irradiation-curable polyolefin formulation

专利摘要:
A (electron beam) curable (EBC) formulation comprising an EBC polyolefin compound having a crystallinity of 0 to less than 50 weight percent (% by weight) and / or having a density of 0.930 gram per cubic centimeter (g / cm3) or less; and an alkenyl-functional monocyclic organosiloxane (silicon-based coagent). Also included are a cured polyolefin product prepared by electron beam irradiation of the EBC formulation; methods of making and using the EBC formulation or cured polyolefin product; and articles containing or made from the EBC formulation or cured polyolefin product.
公开号:BR112019026362A2
申请号:R112019026362-4
申请日:2018-05-30
公开日:2020-07-21
发明作者:Yongyong Yang；Yabin Sun；Kainan Zhang；Jeffrey M. Cogen；Timothy J. Person；Paul J. Caronia
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

[1] [1] Polyolefin compositions, electron beam curing, methods and articles. CROSS REFERENCE TO RELATED ORDER (S)
[2] [2] This application claims priority benefit and, by means of this document, incorporates by reference the entire contents of PCT International Patent Application Number PCT / CN2017 / 090770, filed on June 29,
[3] [3] - Publications for patent applications in the field include CN103865420A, CN104277182A, DE 102006017346A1, EP1433811A2, EP2889323A1, US20020198335A1 and US20080176981A1. Patents in the field include US4005254, US5367030, US6187847B1, US6191230B1, US6936655B2, US8426519B2, US8449801B1, US8691984B2 and US9147784B2.
[41] [41] Electron beam irradiation is useful in a method to cure (reticular) polyolefins. The method comprises applying an electron beam irradiation dose to a curable (electron beam) polyolefin compound (EBC) to give a cured polyolefin product. The method forms covalent bonds directly between polyolefin macromolecules of the polyolefin compound EBC. The electron beam curing method can be used to cure various types of polyolefins, including low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE).
[5] [5] We have problems with: (a) how to improve the hot creep performance (hot cure) of electron beam cured polyethylenes, (b) how to increase the electron beam irradiation cure of curable polyolefin compounds by (electron beam) (EBC) and (c) how to make a power cable containing an insulating layer cured by electron beam.
[6] [6] Cross-linked low density polyethylene (XLDPE) and linear cross-linked low density polyethylene (XLLDPE) are used in various industrial applications where they are exposed to high operating temperatures, such as hot water pipes and cable insulation layers. of electricity. For these applications, cross-linked polyethylenes must have adequate performance of hot creep (hot curing) (that is, it retains its shape at the operating temperature). The hot creep performance of crosslinked high density polyethylene (electron beam) is generally weaker than linear crosslinked low density polyethylene (electron beam). Thus, simply mixing a high density polyethylene into a linear low density polyethylene followed by electron beam curing of the mixture would not be expected to improve the hot creep performance over that of linear low density polyethylene alone.
[7] [7] If the dose of electron beam irradiation is too high, undesirable side effects will occur. These include generating excessive amounts of heat, electrical charges and / or H2 gas. Excessive heat can lead to oxidation or deterioration of the cured polyolefin product. Excessive H2 gas can lead to bubble formation in the cured polyolefin product. Excessive electrical charges can lead to electrical discharges of the cured polyolefin product. If the applied dose is too low, the compound does not cure properly or reach a sufficient cure state (extension of cure density or crosslinking) and the performance of the incompletely cured polyolefin product may be inadequate for an intended purpose, such as protecting a cable. SUMMARY
[8] [8] We disclose a technical solution to one or more of the problems presented by: (a) how to improve the hot creep performance (hot cure) of electron beam cured polyethylene, (b) how to increase the irradiation cure electron beam of (electron beam) curable polyolefin compounds (EBC) and (c) how to make a power cable containing an electron beam cured insulation layer. The technical solution includes an (electron beam) curable (EBC) formulation comprising an EBC polyolefin compound ("host resin") having a crystallinity of O at less than 50 weight percent (% by weight) and / or a density of 0.930 grams per cubic centimeter (g / cm3) or less; and an alkenyl-functional monocyclic organosiloxane (“silicon-based coagent”). Modalities also include a cured polyolefin product (cured by electron beam) prepared for electron beam irradiation of the EBC formulation; methods of making and using the EBC formulation or cured polyolefin product; and articles containing or made from the EBC formulation or cured polyolefin product. The inventive formulation and product are useful in any application in which polyolefins are used, including cross-linked polyolefins, including coatings, films, sheets and injection molded articles.
[9] [9] The severity of the problems caused by too high irradiation doses can be alleviated by mixing a smaller amount of silicon-based coagent in the EBC polyolefin compound to give the EBC formulation. The EBC formulation can be cured in the absence of a heat-induced free radical generator compound, such as an organic peroxide. The EBC formulation can be cured at a lower dose of electron beam irradiation than the dose used to cure the EBC polyolefin compound without the silicon-based coagent. In addition, due to the additional cross-linking effect of multivalent cross-linking groups derived from the silicon-based coagent, the resulting cured polyolefin product can achieve a curing state equal to or greater than that of a comparative cured polyolefin product prepared without the coagent. silicon-based in the same lower EB dose. All other things being equal, the higher the loading of the silicon-based coagent in the EBC formulation, the lower the electron beam irradiation dose that can be used to achieve a given curing state (extent of crosslinking density or reticles). DETAILED DESCRIPTION
[10] [10] The Summary and Summary are incorporated by reference for this document. Examples of modalities include the aspects numbered below.
[11] [11] Aspect 1. A (electron beam) curable (EBC) formulation comprising constituents (A) and (B): (A) a (electron beam) curable polyolefin compound (EBC) (“host resin”) ) having a crystallinity of O at less than 50 weight percent (% by weight), alternatively from 10 to less than 50 weight percent, as measured by the Crystallinity Test Method using differential scanning calorimetry (DSC) and / or having a density of 0.930 grams per cubic centimeter (g / cm3) or less, alternatively 0.925 g / cm3 or less, as measured by ASTM D792-13, Method B; and (B) an alkenyl-functional monocyclic organosiloxane of formula (1): [R1, R2SiO2 / 2] n (1), where the subscript n is an integer greater than or equal to 3; each R1 is independently an (C2-C4) alkenyl or an H2C = C (R1a) -C (= 0) -0- (CH2) m- where Ria is H or methyl and the subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C4) alkyl, phenyl or R1 ("silicon based coagent"); where (A) is 50.0 to 99.99% by weight (% by weight), alternatively 80.0 to 99.99% by weight, alternatively 90 to 99.9% by weight, alternatively 95.0 99.4% by weight and (B) is 50.0 to 0.01% by weight, or 20.0% to 0.01% by weight, alternatively 10 to 0.1% by weight, alternatively 5, 0 to 0.6% by weight, of the combined weight of constituents (A) and (B); and with the proviso that the EBC formulation is free of each of a phosphazene base, a semicrystalline polyolefin having a crystallinity of 50% by weight or greater and an organic peroxide. The amount of (B) in the EBC formulation is effective in allowing the EBC polyolefin compound (A) of the EBC formulation to be cured by electron beam at lower irradiation doses than in the absence of (B). In addition to the foregoing excluded materials (phosphazene based, semicrystalline polyolefin having a crystallinity of 50% by weight or greater and organic peroxide), the constituents of the EBC formulation are not particularly limited. Certain modalities are described later “as optionally excluding one or more additional materials.
[12] [12] Aspect 2. The EBC formulation of aspect 1, wherein the polyolefin compound EBC (A) is characterized by any of the limitations (i) to (xv): (i) a crystallinity of> O less than 50.0 wt% (wt%), alternatively 10 to 45 wt%, alternatively 15 to 40 wt%, alternatively 20 to 35 wt%, as measured by the Crystallinity Test Method using calorimetry differential scanning (DSC); (ii) a density of 0.930 g / cm3 or less, alternatively from 0.860 to 0.929 g / cm3, alternatively from 0.880 to 0.929 g / cm3, alternatively from 0.900 to 0.929 g / cm3, or alternatively from 0.910 to 0.929 g / em3, as measured by ASTM D792-13, Method B; (ii) both (i) and (ii); (iv) a melting index (12, 190ºC / 2.16 kg of load) of 0.1 to 20 grams for 10 minutes (9/10 min.), alternatively 0.2 to 20 g / 10 min., alternatively 0.5 to 10 g / 10 min., All measured according to the Fusion Index Test Method (described later) and is a polyethylene; (v) a melt flow rate (MFR) of 0.5 to 20 g / 10 min. (230ºC / 2.16 kg of load) measured according to the Fusion Flow Rate Test Method (described below) and is a polypropylene; (vi) a molecular weight distribution (MWD) that is monomodal; (vi) an MWD that is multimodal, alternatively bimodal; (viii) in which the combined weight of constituents (A) and (B) is 50 to 100% by weight, alternatively from 70 to 100% by weight, alternatively from 80 to 100% by weight, alternatively from 90 to 100% by weight, alternatively from 50 to 99.9% by weight, alternatively from 70 to 99.9% by weight, alternatively from 80 to 99.9% by weight, alternatively from 90 to 99.9% by weight of the EBC formulation ; (ix) the polyolefin compound EBC (A) is a low density polyethylene (LDPE) having a density of 0.910 to 0.925 g / cm3; (x) the polyolefin compound EBC (A) is a linear low density polyethylene (LLDPE) having a density of 0.910 to 0.925 g / cm3; (xi) the polyolefin compound EBC (A) is a polyethylene elastomer selected from elastomers based on ethylene copolymers, such as an ethylene-propylene rubber (EPR), an ethylene-1-butene rubber (EBR) and an ethylene-1-octene boracha (EOR); (xii) the polyolefin compound EBC (A) is a copolymer of ethylene / (C3-C20) alpha-olefin); (xiii) the polyolefin compound EBC (A) is an ethylene-propylene copolymer (EPP); (xiv) the polyolefin compound EBC (A) is a copolymer of ethylene-propylene-monomer diene (EPDM); and (xv) the polyolefin compound EBC (A) is a combination of any two or more of (i) to (xiv).
[13] [13] Aspect 3. The EBC formulation of the aspect | or 2 where in the (B) alkenyl-functional monocyclic organosiloxane of formula (1) the subscript n is 3 and where the EBC formulation is described by any of the limitations (i) to (x): () each R1 it is independently a (C2-C3) alkenyl; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (ii) each R1 is vinyl; and each R2 is independently (C1-C2) alkyl; (iii) each R1 is vinyl; and each R2 is methyl; (iv) each R1 is allyl; and each R2 is independently (C1-C2) alkyl; (v) each R1 is allyl; and each R2 is methyl; (vi) each R1 is independently H2C = C (R1a) - C (= 0) -O- (CH2) m- where R1a is H or methyl and the subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (vii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where R1a is H and the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (viii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Ria is methyl and the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (ix) the EBC formulation does not contain 24% by weight or more, alternatively does not contain 22% by weight or more, alternatively does not contain 20.0% by weight or more, alternatively does not contain 15% by weight or more , alternatively does not contain 10% by weight or more, alternatively, it is free of an inorganic filler selected from the group consisting of aluminum oxide, aluminum silicate, calcium silicate, magnesium silicate, silica, titanium dioxide and mixtures thereof ; and (x) a combination of limitation (ix) and any of the limitations (i) to (viii).
[14] [14] Aspect 4. The EBC formulation of the aspect | or 2 where in the (B) alkenyl-functional monocyclic organosiloxane of formula (1) the subscript n is 4 and where the EBC formulation is described by any of the limitations (i) to (x): () each R1 it is independently a (C2-C3) alkenyl; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (ii) each R1 is vinyl; and each R2 is independently (C1-C2) alkyl; (iii) each R1 is vinyl; and each R2 is methyl; (iv) each R1 is allyl; and each R2 is independently (C1-C2) alkyl; (v) each R1 is allyl; and each R2 is methyl; (vi) each R1 is independently H2C = C (R1a) - C (= 0) -O- (CH2) m- where R1a is H or methyl and the subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (vii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where R1a is H and the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (viii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Ria is methyl and the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (ix) the EBC formulation does not contain 24% by weight or more (that is, it contains 0 to <24% by weight), alternatively, it does not contain 22% by weight or more, alternatively, it does not contain 20.0% by weight or more, alternatively does not contain 15% by weight or more, alternatively does not contain 10% by weight or more, alternatively, it is free of any inorganic fillers; and (x) a combination of limitation (ix) and any of the limitations (i) to (viii).
[15] [15] Aspect 5. The EBC formulation of aspect 1 or 2 where in the (B) alkenyl-functional monocyclic organosiloxane of formula (1) the subscript n is ou6 and where the EBC formulation is described by any of the limitations () to (): () each R1 is independently a (C2-C3) alkenyl; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (ii) each R1 is vinyl; and each R2 is independently (C1-C2) alkyl; (iii) each R1 is vinyl; and each R2 is methyl; (iv) each R1 is allyl; and each R2 is independently (C1-C2) alkyl; (v) each R1 is allyl; and each R2 is methyl; (vi) each R1 is independently H2C = C (R1a) - C (= 0) -O- (CH2) m- where R1a is H or methyl and the subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (vii)
[16] [16] Aspect 6. The EBC formulation of any of aspects 1 to 5 as well - comprising at least one additive selected independently of optional constituents (additives) (C) to (O): (C) a carbon-based coagent ; (D) a flame retardant; (E) an antioxidant; (F) a processing aid; (G) a dye (for example, carbon black); (H) a metal deactivator; (1) a hydrolyzable silane free of (unsaturated carbon-carbon bond); (J) a corrosion inhibitor; (K) a hindered amine light stabilizer; (L) an ethylene-based copolymer that is different from constituent (A) and different from semicrystalline polyolefin having a crystallinity of 50% by weight or greater, where (L) is an ethylene / (C4-C20) alpha copolymer - olefin, an unsaturated ethylene / carboxylic ester copolymer or a propylene / ethylene based copolymer; (M) a filling; (N) a nucleating agent; and (O) a afforestation retardant, such as a water afforestation retardant or an electric afforestation retardant (i.e., voltage stabilizer). When the EBC formulation contains one or more optional additives, the total amount of the optional additive is> 0 to 70% by weight, alternatively from> 0 to 60% by weight, alternatively from> 0 to 40% by weight, alternatively from > 0 to 20% by weight of the EBC formulation. The filling
[17] [17] Aspect 7. A method for making a (electron beam) curable formulation of any one of aspects 1 to 6, the method comprising mixing together a solid divided or molten form of (A) polyolefin compound EBC; and (B) alkenyl-functional monocyclic organosiloxane of formula (1); and any optional constituents (C) to (O), alternatively (D) to (O), to give a mixture consisting essentially of constituents (A), (B) and any optional constituents (C) to (O), alternatively (D) to (O), in order to make the formulation curable by (electron beam) (EBC); with the proviso that the method is free of each of a phosphazene base, a semicrystalline polyolefin having a crystallinity of 50% by weight or greater and an organic peroxide. The mixture may comprise mixing by melting, soaking or direct injection of (B) into (A). The melt mix can comprise composition, extrusion or kneading and can be performed using a Farrel Continuous Mixer (FCM), double extruder, buss kneader or the like. Alternatively, the (B) alkenyl-functional monocyclic organosiloxane of formula (1) can be soaked alone, or with one or more other soaking liquid additives, in (A) the EBC polyolefin compound (eg pellets) to give the formulation of EBC. Alternatively, (B) can be injected directly into (A) during the extrusion or profile molding of (A). The resulting EBC formulation can be irradiated with electron beam irradiation to give the cured polyolefin product. The extruded EBC formulation can be pelletized to give the EBC formulation as solid pellets. Alternatively, the extruded EBC formulation can be cooled to give the EBC formulation as a formed solid, such as an insulation layer on a cable.
[18] [18] Aspect 8. A method for curing by electron beam a formulation in need thereof, the method comprising radiating the EBC formulation from any of aspects 1 to 6, or the formulation curable by (electron beam) made by method of aspect 7, with an effective dose of electron beam irradiation, in order to give a cured polyolefin product by electron beam. The EBC formulation in a formed solid form can be cured by the method to give a formed form of the electron beam cured polyolefin product. Alternatively, the EBC formulation can be cured when in a divided solid form, such as powder, granules, pellets or a combination of any two or more of them.
[19] [19] Aspect 9. An electron beam cured polyolefin product made by the method of aspect 8. The product may have a defined shape, such as coating, film, or molded or extruded shape.
[20] [20] Aspect 10. An article manufactured comprising the polyolefin product cured by electron beam cured of aspect 9 and a component in operative contact with it. The component is made of a material other than the electron beam cured polyolefin product or the EBC formulation. The component can be a substrate to support the EBC polyolefin product.
[21] [21] Aspect 11. A coated conductor comprising a conductive core and a polymeric layer surrounding at least partly the conductive core, wherein at least a portion of the polymeric layer comprises the electron beam cured polyolefin product of aspect 9. The conductor The sheath may be an insulated electrical conductor (power cable) and the polymeric layer may be an insulating layer thereof. Insulated electrical conductors typically comprise a conductive core covered by an insulation layer. The conductive core can be solid or twisted (for example, a bundle of wires). Some isolated electrical conductors may also contain one or more additional elements, such as a semiconductor layer (s) and / or a protective jacket (for example, coiled wire, tape or shield). Examples are coated metal wires and power cables,
[22] [22] Aspect 12. A method of conducting electricity, the method comprising applying a voltage across the conductive core of the conductor coated in aspect 11, so as to generate a flow of electricity through the conductive core.
[23] [23] The inventive EBC formulation can be cured (crosslinked) by electron beam irradiation without ring opening of the alkenyl-functional monocyclic (B) organosiloxane. The curing reaction is conducted in such a way that the (B) alkenyl-functional monocyclic organosiloxane does not give a siloxane (silicone polymer) or polymerized silsesquioxane. We believe that the (B) alkenyl-functional monocyclic organosiloxane functions as a coagent (crosslinking agent) during the electron beam curing of the EBC formulation and that the resulting cured polyolefin product has both direct polyolefin-polyolefin and crosslinked polyolefin bonds via a multivalent cross-linking group derived from the (B) alkenyl-functional monocyclic organosiloxane. Without being limited by theory, it is believed that the constituents of the EBC formulation are chosen so that, during electron beam curing of the EBC formulation, the (B) alkenyl-functional monocyclic organosiloxane does not open the ring to give a open ring (linear or branched) organosiloxane silane (S-OH) oligomer and therefore a polymerized siloxane (silicone polymer) or silsesquioxane is not formed in situ. Without being limited by theory, it is believed that the (B) alkenyl-functional monocyclic organosiloxane cannot undergo ring opening at least in part because the EBC formulation does not contain, and thus, as the curing reaction is conducted in the absence of , (b) ring opening catalyst which is a phosphazene base. In the absence of the phosphazene base, the EBC formulation undergoes cross-linking of the alkenyl-functional monocyclic (B) organosiloxane to the polyolefin polymer via free radical curing to form the cured polyolefin product. Cross-linking occurs beneficially without opening the alkenyl-functional (B) monocyclic organosiloxane (B), even in the presence of ambient humidity.
[24] [24] Additive: a compound or solid or liquid substance that gives a desired property to a host polymer, or to a formulation comprising a master batch polymer or host, or to a reaction product prepared therefrom. The property can be a chemical, electrical, mechanical, optical, physical and / or thermal property.
[25] [25] Alpha-olefin: a compound of formula (1): H2C = C (H) -R (1), where R is a straight chain alkyl group.
[26] [26] The crystallinity of a semicrystalline polyolefin can be determined by differential scanning calorimetry (DSC) according to ASTM D3418-15 or by the Crystallinity Test Method using DSC described below. For a semicrystalline polyethylene resin, wt% crystallinity = (AHf * 100%) / 292 J / g. For a semicrystalline polypropylene resin, wt% crystallinity = (AHf * 100%) / 165 J / g. In the respective equations AHf is the melting calluses of the second heating curve for polyethylene resin or polypropylene resin, as the case may be, * indicates mathematical multiplication, / indicates mathematical division, 292 J / g is a value in the literature melting point (AH) for a 100% crystalline polyethylene and 165 J / g is a value in the literature of the heat of fusion (AHf) for a 100% crystalline polypropylene. Preferably, crystallinity is determined by DSC according to the Crystallinity Test Method described below.
[27] [27] Curing agent: a radical-generating compound (in situ) that upon activation forms a free radical and initiates or intensifies reactions involving cross-linking of macromolecules. Activation of the curing agent can be achieved by subjecting the curing agent to heat or light. Examples of curing agents are peroxides, diazo-functional organic compounds and 2,3-dimethyl-2,3-diphenylbutane. Examples of peroxides are organic hydrogen peroxides of the formula H-O-O-R and organic peroxides of the formula R-O-O-R, where each R is independently a hydrocarbyl group. In some aspects, the EBC formulation and the cured polyolefin product prepared therefrom are free of a curing agent, such as a peroxide, such as an organic hydrogen peroxide or an organic peroxide.
[28] [28] Curing: crosslinking to form a crosslinking product (mesh polymer).
[29] [29] Day: any consecutive 24-hour period.
[30] [30] Divided solid: a particulate material in a state of matter characterized by a relatively stable shape and volume. Examples are powders, granules and pellets.
[31] [31] Effective dose: an absorbed amount (absorbed dose) sufficient to result in the crosslinking of a polyolefin in need of it and absorption of the amount.
[32] [32] Electron beam curable: able to be cured by irradiation (treatment) with high energy beta radiation, such as a high energy electron beam accelerator. Irradiation induces covalent bonding (crosslinking) between adjacent macromolecules to form a network polymer.
[33] [33] High density polyethylene (HDPE): having a density of 0.941 to 0.990 g / cm3, an alpha-olefin comonomeric unit content greater than 0% by weight and short chain branching.
[34] [34] Linear low density polyethylene (LLDPE): having a density of 0.910 to 0.925 g / em3, a comonomeric unit content of alpha-olefin greater than 0% by weight and short chain branching. The LLDPE can have a comonomer distribution width index (CDBI) of 70 to less than 100 weight percent.
[35] [35] Low density polyethylene (LDPE): a polyethylene homopolymer (0% by weight of comonomeric unit content, CDBI = 100%, free of short chain branches) having a density of 0.910 to 0.925 g / em3. LDPE can be done via a free radical polymerization mechanism in a catalyst free high pressure polymerization process.
[36] [36] Medium density polyethylene (MDPE): having a density of 0.926 to 0.940 g / cm3.
[37] [37] Manufactured article: something made by man (by hand or machine).
[38] [38] Fusion: a liquid formed by heating a solid material above its highest melting temperature.
[39] [39] Polyolefin: a macromolecule, or collection of macromolecules, composed of constitutional units derived from polymerizable olefins.
[40] [40] Semicrystalline: a solid material having a first region that is crystalline and a second region that is amorphous. Having a percentage of crystallinity, typically between 5% and 90%, as measured by the Crystallinity Test Method described below.
[41] [41] Solid formed: a state of matter of relatively constant volume and external form that is man-made (by hand or machine). For example, extruding, molding or coating a fluid in the outer form, followed by cooling the outer form in place to give a solid formed.
[42] [42] Store: keep or preserve.
[43] [43] Resudation: slow release of an additive from a solid material containing the additive in it.
[44] [44] Constituent (A) electron-curable polyolefin (EBC) (“Host Polymer”). The EBC polyolefin compound (A) can be a low density polyethylene (LDPE, linear low density polyethylene (LLDPE), a polyolefin elastomer, an ethylene / (C3-C40) alpha-olefin copolymer) or a combination (e.g. , mixture or molten mixture) of any two or more of them. LDPE can have a density of 0.910 to 0.925 g / cm3. LLDPE can have a density of 0.910 to 0.925 g / cm3. The polyolefin elastomer based on ethylene copolymer can be selected from EPR and EBR, alternatively from EPR and EOR, alternatively from EBR and EOR,
[45] [45] Prior to the mixing step used to prepare the EBC formulation, the (A) polyolefin compound EBC can be in a divided solid form, such as a powder, granules and / or pellets.
[46] [46] Alkenyl-functional monocyclic organosiloxane (B) constituent (silicon based coagent). A molecule that contains a backbone or ring substructure containing silicon and oxygen atoms and two or more propenyl, acrylate and / or vinyl groups attached to it, or a collection of these molecules.
[47] [47] Constituent (B) is as previously defined and is used in the formulation of EBC in an effective amount of crosslinking. The crosslinking effective amount of (B) can be from 0.01 to 50% by weight, alternatively from 0.1 to 25% by weight, alternatively from 0.5 to 10% by weight, alternatively from 0.9 to 5 % by weight, alternatively from 1 to 4% by weight, based on the total weight of the EBC formulation. The effective amount of crosslinking of (B) in the EBC formulation can vary depending on the circumstances described above. For example, the effective amount of crosslinking of (B) may be higher in modalities of the polyolefin composition that contain (d) inorganic filler than in modalities of the polyolefin composition that are free of (d) inorganic filler.
[48] [48] Regarding the determination of the effective amount of crosslinking of constituent (B), the presence of crosslinking can be detected as a percentage solvent extraction (Ext%). Ext% = W1 / Wo "* 100%, where Wi is the weight after extraction, Wo is the original weight before extraction, / indicates division and * indicates multiplication. The absence, or a reduced level, of the carbon- carbon of the unsaturated organogroup (eg R1) of (B) in the cross-linked polyolefin product (due to a coupling with the polyolefin compound EBC (A) can be detected by carbon-13 or silicon-nuclear magnetic resonance spectroscopy 29 (13C-NMR and / or 29Si-NMR spectroscopy).
[49] [49] The optional carbon-based constituent (C). The carbon-based coagent (C) comprises a sub-structural group linked to two or more olefinic cross-linking groups, in which the sub-structural group is an acyclic or cyclic multivalent group comprising a backbone or ring, respectively, containing in the backbone or carbon atoms in the ring and, optionally, nitrogen and / or oxygen atoms, but not silicon atoms. Examples are 2-allylphenyl allyl ether; 4-isopropenyl-2,6-dimethylphenyl allyl ether; 2,6-dimethyl-4-allylphenyl allyl ether; 2-methoxy-4-allylphenyl allyl ether; 2,2'-diallyl-bisphenol A; 0.0 "- diallyl-bisphenol A; or tetramethyl-diallybisphenol A; 2,4-diphenyl-4-methyl-1-pentene; 1,3-diisopropenylbenzene; trialyl isocyanurate; trialyl cyanurate; trialyl trimellitate; NN , N ', N', No. Nº-hexa-allyl-1,3,5-triazine-2,4,6-triamine; trialyl orthoformate; pentaerythritol | trialyl ether; trialyl citrate; trialyl aconitate; trimethylolpropane triacrylate; trimethylolpropane trimethylacrylate; bisphenol A ethoxylated dimethacrylate; 1,6-hexanediol diacrylate; pentaerythritol tetracrylate; dipentaerythritol pentacrylate; triacrylate tris (2-hydroxyethyl) isocyanurate; glycerol triacrylate less than 50% polypropylene content; 2-vinyl; trivinyl cyclohexane; and mixtures of any two or more of them. In some aspects (C) it is not present in the inventive master batch formulation and / or in the product. In some aspects (C) it is present in the formulation of inventive master batch and / or in the product at a concentration of 0.1 to 10% in feet o, alternatively | at 5% by weight; and alternatively 2 to 5% by weight; all based on its total weight.
[50] [50] Optional constituent (additive) (D) flame retardant. Flame retardant (D) is a compound that inhibits or delays the spread of fire, suppressing chemical reactions in a flame. In some respects the (D) flame retardant is (D1) a mineral, (D2) an organohalogen compound, (D3) a (organo) phosphorus compound; (D4) a halogenated silicone; or (D5) a combination of any two or more from (D1) to (D4). In some respects (D) it is not present in the inventive master batch formulation and / or in the product. In some aspects (D) it is present in the inventive master batch formulation and / or in the product at a concentration of 0.1 to 20% by weight, alternatively 1 to 10% by weight; and alternatively 5 to 20% by weight; all based on its total weight.
[51] [51] Optional constituent (additive) (E) antioxidant. A compound to inhibit oxidation of a polyolefin. Examples of suitable second antioxidants are polymerized 1,2-dihydro-2,2,4-trimethylquinoline (Agerite MA); tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione (Cyanox 1790); distearyl-3,3-thiodiproprionate (DSTDP); tetrakismethylene (3,5-di-tert-butyl-4-hydroxyhydrocinamate) methane (Irganox 1010); 1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinamoyl) hydrazine (Irganox 1024); bis (4,6-dimethylphenyl) isobutylidene (Lowinox 22IB46); and 4,4-thiobis (2-tert-butyl-5-methylphenol) (TBM6). In some aspects (E) it is not present in the inventive master batch formulation and / or in the product. In some aspects (E) it is present in the inventive master batch formulation and / or in the product at a concentration of 0.01 to 10% by weight, alternatively 0.05 to 5% by weight, alternatively 0.1 to 3% by weight weight, based on its total weight.
[52] [52] Optional constituent (additive) (F) processing aid. Constituent (F) can improve the flow of a fusion of the master batch of coagent through a machine. (F) can be an organic processing aid, such as a fluoropolymer processing aid or a silicone processing aid, such as a fluoro-functionalized polyorganosiloxane or polyorganosiloxane. In some aspects (F) it is not present in the inventive master batch formulation and / or in the product. In some aspects (F) it is present in the inventive master batch formulation and / or in the product at a concentration of 1 to 20% by weight, alternatively 2 to 18% by weight, alternatively 3 to 15% by weight, based on its weight total.
[53] [53] Optional constituent (additive) (G) a dye. For example, a pigment or dye. For example, carbon black or titanium dioxide. Carbon black can be supplied as a master batch of carbon black which is a poly (1-butene-co-ethylene) copolymer formulation (from> 95% by weight to <100% by weight of the total weight of the batch master) and carbon black (from> 0% by weight to <5% by weight of the total weight of the carbon black master batch. In some respects (G) it is not present in the inventive master batch formulation and / or in the product In some aspects (G) coloring is present in the inventive master batch formulation and / or in the product from 0.1 to 35% by weight, alternatively 1 to 10% by weight based on the total weight thereof.
[54] [54] Optional constituent (additive) (H) a metal deactivator. For example, oxailyl bis (benzylidene hydrazide) (OABH). In some aspects (H) it is not present in the inventive master batch formulation and / or in the product. In some aspects (H) it is present in the inventive master batch formulation and / or in the product from 0.001 to 0.2% by weight, alternatively 0.01 to 0.15% by weight, alternatively 0.01 to 0.10% in weight, based on its total weight.
[55] [55] Optional constituent (additive) (1) hydrolyzable silane free of (unsaturated carbon-carbon bond). Useful to eliminate moisture. The constituent (1) can be any monosilane containing at least 1, alternatively at least 2, alternatively at least 3, alternatively 4 hydrolyzable groups (for example, R2 as defined above); and at most 3, alternatively at most 2, alternatively at most 1, alternatively O non-hydrolyzable groups (unsaturated carbon-carbon bond), such as alkyl or aryl groups. Examples of (II) are acetoxytrimethylsilane, 4-benzylphenylsulfonoxytributylsilane, dimethylamino-methoxy-dioctylsilane, octyltrimethoxysilane and tetramethoxysilane. In some respects (1) it is not present in the inventive master batch formulation and / or in the product. In some aspects (|) it is present in the inventive master batch formulation and / or in the product of 0.1 to 2% by weight, alternatively 0.1 to 1.5% by weight, alternatively 0.1 to 1.0% in weight, all based on the total weight of the same.
[56] [56] Optional constituent (additive) (J) a corrosion inhibitor. For example, tin (II) sulfate. In some respects (J) it is not present in the inventive master batch formulation and / or in the product. In some aspects (J) it is present in the inventive master batch formulation and / or in the product from 0.00001 to 0.1% by weight, alternatively 0.0001 to 0.01% by weight, based on the total weight of the same .
[57] [57] Optional constituent (additive) (K) hindered amine light stabilizer O (K) is a compound that inhibits oxidative degradation. Examples of suitable (K) are butanedioic acid dimethyl ester, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol (CAS No. 65447-77-0, commercially LOWILITE 62) and polill6- [(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-di-iIN [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1 , 6 hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino]]) (CAS 71878-19-8 / 70624-18-9, Chimassorb 994 LD, BASF). In some aspects (K) it is not present in the inventive master batch formulation and / or in the product. In some aspects (K) it is present in the inventive master batch formulation and / or in the product from 0.001 to 0.4% by weight, alternatively 0.001 to 0.2% by weight, alternatively 0.01 to 0.15% by weight , alternatively 0.01 to 0.10% by weight, based on the total weight thereof.
[58] [58] Optional constituent (additive) (L) ethylene-based copolymer additive. Constituent (L) is different from constituents (A) and (C). (L) is an LDPE, an ethylene / alpha-olefin copolymer, an unsaturated ethylene / carboxylic ester copolymer (for example, ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate (EEA) copolymer) or ethylene / ethyl acrylate (EEA) copolymer or ethylene / ethyl methacrylate (EEMA) copolymer. In some aspects (L) it is not present in the inventive master batch formulation and / or in the product. In some aspects (L) it is present in the inventive master batch formulation and / or in the product at a concentration of 0.1 to 20% by weight, alternatively 1 to 10% by weight; and alternatively 5 to 20% by weight; all based on its total weight.
[59] [59] The optional constituent (M) filler: a finely divided particulate solid or gel that takes up space and optionally affects the function of a host material. The (M) filler may be a calcined clay, an organo-clay or a hydrophobized fumed silica, such as those commercially available under the trade name CAB-O-SIL from Cabot Corporation. The (M) filler can have flame retardant effects. In some respects, the inventive formulation and the product are free of (M). When present, the (M) filler can be from 1 to 40% by weight, alternatively 2 to 30% by weight, alternatively 5 to 20% by weight of the inventive formulation and the product.
[60] [60] Regarding (M) filling, in some aspects, the inventive formulation and the product do not contain 20% by weight or more, alternatively, do not contain 15% by weight or more, alternatively, do not contain 10% by weight or more , alternatively it is free of an inorganic filler selected from the group consisting of aluminum oxide, aluminum silicate, calcium silicate, magnesium silicate, silica, titanium dioxide and mixtures thereof. The inventive formulation and the product may not contain 20% by weight or more, alternatively, do not contain 15% by weight or more, alternatively, do not contain 10% by weight or more, alternatively, they are free of any inorganic fillers selected from the group that consists of: solids containing Al, solids containing Ca, solids containing Mg, solids containing Si, solids containing Ti and mixtures thereof. For the avoidance of doubt, the term “inorganic filler” does not include carbon black.
[61] [61] The optional constituent (N) nucleating agent. An organic or inorganic additive that enhances the crystallization rate of a polyolefin polymer. Examples of (N) are calcium carbonate, titanium dioxide, barium sulfate, ultra high molecular weight polyethylene, hydrogen potassium phthalate, benzoic acid compounds, sodium benzoate compounds, disodium bicycles [2.2.1] heptane- 2,3-dicarboxylate, zinc monoglycerolate and 1,2-cyclohexanedicarboxylic acid, calcium salt: zinc stearate. In some respects, the inventive formulation and the product are free of (N). When present, (N) can be in a concentration of 0.01 to 1.5% by weight, alternatively, 0.05 to 1.2% by weight, alternatively, 0.1 to 1.0% by weight of inventive and product formulation.
[62] [62] The optional afforestation retardant (O) constituent. The (O) afforestation retardant is a molecule that inhibits water and / or electrical afforestation, or a collection of these molecules. The afforestation retardant can be a water afforestation retardant or an electric afforestation retardant. Water afforestation retardant is a compound that inhibits water afforestation, which is a process by which polyolefins degrade when exposed to the combined effects of an electric field and moisture or moisture. The electrical afforestation retardant, also called voltage stabilizer, is a compound that inhibits electrical afforestation, which is a process of electrical pre-breaking in solid electrical insulation due to partial electrical discharges. Electrical afforestation can occur in the absence of water. Water afforestation and electrical afforestation are problems for electrical cables that contain a sheathed conductor in which the sheath contains a polyolefin. The (O) afforestation retardant can be a poly (ethylene glycol) (PEG).
[63] [63] Other optional constituents. In some respects, the inventive formulation and the product do not contain any optional constituents. In some respects, the inventive formulation and the product do not contain any optional constituents other than constituents (C) to (O). In some respects, the inventive formulation and / or the product still contains at least one optional constituent
[64] [64] Any optional constituent can be useful to transmit at least one feature or property to the inventive master batch formulation and / or product in need of it. The feature or property can be useful to improve the performance of the inventive formulation and / or the product in operations or applications where the inventive formulation and / or the product is exposed to high operating temperature. Such operations or applications include a mixture of fusion, extrusion, molding, hot water pipe and insulation layer of an electric power cable.
[65] [65] Electron beam curable formulation. The total weight of all constituents and additives in the inventive formulation and in the product independently is 100.00% by weight. The electron beam curable formulation can be a one-part formulation, alternatively a two-part formulation. The two-part formulation can comprise first and second parts, where the first part consists essentially of constituents (A) and (B and the second part essentially consists of one or more optional constituents (C) to (O).
[66] [66] The EBC formulation and the cured polyolefin product made from it are free from the phosphazene base. The phosphazene base is a type of ring opening catalyst. The excluded phosphazene base has a P = N core structure, in which free N valences are linked to hydrogen, hydrocarbyl, -P = N Ou = P — N and free P valences are linked to = N or —N. Examples of phosphazene bases are found in US 8,426,519 B2, column 9, line 29, column 10, line 31. The excluded phosphazene base includes combinations of two or more of the same.
[67] [67] In addition to the excluded phosphazene base, certain embodiments of the EBC formulation and the cured polyolefin product made from it may also be free from other ring-opening catalysts. Examples of other ring-opening catalysts are found in F.O. Stark et al., Silicones, Comprehensive Organometallic Chemistry, volume 2, 305, Pergamon Press (1982) They include strong acids, such as trifluoromethanesulfonic acid and its metallic salts, sulfuric acid, perchloric acid and hydrochloric acid; cationic ring opening catalysts, such as metal halides; and anionic ring-opening catalysts, such as organolytes, alkali metal oxides and alkali metal hydroxides; and mixing any two or more of them. For example, the EBC formulation and the cured polyolefin product made from it can be free of acid condensation catalysts which are (i) an organosulfonic acid, an organophosphonic acid or a hydrogen halide; (ii) an organosulfonic acid; (iii) an arylsulfonic acid substituted by alkyl; (iv) an alkyl substituted arylsulfonic acid, where there are / are 1 or 2 (C5-C20) alkyl substituents and 1 aryl group that is phenyl or naphthyl; (v) a (C1-C5) alkylphosphonic acid, wherein the (C1-C5) alkyl is unsubstituted or substituted by an -NH2 group; (vi) HF, HCl or HBr; (vii) a Lewis acid; or (viii) a combination of any two or more of (i) to (vii). The other excluded ring-opening catalysts include combinations of two or more of the same.
[68] [68] The EBC formulation and the cured polyolefin product made therefrom are free of semicrystalline polyolefin having a crystallinity of 50% by weight or greater. The excluded semicrystalline polyolefin can have a crystallinity of at least 55% by weight, alternatively at least 58% by weight, alternatively at least 59% by weight. In any of the foregoing aspects, crystallinity can be a maximum of 90% by weight, alternatively a maximum of 80% by weight, or a maximum of 78% by weight. In some aspects, crystallinity is 55 to 80% by weight, alternatively from 58 to 78% by weight, alternatively from 58 to 76% by weight, alternatively from 62 to 78% by weight, alternatively any of 59 + 1% by weight, 62 + 1% by weight, 76 + 1% by weight and 77 + 1% by weight. Excluded semicrystalline polyolefin having a crystallinity of 50% by weight or greater includes combinations of two or more of the same.
[69] [69] The excluded semicrystalline polyolefin may be a semicrystalline polyethylene having a crystallinity of 50% by weight or greater. Examples are semicrystalline medium density polyethylene (MDPE), semicrystalline high density polyethylene (HDPE) or a combination thereof, all having a crystallinity of 50% by weight or greater. The excluded semi-crystalline HDPE can have a maximum density of 0.970 g / cm3, alternatively a maximum of 0.960 g / cm3, alternatively a maximum of 0.950 g / hundred3. The excluded semi-crystalline HDPE can have a density of> 0.935 to 0.970 g / cm3, alternatively 0.935 to 0.965 g / cm3. Density can be measured by ASTM D-1505, this Method for Density of Plastics by the Density-Gradient Technique. Excluded semicrystalline polyolefin may have a melting index (12, 190ºC / 2.16 kg load) of 10 to 20 9/10 min., Alternatively 0.1 to 10 9/10 min, alternatively 0.20 to 9 g / 10 min. I2 can be determined by ASTM D1238 as described below. The excluded semicrystalline polyolefin can be characterized by a molecular weight distribution (MWD) that is monomodal, alternatively multimodal, for example, bimodal. The excluded semicrystalline polyolefin can be a semicrystalline HDPE which is bimodal and has a density of 0.950 to 0.958 g / cm3 and a melt index of 0.20 to 0.40 g / 10 min. The excluded semicrystalline polyolefin can be a semicrystalline HDPE which is monomodal and has a density of 0.930 to 0.970 g / em3 and a melt index of 0.65 to 9 g / 10 min., Alternatively, a density of 0.935 to 0.965 g / em3 and a melt index of 0.7 to 8.59 / 10 min.
[70] [70] The EBC formulation and the cured polyolefin product made from it are free of organic peroxide. Excluded organic peroxide is a molecule containing carbon atoms, hydrogen atoms and two or more oxygen atoms and having at least one -OO- group, with the proviso that when there is more than one -OO- group, each group - OO- is indirectly linked to another group -OO- by means of one or more carbon atoms or collection of such molecules. The excluded organic peroxide includes a monoperoxide of the formula RO-O-O-RO, wherein each RO is independently a (C1-C20) alkyl group or a (C6-C20) aryl group. Each (C1-C20) alkyl group of RO is independently unsubstituted or substituted by 1 or 2 (C6 -C12) aryl groups. Each RO (C6-C20) aryl group is independently unsubstituted or substituted by 1 to 4 (C1-C10) alkyl groups. The excluded organic peroxide also includes a diperoxide of the formula RO-OOR-0-O0-RO, where R is a divalent hydrocarbon group, such as a (C2-C10) alkylene, (C3-C1O) cycloalkylene or phenylene, and each RO is as defined above. Excluded organic peroxide includes bis (1,1-dimethylethyl) peroxide; bis (1,1-dimethylpropyl) peroxide; 2,5-dimethyl-2,5-bis (1,1-dimethylethylperoxy) hexane; 2,5-dimethyl-2,5-bis (1,1-dimethylethylperoxy) hexino; 4,4-bis (1,1-dimethylethylperoxy) valeric acid; butyl ester; 1,1-bis (1,1-dimethylethylperoxy) -3,3,5-trimethylcyclohexane; benzoyl peroxide; tert-butyl peroxybenzoate; di-tert-amyl peroxide ("DTAP"); bis (alpha-t-butyl-peroxy-isopropyl), benzene ("BIPB"); isopropylcumyl-t-butyl peroxide; t butylcumylperoxide; di-t-butyl peroxide; 2,5-bis (t-butylperoxy) -2,5-dimethylhexane; 2,5-bis (t-butylperoxy) -2,5-dimethyl-hexino-3,1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane; isopropylcumil cumylperoxide; butyl 4,4-di (tert-butylperoxy) valerate; or di (phisopropylcumyl) peroxide; or dicumyl peroxide. The excluded organic peroxide includes combinations of two or more of these organic peroxides.
[71] [71] Some modalities of EBC formulation and the cured polyolefin product made from it can also be free of an inorganic filler that is chosen from aluminum oxide, aluminum silicate, calcium silicate, magnesium silicate, silica, carbon dioxide titanium and mixtures of any two or more of them.
[72] [72] Some modalities of the EBC formulation and the cured polyolefin product made from it are free of each of the phosphazene base, the semicrystalline polyolefin having a crystallinity of 50% by weight or higher, of the organic peroxide, of the opening catalysts non-phosphazene-based ring and inorganic filler. In some of these modalities, the EBC formulation and the cured polyolefin product made from it are also free of the (C) carbon-based coagent, TiO2, or both (C) carbon-based coagent and TiO2. The inventive formulation and the product can be free of a silsesquioxane, alternatively any siloxane, except constituent (B) and electron beam curing reaction (crosslinking) products. of (B).
[73] [73] (C3-C20) alpha-olefin and (C3-C20) alpha-olefin. A compound of formula (1): H2C = C (H) -R (1), where R is either a straight chain (C1-C18) alkyl group or a straight chain (C2-C18) group, respectively. (C3) alpha-olefin is 1-propene and its group R in formula (1) is methyl. The (C2-C18) alpha-olefin group is an unsubstituted monovalent saturated hydrocarbon having 2 to 18 carbon atoms. Examples of (C2-C18) alkyl are ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. In some embodiments, (C4-C20) alpha-olefin is 1-butene, 1-hexene or 1-octene; alternatively 1-butene, 1-hexene or 1-octene; alternatively 1-butene or 1-hexene; alternatively 1-butene or 1-octene; alternatively 1-hexene or 1-octene; alternatively 1-butene; alternatively 1-hexene; alternatively 1-octene; alternatively, a combination of any two of 1-butene, 1-hexene and 1-octene.
[74] [74] Any compound in this document includes all its isotopic forms, including naturally abundant forms and / or isotopically enriched forms, which may have additional uses, such as medical or anti-counterfeiting applications.
[75] [75] Method of curing by electron beam irradiation. The method may comprise radiating the EBC formulation with an effective dose of electron beam irradiation with an electron beam. The effective or absorbed dose of electron beam irradiation can be from 49 to 201 kilojoules of energy per kilogram of EBC formulation (KJ / kg), alternatively from 49 to 160 kJ / Kkg, alternatively from 80 to 201 kJ / kg, alternatively from 80 to 160 kJ / Kkg, alternatively from 50 to 80 kJ / kg, alternatively from 100 to 140 kJ / Kkg, alternatively from 160 to 201 kJ / kg. 100 kJ / kg is equal to 10 megarad
[76] [76] The following applies, unless otherwise indicated. Alternatively, a separate modality precedes ASTM means the organization of standards ASTM International, West Conshohocken, Pennsylvania, USA. IEC stands for the International Electrotechnical Commission standards organization, Geneva, Switzerland. Any comparative example is used for illustration purposes only and will not be prior art. Free of or lacking means a complete absence of; alternatively undetectable. IUPAC is International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, North Carolina, USA). It may confer an allowed choice, not an imperative. Operative means functionally capable or effective. Optional (mind) means to be absent (or excluded), alternatively, to be present (or included). PPM is based on weight. Properties are measured using a test method and standard conditions for measurement (for example, viscosity: 23ºC and 101.3 kPa). The ranges include extreme points, sub-ranges and integer and / or fractional values included in them, with the exception of a range of integers that does not include fractional values. The ambient temperature is 23º C. + 1º C. Replaced, when referring to a compound,
[77] [77] Crystallinity Test Method. To determine crystallinity in% by weight of a semicrystalline polyolefin resin, such as (A) semicrystalline polyolefin carrier resin. Determine melting peaks and weight percent (% by weight) of crystallinity using the DSC DSC Q1000 instrument (TA Instruments) as follows. Procedure (A) baseline calibration instrument. Use software calibration wizard. First, obtain a baseline by heating a cell from - 80º to 280º C without any sample in an aluminum DSC pan. Then, use sapphire patterns as instructed by the calibration wizard. Analyze 1 to 2 milligrams (mg) of a fresh Indian sample by heating the standard sample to 180ºC, cool to 120ºC at a cooling rate of 10ºC / minute, then keep the standard sample isothermally at 120º C. for 1 minute, followed by heating the standard sample from 120º to 180º C at a heating rate of 10º C./minute. Determine that the standard sample of indium has heat of fusion (Hf) = 28.71 + 0.50 Joules per gram (J / g) and start of fusion = 156.6º + 0.5º C. Perform DSC measurements on samples of test using the same DSC instrument. For polyethylene test samples, see procedure (B) below. For polypropylene test samples, see procedure (C) below. The weight percent crystallinity values determined using DSC will be approximately 3 weight percent lower than the weight percent crystallinity values determined according to a density based method.
[78] [78] Procedure (B) DSC on Polyethylene Test Samples. Press the polymer test sample in a thin film at a temperature of 160º C. Weigh 5 to 8 mg of test sample film in a DSC pan. Crimp the lid on the pan to seal the pan and ensure a closed atmosphere. Place the sealed pan in the DSC cell, balance the cell at 30ºC and heat at a rate of about 100º C. / minute to 140ºC., Keep the sample at 140º C. for 1 minute, cool the sample at a rate of 10º C./minute up to 0ºC. or less (for example, -40º C.) to obtain a cold curve melting heat (Hf) and keep isothermally at 0º C. or lower (for example, -40º C.) for 3 minutes. Then, heat the sample again at a rate of 10º C./minute to 180º C to obtain a second heating curve melting heat (AHf). Using the resulting curves, calculate the heat of the cold curve melting (J / g) integrating from the beginning of crystallization to 10º C. Calculating the second heating curve melting heat (J / g) integrating at 10º C. until the end fusion Measure crystallinity in weight percentage (% by weight of crystallinity) of the polymer from the second heat of melting of the test sample (AHf) heating curve and its normalization to the melting heat of 100% crystalline polyethylene, in which% by weight crystallinity = (AHf * 100%) / 292 J / g, where AHf is as defined above, * indicates mathematical multiplication, / indicates mathematical division and 292 J / g is a fusion heat literature value (AHf) for a 100% crystalline polyethylene.
[79] [79] Procedure (C) DSC on Polypropylene Test Samples. Press the polypropylene test sample in a thin film at a temperature of 210º C. Weigh 5 to 8 mg of test sample film in a DSC pan. Crimp the lid on the pan to seal the pan and ensure a closed atmosphere. Place the sealed pan in the DSC cell and heat at a rate of about 100º C. / minute to 230º C., keep the sample at 230º C. for 5 minutes, cool the sample at a rate of 10º C. / minute until -20ºC. to obtain a cold curve melting heat and keep isothermally at -20º C. for 5 minutes. Then, heat the sample again at a rate of 10º C./minute until the melting is complete to obtain a second heating curve melting heat ((AHf)). Using the resulting curves, calculate the cold curve melting heat (J / g) integrating from the start of crystallization to 10º C. Calculate the second heating curve melting heat (J / g) integrating at 10º C. until the end fusion Measure crystallinity in weight percentage (% by weight of crystallinity) of the polymer from the second heat of melting of the test sample (AHf) heating curve and its normalization to the melting heat of 100% crystalline polypropylene, in which% by weight crystallinity = (AHf * 100%) / 165 J / g, where AHf is as defined above, * indicates mathematical multiplication, / indicates mathematical division and 165 J / g is a fusion heat literature value (AHf) for a 100% crystalline polypropylene.
[80] [80] Density Test Method: measured according to ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, for example , in 2-liquid propanol). Reports the results in units of grams per cubic centimeter (g / cm3).
[81] [81] Gel Content Test Method: measured by ASTM D2765-01 (2006), Standard Test Methods for Determination of Gel Content and Swell Ratio of Crosslinked Ethylene Plastics, Test Method A.
[82] [82] Hot Creep Test Method (Hot Curing): A test sample (dog bone shape of dimensions specified in ASTM 638-34; thickness <2mm (mm); marker lines 20mm apart ) is placed in an oven at 200 ºC, and the test sample is weighted equal to a force of 20 Newtons per square centimeter (N / cm2). Elongation of the test sample (distance between the marker lines) under these conditions is then measured and expressed as a percentage of the initial 20 mm distance. To illustrate, if the distance between the marker lines extends up to 40 mm, the hot creep is 100% (100 * (40-20) / 20) = 100%), if it extends to 100 mm, the hot creep is 400%. All other things being equal, the lower the level of crosslinking in the test sample, the greater the extent of its elongation in the Hot Fluid Test Method. On the other hand, the higher the level of crosslinking in the test sample, the less the extent of its elongation. If the level of crosslinking in the test sample is low enough, the test sample may fail to break, which can occur within a few minutes or even seconds of the start of your test pass. Although power cables may not experience operating temperatures as high as 200º C., this test is a reliable way for the industry to evaluate materials for use in their insulation layers. The lower the percentage of hot creep, the better the performance of the material. In the power cable industry, a hot creep of less than 175% after the test sample has been maintained for 15 minutes at 200 ° C passes the hot creep test. And a hot creep of less than 100% after 15 minutes at 200º C. is especially desirable. If the test sample is intact after 15 minutes, the weight is removed, the test sample is removed from the oven and allowed to settle to room temperature. The residual elongation of the test sample after cooling is measured. For a power cable, the residual elongation at room temperature must be less than 15% of the hot creep value measured at 200º C.
[83] [83] Fusion Flow Rate test method (230º C., 2.16 kg (Kg), “MFR”): for propylene-based (co) polymer is measured according to ASTM D1238-13, using 230º C./2.16 kg conditions, formerly known as “Condition E" and also known as MFR Results reported in gram units eluted for 10 minutes (9/10 min.) or the equivalent in decigrams per 1.0 minute (dg / 1 min.) 10.0 dg = 1.00 g.
[81] [81] Melting index test method (190 ºC, 2.16 kg (Kg), “I2”): for ethylene-based (co) polymer it is measured according to ASTM D1238-13, using 190 º C / 2.16 kg, formerly known as "Condition E" and also known as | 2. Results reported in units of grams eluted for 10 minutes (g / 10 min.) Or the equivalent in decigrams for 1.0 minute (dg / 1 min.). 10.0 dg = 1.00 g.
[85] [85] Resudation Test Method (Qualitative): Add sample of polyethylene pellets with coagent to a separate, unused, pressure-sealed polyethylene plastic bag (also known as zip lock or click seal bags). Sealing bags. Press the pellets into bags. Store bags and contents at room temperature for 14 days. At 14 days, observe the bags for traces of oil left on the surfaces of the bags under light. Trace of oil indicates surface migration and poor solubility. More traces of oil on the bag surface, more coagent resud. Classify the progressive amount of resudation by characterizing the traces of oil as none, very little, little or obvious (more than a little). EXAMPLES
[86] [86] EBC polyolefin compound (A1): a low density polyethylene (LDPE) product number DXM-446, which has 45% w / w crystallinity, a density of 0.92 g / cm3 and a melting index ( 12) 2 g / 10 min. and is obtained from The Dow Chemical Company.
[87] [87] EBC polyolefin compound (A2): an ethylene propylene diene copolymer (EPDM) product number NORDEL 4725 having a crystallinity of 12% by weight, a density of 0.88 g / cm3 and a Mooney viscosity 25 ML 1 + 4 at 125º C. determined by ASTM D1646; and is obtained from The Dow Chemical Company.
[88] [88] EBC polyolefin compound (A3): an ethylene-octene copolymer (POE) ENGAGE product number 8150 having a crystallinity of 16% by weight, a density of 0.868 g / cm3 and a melting index (12) of 0.5 g / 10 min. and is obtained from The Dow Chemical Company.
[89] [89] Alkylene-functional monocyclic organosiloxane (B1): tetramethyl-tetravinyl-cyclotetrasiloxane (ViD4) is obtained from The Dow Chemical Company.
[90] [90] Compounds (A1) to (A3) were free of antioxidant and stabilizer.
[91] [91] Carbon-based (C1) coagent: trimethylolbpropane trimethylacrylate (TMPTMA).
[92] [92] Carbon-based coagent (C2): trialyl isocyanurate (TAIC).
[93] [93] Comparative Examples 1 to 9 (CEI to CE9): comparative EBC formulations CE1 to CE9: fusion mixture of LDPE (A1), EPDM (A2) or POE (A3), as appropriate, as described later in the Tables ; and none or a carbon-based coagent (C1) or (C2) in a Banbury composer using a composition temperature of 155 ° C, rotor speed of 60 to 65 revolutions per minute (rpm), followed by extrusion of the melting coagent master batch with air cooling to give extruded coagent master batch and pelletizing the extruded coagent master batch to give comparative EBC formulations from CEI to CES9, respectively, as pellets. See Table 1 for composition data.
[941] [941] Comparative Examples A and | (CE (A) to CE (I)): comparative cured polyolefin products prepared by hot pressing a different one from the comparative formulations CE1 to CE9 at 120º C. to shape the formulations as a 1 mm thick sheet and then cure the sheet with an irradiation dose of 100 kilojoules per kilogram (KJ / Kkg) of electron beam to give comparative cured products from CE (A) to CE (I), respectively. See Table 1 for property data.
[95] [95] Inventive Examples 1 to 5 (IE1 to IE5): inventive EBC formulations 1 to 4. Mix in fusion LDPE (A1), EPDM (A2) or POE (A3), as appropriate, as described later in the Tables; and silicon-based coagent (B1) in a Banbury composer using a composition temperature of 155º C., rotor speed from 60 to 65 revolutions per minute (rpm), followed by extrusion of the EBC formulations fusion with air cooling for giving EBC formulations and pelletizing EBC formulations to give EBC EE formulations to HEIs, respectively, as pellets. See Table 2 for composition data.
[96] [96] Inventive Examples A to E: inventive cured polyolefin products IE (A) to IE (E). prepared by curing the EBC formulations from IE1 to IE5, respectively, with an irradiation dose of 100 kilojoules per kilogram (kJ / Kkg) of electron beam to give the cured polyolefin products IE (A) to IE (E), respectively. See Table 2 for property data.
[97] [97] The hot flow data from Tables 1 and 2 show that the inventive EBC formulations are significantly better at curing to give inventive cured polyolefin products having improved (decreased) hot flow at 200º C. which are the products of comparative cured polyolefin prepared from comparative EBC formulations. Inventive EBC formulations also have less ViD4 (B1) uptake than comparative EBC formulations have TAIC (C1) or TMPTMA (C2) uptake, which beneficially allows for higher loading of (B) into the EBC polyolefin compound (A), such as an LDPE, EPDM or POE, in inventive EBC formulations than the loading of (C) carbon-based coagent in the same LDPE, EPDM or POE as comparative EBC formulations. Higher loading of (B) in inventive EBC formulations can improve (increase) their electron beam curing efficiency, allowing lower doses of absorbed electron beam irradiation to be used to achieve a given cure state or allowing the same dose of absorbed electron beam radiation to give a greater healing state (greater amount of crosslinking).

权利要求:
Claims (12)
[1]
1. Formulation curable by (electron beam) (EBC), characterized by the fact that it comprises the constituents (A) and (B): (A) a polyolefin compound curable by (electron beam) (EBC) having a crystallinity O to less than 50% by weight (% by weight), as measured by the Crystallinity Test Method using differential scanning calorimetry (DSC) and / or having a density of 0.930 gram per cubic centimeter (9g / cm3) or less, as measured by ASTM D792-13, Method B; and (B) an alkenyl-functional monocyclic organosiloxane of formula (1): [R1, R2SiO2 / 2] n (1), where the subscript n is an integer greater than or equal to 3; each R1 is independently an (C2-C4) alkenyl or an H2C = C (R1a) -C (= 0) -O- (CH2) m- where Ria is H or methyl and the subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C4) alkyl, phenyl or R1; wherein (A) is 50.0 to 99.99% by weight and (B) is 50.0 to 0.01% by weight of the combined weight of constituents (A) and (B); and with the proviso that the EBC formulation is free of each of a phosphazene base, a semicrystalline polyolefin having a crystallinity of 50% by weight or greater and an organic peroxide.
[2]
2. Formulation curable by (electron beam), according to claim 1, characterized by the fact that (A) is characterized by any of the limitations (i) to (xv): (i) a crystallinity of> O less than 50.0 weight percent as measured by the Crystallinity Test Method using differential scanning calorimetry (DSC); (ii) a density of 0.930 g / em3 or less, as measured by ASTM D792-13, Method B; (iii) both (i) and (ii); (iv) a melting index (12, 190ºC / 2.16 kg load) of 0.1 to 20 grams for 10 minutes (g / 10 min.) measured according to the Melting Index Test Method and is a polyethylene; (v) a melt flow rate (MFR) of 0.5 to 20 g / 10 min. (230ºC / 2.16 kg of load) measured according to the Fusion Flow Rate Test Method and is a polypropylene; (vi) a molecular weight distribution (MWD) that is monomodal; (vii) an MWD that is multimodal; (viii) in which the combined weight of constituents (A) and (B) is 50 to 100% by weight of the formulation curable by (electron beam); (ix) the polyolefin compound EBC (A) is a low density polyethylene (LDPE) having a density of 0.910 to 0.925 g / cm3; (x) the polyolefin compound EBC (A) is a linear low density polyethylene (LLDPE) having a density of 0.910 to 0.925 g / cm3; (xi) the polyolefin compound EBC (A) is a polyethylene elastomer selected from ethylene-propylene rubber (EPR), an ethylene-1-butene rubber (EBR) and an ethylene-1-octene boracha (EOR) ; (xii) the polyolefin compound EBC (A) is a copolymer of ethylene / (C3-C20) alpha-olefin); (xiii) the polyolefin compound EBC (A) is an ethylene-propylene copolymer (EPP); (xiv) the polyolefin compound EBC (A) is a copolymer of ethylene-propylene-monomer diene (EPDM); and (xv) the polyolefin compound EBC (A) is a combination of any two or more of (i) to (xiv).
[3]
3. Formulation curable by (electron beam), according to claim 1 or 2, characterized by the fact that in the (B) alkenyl-functional monocyclic organosiloxane of formula (1) the subscript n is 3 and in which the formulation of EBC is described by any of the limitations (|) to (x): () each R1 is independently a (C2-C3) alkenyl; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (il) each R1 is vinyl and each R2 is independently (C1-C2) alkyl; (iii) each R1 is vinyl; and each R2 is methyl; (iv) each R1 is allyl; and each R2 is independently (C1-C2) alkyl; (v) each R1 is allyl; and each R2 is methyl; (vi) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Ria is H or methyl and the subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (vii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Rla is He and the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (vii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Ria is methyl the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (ix) the EBC formulation does not contain 24% by weight or more of an inorganic filler selected from the group consisting of aluminum oxide, aluminum silicate, calcium silicate, magnesium silicate, silica, titanium dioxide and mixtures thereof ; and (x) a combination of limitation (ix) and any of the limitations (i) to (viii).
[4]
4. Formulation curable by (electron beam), according to claim 1 or 2, characterized by the fact that in the (B) alkenyl-functional monocyclic organosiloxane of formula (1) the subscript n is 4 and in which the formulation of EBC is described by any of the limitations (i) to (x): (i) each R1 is independently an (C2-C3) alkenyl; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (il) each R1 is vinyl and each R2 is independently (C1-C2) alkyl; (iii) each R1 is vinyl; and each R2 is methyl; (iv) each R1 is allyl; and each R2 is independently (C1-C2) alkyl; (v) each R1 is allyl; and each R2 is methyl; (vi) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Ria is H or methyl and the subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (vii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Rla is He and the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (viii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Ria is methyl the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (ix) the EBC formulation does not contain 24% by weight or more of any inorganic fillers; and (x) a combination of limitation (ix) and any of the limitations () to (viii).
[5]
5. Formulation curable by (electron beam), according to claim 1 or 2, characterized by the fact that in the (B) alkenyl-functional monocyclic organosiloxane of formula (1) the subscript n is 5 or 6 and in which the EBC formulation is described by any of the limitations (i) to (x): () each R1 is independently an (C2-C3) alkenyl; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (il) each R1 is vini; and each R2 is independently (C1-C2) alkyl; (iii) each R1 is vinyl; and each R2 is methyl; (iv) each R1 is allyl; and each R2 is independently (C1-C2) alkyl; (v) each R1 is allyl; and each R2 is methyl; (vi) each R1 is independently H2C = C (R1a) -C (= 0) -O-
(CH2) m- where Ria is H or methyl and the subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C2) alkyl or (C2-C3) alkenyl; (vii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Rla is He and the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (viii) each R1 is independently H2C = C (R1a) -C (= 0) -O- (CH2) m- where Ria is methyl the subscript m is 3; and each R2 is independently (C1-C2) alkyl; (ix) the EBC formulation does not contain 24% by weight or more of an inorganic filler selected from the group consisting of aluminum oxide, aluminum silicate, calcium silicate, magnesium silicate, silica, titanium dioxide and mixtures thereof ; and (x) a combination of limitation (ix) and any of the limitations (i) to (viii).
[6]
6. Formulation curable by (electron beam) according to any one of claims 1 to 5, characterized by the fact that it comprises at least one additive selected independently of optional constituents (C) to (O): (C) a coagent carbon based; (D) a flame retardant; (E) an antioxidant; (F) a processing aid; (G) a dye (for example, carbon black); (H) a metal deactivator; (1) a hydrolyzable silane free of (unsaturated carbon-carbon bond); (J) a corrosion inhibitor; (K) a hindered amine light stabilizer; (L) an ethylene-based copolymer that is different from constituent (A) and different from semicrystalline polyolefin having a crystallinity of 50% by weight or greater, where (L) is an ethylene / (C4-C20) alpha copolymer -olefin, an unsaturated ethylene / carboxylic ester copolymer or a propylene / ethylene based copolymer; (M) a filling; (N) a nucleating agent; and (O) a afforestation retardant.
[7]
Method for making a (electron beam) curable formulation of any one of claims 1 to 6, the method characterized by the fact that it comprises mixing together a divided solid form or molten form of the (A) polyolefin compound EBC; and (B) alkenyl-functional monocyclic organosiloxane of formula (1); and any optional constituents (C) to (O), so as to give a mixture consisting essentially of constituents (A), (B) and any optional constituents (C) to (O), in order to make the formulation curable by ( electron beam) (EBC); with the proviso that the method is free of each of a phosphazene base, a semicrystalline polyolefin having a crystallinity of 50% by weight or greater and an organic peroxide.
[8]
8. Method for curing by electron beam a formulation in need thereof, the method comprising irradiating the EBC formulation of any one of claims 1 to 6, or the formulation curable by (electron beam) made by the method of claim 7, with an effective dose of electron beam irradiation, in order to give an electron beam cured polyolefin product.
[9]
9. Polyolefin product cured by electron beam, characterized by the fact that it is made by the method of claim 8.
[10]
10. - Manufactured article, characterized by the fact that it comprises the electron beam cured polyolefin product of claim 9 and a component in operational contact with it.
[11]
Coated conductor, characterized in that it comprises a conductive core and a polymeric layer surrounding at least partially the conductive core, wherein at least a portion of the polymeric layer comprises the electron beam cured polyolefin product of claim 9.
[12]
12. Method for conducting electricity, the method characterized by the fact that it comprises applying a voltage across the conductive core of the coated conductor of claim 11, so as to generate a flow of electricity through the conductive core.

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法律状态:
2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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PCT/CN2017/090770|WO2019000311A1|2017-06-29|2017-06-29|Polyolefin composition|

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CNCN2017090770|2017-06-29|

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PCT/CN2018/088965|WO2019001206A1|2017-06-29|2018-05-30|Irradiation-curable polyolefin formulation|

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