeation Chromatography system (GPC-3D or TDGPC) consisting of a Polymer Laboratories (now Agilent) Model 220 high temperature chromatograph equipped with a light scattering (LS) detector of Model 2040 biangular laser (Precision Detectors, now Agilent), an IR-4 infrared detector from Polymer Char (Valencia, Spain), and a 4 capillary solution (DP) viscometer (Viscotek, now Malvern) were used. Data collection was performed using a Polymer Char DM 100 data acquisition box and corresponding software (Valencia, Spain). The system was also equipped with an on-line solvent degassing device from Polymer Laboratories (now Agilent).
    [0136] High temperature GPC columns consisting of four 30 cm, 20 µm LS mixed A columns from Polymer Laboratories (now Agilent) were used. The sample carousel compartment was operated at 140oC, and the column compartment was operated at 150oC. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent was 1,2,4-trichlorobenzene (TCB) containing 200 ppm of 2,6-di-tert-butyl-4-methylphenol (BHT). The solvent was sparged with nitrogen. The polymer samples were gently shaken at 160°C for four hours. The injection volume was 200 microliters. The flow rate through the GPC was set at 1.0 mL/minute.
    [0137] Column calibration calculations and molecular weight of samples were performed using Polymer Char's “GPC One” software. Calibration of the GPC columns was performed with 21 polystyrene standards with narrow molecular weight distribution. The molecular weights of the polystyrene standards ranged from 580 to 8,400,000 g/mol, arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights.
    [0138] Peak molecular weights of polystyrene standards were converted to polyethylene molecular weights using the following equation (as described by Williams and Ward, J. Poly, Sci., Polym. Let., 6, 621 (1968): Mpolyethylene = A(Mpolystyrene) Here, B has a value of 1.0, and the experimentally determined value for A is about 0.38 to 0.44.
    [0139] The column calibration was obtained by fitting a first order polynomial to the respective polyethylene equivalent calibration points obtained from the above equation for the observed elution volumes.
    [0140] Numerical, weight and z average molecular weights were calculated according to the following equations:
    where Wfi is the weight fraction of the ith component and Mi is the molecular weight of the ith component. The molecular weight distribution (MWD) is expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).
    [0141] The A value was determined by adjusting the A value in the Williams and Ward equation, to Mw, the weight average molecular weight, calculated using the above equation, and the corresponding retention volume polynomial agreeing with the independently determined Mw value , obtained according to the linear homopolymer reference with the known weight average molecular weight of 115,000 g/mol.G' Rheological
    [0142] The sample used in the measurement of G' was prepared from a compression molded plate. A piece of aluminum foil was placed on a backing plate, and a template or mold was placed on the backing plate. Approximately 12 grams of resin was placed in the mold, and a second piece of aluminum foil was placed over the resin and mold. A second backing plate was then placed over the aluminum laminate. The entire assembly was then placed on a compression molding press, which was operated under the following conditions: 3 min at 150°C, at a pressure of 10 bar, followed by 1 min at 150°C, at 150 bar, followed by quenching. from “1.5 min” to room temperature at 150 bar. A 25 mm disc was stamped from the compression molded plate. The thickness of this disc was approximately 2.0 mm.
    [0143] The rheology measurement to determine G' was performed in a nitrogen environment, at 170oC, and a strain of 10%. The stamped disc was placed between the two parallel plates of “25 mm” located in the oven of an ARES-1 rheometer (Rheometrics SC), which was preheated for at least 30 minutes at 170oC, and the gap of the parallel plates from “25 mm” was slowly reduced to 1.65 mm. The sample was then allowed to stand exactly 5 minutes under these conditions. The oven was then opened, excess sample was carefully trimmed around the edges of the plates, and the oven was closed. The sample's storage modulus and loss modulus were measured by means of a small-aperture, oscillatory shear according to a decreasing frequency sweep from 100 to 0.1 rad/s (when able to obtain a value of G ” lower than 500 Pa at 0.1 rad/s) or 100 to 0.01 rad/s. For each frequency sweep, 10 points (logarithmically spaced) per frequency decade were used.
    [0144] The data were plotted (G'(Y-axis) against G”(X-axis) on a log-log scale. The Y-axis scale covered the range from 10 to 1000 Pa, while the Y-axis dos X covered the range from 100 to 1000 Pa. For Software A, Orchestrator software was used to select the data in the region where G” was between 200 and 800 Pa (or using 4 data points). polynomial model using the fitting equation Y = C1+C2 ln(x) Using the Orchestrator software, G', at G” equal to 500 Pa, was determined by interpolation.
    [0145] For software B, data were extrapolated using the Akima spline interpolation algorithm with piecewise polynomial 3rd order fits. This is described in detail in Hiroshi Akima “A new method of interpolation and smooth curve fitting based on local procedures”, J. ACM, 17(4), 589-602 (1970).
    [0146] In some cases, the G'(at a G" of 500 Pa) was determined for test temperatures of 150oC and 190oC. The value at 170oC was calculated by a linear interpolation of the values at these two temperatures. Cast Strength
    [0147] Melt strength measurements were conducted on a Gottfert Rheotens 71.97 (Goettfert Inc.; Rock Hill, SC) attached to a Gottfert Rheotester 2000 capillary rheometer. A polymer melt (about 20-30 grams, pellets) was extruded. through a capillary array with a flat entry angle (180 degrees) with a capillary diameter of 2.0 mm and an aspect ratio (capillary length/capillary diameter) of 15.
    [0148] After equilibrating the samples at 190oC for 10 minutes, the piston was operated at a constant piston speed of 0.265 mm/second. The standard test temperature was 190oC. The sample was uniaxially extracted onto a set of accelerator puller rollers located 100 mm below the die, with an acceleration of 2.4 mm/second2. Tensile force was recorded as a function of the winding speed of the puller rolls. Melt strength was reported as the stabilizing force (cN) before the continuous filament broke. The following conditions were used in the melt strength measurements: piston speed = 0.265 mm/second; roll acceleration = 2.4 mm/s2; capillary diameter = 2.0 mm; capillary length = 30 mm; and cylinder diameter = 12 mm. Nuclear Magnetic Resonance (C13 NMR)
    [0149] Samples were prepared by adding approximately “3 g of a 50/50 mixture of tetrachloroethane-d2/orthodichloro benzene, containing 0.025 M Cr(AcAc)3, to a polymer sample of “0.25 to 0.40 g”, in a 10 mm NMR tube. Oxygen was removed from the sample by placing the open tubes in a nitrogen environment for at least 45 minutes. The samples were then dissolved and homogenized by heating the tube and its contents to 150oC, using a heating block and a heat gun. Each dissolved sample was visually inspected to ensure homogeneity. Samples were judiciously mixed immediately prior to analysis and not allowed to cool prior to insertion into heated NMR sample loops.
    [0150] All data were collected using a 400 MHz Bruker spectrometer. Data were acquired using a six second pulse repetition delay, 90 degree deflection angles, and reverse gate decoupling, with a sample temperature of 125oC. All measurements were made on non-rotating samples in locked mode. Samples were allowed to thermally equilibrate for seven minutes prior to data acquisition. C13 NMR chemical shifts were internally referenced to the EEE triad at 30.0 ppm. The C6+ value was a direct measure of C6+ branches in LDPE, where long branches were not distinguished from chain ends. The peak of 32.2 ppm, representing the third carbon from the end of all chains or branches of six carbons or more, was used to determine the value of C6+.Nuclear Magnetic Resonance (H1 NMR) Sample Preparation
    [0151] Samples were prepared by adding approximately 130 mg of sample to “3.25 g of a 50/50 mixture of tetrachloroethane-d2/perchlorethylene”, with 0.001 M Cr(AcAc)3, into a NORELL 1001- 7, 10 mm. The samples were purged by bubbling N2 through the solvent, through a pipette inserted into the tube, for approximately five minutes, in order to avoid oxidation. Each tube was capped, sealed with TEFLON tape, and then soaked overnight at room temperature to facilitate sample dissolution. Samples were kept in an N2 purge box during storage and after preparation to minimize O2 exposure. The samples were heated and centrifuged at 115oC to ensure homogeneity. Data Acquisition Parameters
    [0152] H1 NMR was performed with a 400 MHz Bruker AVANCE spectrometer, equipped with a Bruker DUL high temperature Cryo-Probe, and a sample temperature of 120oC. Two experiments were processed to obtain the spectra, a control spectrum to quantify the total polymer protons, and a double pre-saturation experiment, which suppressed the intense polymer backbone peaks, and enabled high-sensitivity spectra for quantification. of the terminal groups. The control was operated with ZG pulse, 4 sweeps, SWH 10,000 Hz, AQ 1.64s, D1 14s. The double pre-saturation experiment was performed with a modified pulse sequence, TD 32768, 100 scans, DS 4, SWH 10,000 Hz, AQ 1.64s, D1 1s, D13, 13s. Data Analysis - H1 NMR Calculations
    [0153] The residual H1 signal in TCE-d2 (at 6.0 ppm) was integrated, and adjusted to a value of 100, and the integral from 3 to -0.5 ppm was used as the signal for all the polymer in the control experiment. For the pre-saturation experiment, the TCE signal was also set to 100, and the corresponding integrals for unsaturation (vinylene at about 5.40 to 5.60 ppm, tri-substituted at about 5.16 to 5, 35 ppm, vinyl at about 4.95 to 5.15 ppm, and vinylidene at about 4.70 to 4.90 ppm) were obtained.
    [0154] In the spectrum of the pre-saturation experiment, the cis- and trans-vinylene, tri-substituted, vinyl, and vinylidene regions were integrated. The integral of the entire polymer of the control experiment was divided in two in order to obtain a value representative of X thousands of carbons (ie, if the polymer integral = 28000, this represents 14,000 carbons, and X=14).
    [0155] The integrals of unsaturated groups, divided by the corresponding number of protons contributing to that integral, represent the moles of each type of unsaturation per X thousand carbons. Dividing the moles of each type of unsaturation by X then gives moles of unsaturated groups per 1000 moles of carbon. Experimental A. First Inventive Ethylene-Based Polymers (IE1)
    [0156] The polymerization was carried out in a tubular reactor with three reaction zones. In each reaction zone, pressurized water was used to cool and/or heat the reaction medium, circulating this water through the reactor jacket. The inlet pressure was 210 MPa (2100 bar), and the pressure drop across the entire tubular reactor system was about 30 MPa (300 bar). Each reaction zone had an inlet and an outlet. Each inlet stream consisted of the outlet stream from the previous reaction zone and/or a feed stream rich in fresh ethylene. Ethylene was supplied according to a specification which allowed a trace amount (maximum 5 molar ppm) of acetylene in the ethylene. Therefore, the maximum trace amount of acetylene incorporated into the polymer was less than or equal to 16 molar ppm, based on the total moles of monomer units in the ethylene-based polymer (see conversion level in table 3). The unconverted ethylene, and other gaseous components at the reactor outlet, were recycled through a high-pressure and a low-pressure recycler, and were compressed and distributed again through an impeller, a primary compressor, and a (secondary) hypercompressor. according to the flow scheme shown in figure 1. Organic peroxides were fed to each reaction zone (see table 1). Acetone was used as a chain transfer agent, and it was present at each reaction zone inlet originating from the low pressure and high pressure recycle streams (#13 and #15) as well as the fresh CTA make-up stream. injector #7 and/or chain #6. The polymer was made at a melt index of 3.3 g/10 min.
    [0157] After reaching the first peak temperature (maximum temperature) in reaction zone 1, the reaction medium was cooled with the aid of pressurized water. At the exit of reaction zone 1, the reaction medium was further cooled by injecting a fresh, cold ethylene feed stream (#20), and the reaction was restarted by feeding an organic peroxide. This process was repeated at the end of the second reaction zone, in order to allow additional polymerization in the third reaction zone. The polymer was extruded and pelleted (about 30 pellets per gram) using a “single screw” extruder at a melting temperature of around 230-250°C. The weight ratio of fresh ethylene rich feed streams (9:20:21) for the three reaction zones was 1.00:0.75:0.25. R2 and R3 values were 2.22 each. R values are calculated in accordance with U.S. Provisional Patent Application No. 61/548996 (International Patent Application No. PCT/US12/059469, filed October 10, 2012). Rn (n=reaction zone number, n>1) is the ratio of “mass fraction of fresh ethylene fed to the first reaction zone (RZ1)” to “mass fraction of fresh ethylene fed to the nth reaction zone ( RZn)” or Rn=RZ1/RZn. The internal process speed was approximately 12.5, 9 and 11 m/sec for the 1st, 2nd and 3rd reaction zones, respectively.
    [0158] In this inventive example, the weight ratio of CTA #7 and #6 replacement currents was 3.6. Additional information can be found in tables 2 and 3. Inventivo 2 (IE2)
    [0159] The polymerization was carried out in a tubular reactor with three reaction zones, as discussed above. Peak temperatures were slightly adjusted, and the melt index was lowered to 2.0. In this inventive example, the weight ratio of CTA (acetone) replacement streams #7 and #6 was 1.1. Additional information can be found in tables 2 and 3. Inventive 3 (IE3)
    [0160] The polymerization was carried out in a tubular reactor with three reaction zones, as discussed above, except that both discharge streams (2 and 3) from the primary compressor were sent to the previous feed stream 4 of the reactor. The weight ratio of ethylene rich feed streams (9:20:21) for the three reaction zones was 1.00:0.75:0.25. The polymer was made at a melt index of 1.5 g/10 min.
    [0161] Each of the values of R2 and R3 approached infinity (tt) . In this inventive example, the weight ratio of CTA replacement streams #7 and #6 was 0.09. Additional information can be found in tables 2 and 3. The CTA was propionic aldehyde (PA). Inventive 4 (IE4)
    [0162] The polymerization was carried out in a tubular reactor with three reaction zones, as discussed above, except that both discharge streams (2 and 3) from the primary compressor were sent to the previous feed stream 4 of the reactor. The weight ratio of ethylene rich feed streams (9:20:21) for the three reaction zones was 1.00:0:0. The polymer was made at a melt index of 0.58 g/10 min.
    [0163] Each of the values of R2 and R3 approached infinity (tt). In this inventive example, the replacement stream weight ratio of CTA #7 and #6 was 2. Additional information can be found in Tables 2 and 3. The CTA was propionic aldehyde (PA). Inventive 5 (IE5)
    [0164] The polymerization was carried out in a tubular reactor with three reaction zones, as discussed above, except that both discharge streams (2 and 3) from the primary compressor were sent to the upstream feed stream 4 of the reactor. The weight ratio of ethylene rich feed streams (9:20:21) for the three reaction zones was 1.00:0:0. The polymer was made at a melt index of 0.37 g/10 min.
    [0165] Each of the values of R2 and R3 approached infinity (tt). In this inventive example, the weight ratio of replacement streams from CTA #7 and #6 was 1.35. Additional information can be found in tables 2 and 3. The CTA was propionic aldehyde (PA).
    [0166] In summary, to achieve high melt strength tubular resins suitable as a blending component in extrusion coating compositions, typically together with a low or lower melt strength component, polymerization conditions include polymerization temperatures , reactor inlet pressure, conversion level, and the type, level and distribution of chain transfer agent, maximums.Table 1: Initiators
    Table 2: Pressure and Temperature Conditions (Inventive Examples)
    Table 3: Additional Information (Inventive Examples)
    * When R2 and R3 are 2.16, the flow scheme in figure 1 was used. In inventive example 3, 4 and 5, both primaries A and B (streams 2 and 3) were sent to stream 4.
    [0167] The properties of polymers are shown in tables 4 and 5 below. Table 4: Properties of Polymers
    * EC: Comparative Example; IE: Inventive Example; AC: autoclave base; tub: tubular.** Commercially available polymers from The Dow Chemical Company's “170oC data” are interpolated from 150oC and 190oC data. t all MWD and g' measurements in this table were obtained by GPC Method A. u Software A was used to determine G'.
    aMw(abs)<Ax[(I2)B], where A=5.00x102 (g/mol)/(dg/min)B, and B= -0.40[Mw(abs), GPC Method A]. b MS>Cx[(I2)D], where C=13.5 cN/(dg/min)D, and D= -0.55 {Mold Strength=MS, 190oC]. c w<E x[(I2)F], where E=0.110 (dg/min)-F, and F= -0.38. t: All MWD measurements in this table were obtained by GPC Method A.
    [0168] Table 6 contains the ramifications per 1000C as measured by NMR of C13. These LDPE polymers contain amyl branches, or C5, which are not contained in substantially linear polyethylenes, such as AFFINITY Polyolefin Plastomers, or Ziegler-Natta-catalyzed LLDPEs, such as DOWLEX Polyethylene Resins, both produced by The Dow Chemical Company. . Each inventive LDPE shown in Table 6 contains more than or equal to 2.0 amyl groups (branches) per 1000 carbon atoms. Table 7 contains results of unsaturation by NMR of H1.Table 6: Results of Branching in Branches by 1000C by NMR of C13 of Inventive Examples and Comparative Examples
    ND = not detected.* Values in the C6+ column for the DOWLEX and AFFINITY samples represent octene C6 branches only, and do not include chain ends.Table 7: H1 NMR Unsaturation Results
    B. Mixture Compositions
    [0169] Table 8 lists some examples of second ethylene-based polymers for use in the inventive compositions.

    [0170] Blending components were formulated using an “18mm” (micro-18) twin screw extruder. The twin screw extruder was a Leistritz machine controlled by HAAKE software. The extruder had five heated zones, a feed zone, and a “3mm” continuous filament die. The feed zone was cooled by running river water, while the remaining zones 1-5 and matrix were electrically heated and air cooled to 120, 135, 150, 190, 190, and 190oC, respectively. The pelleted polymer components were combined in a plastic bag, and manually shaken. After preheating the extruder, the load cell and die pressure transducers were calibrated. The extruder drive unit was operated at 200 rpm, resulting in a gear transfer of a screw speed of 250 rpm. The dry mix was then fed (2.7 kg/h to 3.63 kg/h (6-8 lb/h)) to an extruder through a K-Tron twin auger feeder (model #K2VT20) using no - ends of pellets. The feeder hopper was padded with nitrogen, and the extruder feed cone was covered with an aluminum foil in order to minimize air intrusion, thus minimizing the possible degradation of the polymer by oxygen. The resulting continuous filament was quenched in water, dried with an air knife, and pelleted with a Conair chipper.
    [0171] A first set of mixing compositions was made using EO1 or with LDPE 770G or IE3 according to different mixing ratios. Table 9 shows rheological and molecular weight properties of these mixtures. LDPE 770G has been used in practice as a blending component in extrusion coating with second components such as EO1. The mixture containing IE3, at a weight ratio of 70/30, was found to have a similar melt strength compared to the comparative example containing LDPE 770G (weight ratio 70/30), but also a higher G' value. high. Furthermore, the melt strength (MS) and, consequently, the value of G' (storage modulus), for the inventive mix can be further optimized by varying the mix ratio.Table 9: Properties of Mixing Compositions (each percentage in % w/w)
    t All MWD measurements in this table obtained by GPC Method Bu Software B was used to determine G'.
    [0172] A second set of mixtures was made using LDPE 751A, or with LDPE 770G or with IE3 according to different mixing ratios. Table 10 shows rheological and molecular weight properties of the mixtures. The mixture containing IE3, at a weight ratio of 80/20, was found to have a higher melt strength compared to the comparative example containing LDPE 770G (80/20). These blends have a density of about 0.923 g/cm3 and, in view of their I2 and melt strength (MS), are suitable for coating applications. However, inventive blends achieve the desired melt strength at lower blend ratios (except inventive IE3). Furthermore, the melt strength for inventive mixing can be further optimized by varying the mixing ratio.Table 10: Properties of Mixing Compositions
    t All MWD measurements in this table obtained by GPC MethodB.
    [0173] A third set of blends was made using EO2 with LD410E, LD450E, or IE3, according to various weight ratios. Table 11 shows rheological and molecular weight properties of the mixtures. Blends containing IE3 were found to show significantly higher melt strength (MS) and G' values than blends containing LD410E or LD450E at a similar melt index (I2). LD450E is a specially formulated resin for foam applications where high melt strength is required. Here, blends containing IE3 have significantly higher melt strength (MS) and G' values than blends that do not contain IE3. Also, the blend composition containing only 20% w/w IE3 achieved higher melt strength (MS) and G' values compared to the respective blend compositions each containing 40% w/w LD410E and LD45E, despite the higher melt flow rate of the blend composition containing IE3. These unexpected results provide for new coating compositions which require less LDPE, and which have improved melt strength (MS) and G' values, and which also lead to better maintenance of good mechanical properties and sealing properties associated with the second polymer component. Table 11: Properties of Blending Compositions (each percentage in % w/w)
    t All MWD measurements in this table obtained by GPC MethodB.u Software B was used to determine G'.
    [0174] A fourth set of blends was made using IE3 at various mixing ratios with AMPLIFY EA 103. Table 12 shows the rheological and molecular weight properties of these blends. Blends with IE3 were found to exhibit melt strength (MS) values suitable for extrusion coating. With the use of AMPLIFY EA 103 as a secondary blending component, ethyl acrylate functionality was incorporated into the blending composition. Table 12: Properties of Mixing Compositions (each percentage in % w/w)
    t All MWD measurements in this table obtained by GPC MethodB.
    [0175] A fifth set of mixes was made using IE3 according to various mix ratios with ASPUN 6835A. Table 13 shows rheological and molecular weight properties of these mixtures. Blends with IE3 have been found to exhibit melt strength (MS) and G' values suitable for extrusion coating at an increased density of the blend composition.Table 13: Properties of Blend Compositions (each percent in % w/ for)
    t All MWD measurements in this table obtained by GPC MethodB.u Software B was used to determine G'.
    [0176] A sixth set of blends was made using EO3 with 662i LDPE or IE4 or IE5 at a blend ratio of 85% EO3 and 15% LDPE. Table 14 shows the rheological and molecular weight properties of these mixtures. LDPE 662i has been used in practice as a blending component in extrusion coating with second components such as EO3. The blend with IE4 or IE5 was found to have similar or higher melt strength compared to the comparative example containing LDPE 662i.Table 14: Properties of Blend Compositions (each percent in % w/w)
    t All MWD measurements in this table obtained by GPC MethodB.C. Extrusion Coatings
    [0177] Monolayer coatings were performed according to the following adjustments: Extruder Cylinder - 200/250/280/290/290/290oC; Flange/Adaptor/Piping - 290oC (6 zones); and Matrix - 290oC x 10 zones.
    [0178] The blend compositions were extruded with an “88.9 cm” (“3.5 inches”) diameter thread, with a length-to-diameter ratio (L/D) of 32, onto kraft paper of 70 g/m2, in an amount (coating weight) of 25 g/m2. Melt pressure and melt temperature were recorded with thermocouples placed in the adapter. The melt was released through a Davis Standard/Er-We-Pa, Series 510A, flex lip edge filament reducing die, nominally set to a die gap of 0.6 mm. The extraction of the melt and the application of the melt vertically on the moving substrate was carried out at an air gap of 250 mm and a nip lag of 15 mm, towards the pressure roll. ). The melt was applied to the moving substrate on the press roll, which is the point of contact with the press roll, with a surface rubber layer contacting the “water cooled” chiller roll with a matte surface finish, and maintained at a temperature from 15°C to 20°C. The air gap was defined as the vertical distance between the lip die and the press roll. Press roll lag was defined as the horizontal lag of the lip edge relative to the press roll. Dry blends were prepared using a Maguire WSB-240T gravimetric mixer unit (at room temperature), allowing controlled weight percentages of the respective blending components, prior to extrusion.
    [0179] Various fixed line speeds (100 m/min to 300 m/min) were used to determine the lateral shrinkage of the extrudate, according to coating weights of 15 g/m2 and 25 g/m2. Stretchability is defined as the maximum line speed obtainable before web breaks or web defects/edge inconsistency occur, when accelerating the line speed to constant polymer production. The constant polymer production level is adjusted with a coating weight of 15 g/m2 operating at a line speed of 100 m/min. Stretchability is the difference between the final web width and the die width at a fixed line speed. Lateral shrinkage of the extrudate and increased stretchability are both very desirable. Lower extrudate lateral shrinkage indicates better dimensional stability of the web which, in turn, provides better control of the coating on the substrate. Higher stretchability indicates higher speed capability which in turn provides better productivity. The extrudate lateral shrinkage and stretch results are shown in Table 15 for blends of EO1 with LDPE 770G or IE3.
    [0180] The blend compositions, based on 30% w/w 770G LDPE (autoclave) as a minor component, had low extrudate lateral shrinkage, and were used in extrusion coating applications. Typically, it is difficult to achieve low lateral shrinkage of extrudate in a tubular LDPE. IE3 has been shown to have similar melt strength (MS) to 770G, with and without EO1. IE3 has been found to lead to similar or improved coating performance as an AC-based blend benchmark (EO1/770G blend). The inventive compositions could be made in a tubular reactor train, with improved conversion levels and lower energy expenditure, compared to autoclave processes. Furthermore, the inventive compositions make it possible to produce high clarity extrusion films and coatings. For high clarity film applications, gel levels should be extremely low. To achieve low gel levels, a crosslinking agent is typically not desired, and/or a comonomer with crosslinking capability is typically not desired, in polymer formation, especially at a low melt index. Table 15: Extrusion Coating Properties of Mixture Compositions
    * Starting with a coating weight of 15 g/m2
    [0181] Comparative compositions containing EO2 and LD410E or LD450E, could not be manufactured as good continuous coating sheets due to low melt strength (MS), which would result in excessive extrudate lateral shrinkage. Table 16 shows coating results for blends of EO2 with IE3, which show good extrudate lateral shrinkage data and excellent stretch values.Table 16: Extrusion Coating Properties of Blend Compositions
    * Starting at a coating weight of 15 g/m2 at a line speed of 100 m/min.
    [0182] As seen from Figure 6, blend compositions containing IE3 have significantly better (higher) stretchability compared to blend compositions containing 770G LDPE. The lateral shrinkage performance of the extrudate will depend on the weight ratio of polymer components in the blend and the polymer components in particular. Blend compositions containing IE3 have comparable extrudate lateral shrinkage values at the same weight ratio. Additionally, the lateral shrinkage value of the extrudate can be further improved by adjusting the weight ratio of the polymer components, while maintaining better stretch performance.
    [0183] Additional single layer extrusion coatings were performed on a Black-Clawson extrusion coating/laminating line. A 150 horsepower extruder with an 8.89 cm (3.5 inch) diameter screw was used with screw speeds of approximately 90 rpm, resulting in a polymer production of 114 kg/h (250 lb/h) . The temperature in each zone of the extruder was 177, 232, 288, and 316oC (350, 450, 550, and 600oF), respectively, leading to a target temperature of 320oC. The nominal die width of 76 cm (30 inches) was edged to an open die width of 61 cm (24 inches). An air gap of 15 cm was used, with line speeds of 134 m/min (440 ft/min) and 268 m/min (880 ft/min), resulting in 25 micron (1 mil) and 13 micron coatings. (0.15 thousand), respectively. Extrude lateral shrinkage and stretchability were determined in the same manner as with the coating method described above. The maximum speed used was 457 m/min (1500 ft/min). Mixtures of the various components were produced by weighing the pellets, then mixed by shaking the samples, until a homogeneous mixture was obtained (approximately 30 minutes for each sample). The extrudate lateral shrinkage and stretch results are shown in Table 17 for blends of EO3 with LDPE 6621i or IE4 or IE5.
    [0184] Blend compositions based on 15% w/w LDPE 662i (autoclave) as a minor component had low extrudate lateral shrinkage. Typically, it is difficult to achieve low lateral shrinkage of extrudate with tubular LDPE. IE4 and IE5 have been shown to have similar melt strengths (MS) to 662i, with and without EO3. It has been found that a high melt index linear low density ethylene-octene copolymer blend with a low level of tubular LDPE (e.g. IE5) leads to satisfactory coating performance comparable to the AC based blend. reference (EO3/662i mixture). Those skilled in the art can further optimize the extrudate lateral shrinkage/stretchability balance by adjusting the mixing ratio. In particular, improvement in lateral shrinkage of extrudate can be achieved by incrementally increasing the amount of a suitable LDPE component.Table 17: Extrusion Coating Properties of Blend Compositions
    * Starting with a coating thickness of 13 microns at a line speed of 268 m/min.
    权利要求:
    Claims (15)
    [0001]
    1. Composition based on ethylene, characterized in that it comprises a first polymer based on ethylene, formed by a high pressure free radical polymerization process, and comprising the following properties: a) a ratio of Mw(abs) to I2: Mw(abs)< A x [(I2)B], where A=5.00 x 10 2 (kg/mol)/(dg/min)B, and B= -0.40; and b) a ratio of melt strength (MS) to melt index (I2): MS>C x [(I2)D], where C=13.5 cN/(dg/min)D , and D=-0 .55.
    [0002]
    2. Composition according to claim 1, characterized in that the first ethylene-based polymer has a melt index (I2) of 0.3 to less than 4.0 g/10 min.
    [0003]
    3. Composition according to any one of claims 1 or 2, characterized in that the first ethylene-based polymer has a melt strength (MS) greater than or equal to 9.0 cN (at 190oC).
    [0004]
    4. Composition according to any one of claims 1 to 3, characterized in that the first ethylene-based polymer has a "weight fraction (w) of molecular weight greater than 106 g/mol, based on the total weight of polymer, as determined by GPC(abs)”, which meets the following relationship: w<E x [(I2)F], where E= 0.110 (dg/min)-F, and F= -0.38.
    [0005]
    5. Composition according to any one of claims 1 to 4, characterized in that the first ethylene-based polymer is polymerized in at least one tubular reactor.
    [0006]
    6. Composition according to any one of claims 1 to 5, characterized in that the composition additionally comprises a second ethylene-based polymer.
    [0007]
    7. Composition according to claim 6, characterized in that the composition has a fluidity index (I2) from 2 to 50 g/10 min.
    [0008]
    8. Composition according to any one of claims 6 or 7, characterized in that the composition has a density of 0.900 to 0.955 g/cm3.
    [0009]
    9. Composition according to any one of claims 6 to 8, characterized in that the composition has a melt strength value (MS) greater than or equal to 2.5 cN (at 190oC).
    [0010]
    10. Composition according to any one of claims 6 to 9, characterized in that the composition comprises more than 0% w/w, but less than 40% w/w of the first ethylene-based polymer, based on the sum of the weight of the first and second polymers, and the composition having a G' value greater than or equal to 80 Pa (at 170oC).
    [0011]
    11. Composition according to any one of claims 6 to 10, characterized in that the second ethylene-based polymer comprises at least one comonomer selected from a C3-C20 alpha-olefin, an acrylate, an acetate, a carboxylic acid, carbon monoxide, or an ionomer.
    [0012]
    12. Composition according to any one of claims 6 to 11, characterized in that the second ethylene-based polymer is selected from an ethylene/alpha-olefin copolymer, a low density polyethylene (LDPE), a high density (HDPE), or a combination of these.
    [0013]
    13. Article, characterized in that it comprises at least one component formed from the composition as defined in any one of claims 1 to 12.
    [0014]
    14. Article according to claim 13, characterized in that the article is a coating, a film, a foam, a laminate, fibers, or a tape.
    [0015]
    15. Method of polymerization to form a composition based on low density ethylene, as defined in any one of claims 1 to 12, said method being characterized in that it comprises polymerizing ethylene in a reactor configuration that comprises at least one tubular reactor .
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    同族专利:
    公开号 | 公开日
    ES2640018T3|2017-10-31|
    US20180319910A1|2018-11-08|
    US10975179B2|2021-04-13|
    US10017589B2|2018-07-10|
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    JP2018123327A|2018-08-09|
    CN104781290A|2015-07-15|
    JP6325566B2|2018-05-16|
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    EP2922881B1|2017-07-19|
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    JP2015535035A|2015-12-07|
    KR20150087235A|2015-07-29|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-12-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-23| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-06-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-10-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261728341P| true| 2012-11-20|2012-11-20|
    US61/728,341|2012-11-20|
    PCT/US2013/030459|WO2014081458A1|2012-11-20|2013-03-12|Low density ethylene-based polymers with high melt strength|
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