MXPA01011557A

MXPA01011557A - Highly crystalline eaodm interpolymers.

Info

Publication number: MXPA01011557A
Application number: MXPA01011557A
Authority: MX
Inventors: Morgan Mark Hughes
Original assignee: Dupont Dow Elastomers Llc
Priority date: 1999-05-14
Filing date: 2000-05-12
Publication date: 2002-07-30
Also published as: BR0011524A; CN1367801A; AU4847500A; KR20010113933A; EP1183286A1; CA2372056A1; WO2000069930A1; JP2002544344A

Abstract

High crystallinity ethylene/alpha-olefin/polyene interpolymers, whether grafted with an unsaturated monomer or not, and if grafted, whether cross-linked or not, can be used as is to form a polymer composition or blended with other natural or synthetic polymers to form polymer blend compositions. Both the polymer composition and the polymer blend compositions have desirable physical properties that are useful in fabricating a variety of finished products.

Description

INTERPOLIMEROS DE ETILENO / ALFA-OLEF NA / POLYENO ALTAMENTE CRISTALINOS Field of the Invention This invention relates to random ethylene / alpha (a) -olefin / polyene (EAODM) interpolymers containing at least 84 weight percent (% by weight) of ethylene and to the use of such interpolymers in combination with other polyolefins, rubbers, and thermoplastic formulations. This invention also relates to cured or streaked EAODM interpolymers and to the use of such crosslinked interpolymers to produce fabricated articles including, but not limited to, wire and cable products, foams, automotive components, pipe, tape, laminates, coatings and movies. This invention further relates to mixtures of the polymers of this invention with both natural and synthetic polymers, especially with thermoplastic polyolefins (TPO). This invention further relates to EAODM polymers which are grafted with other monomers, such as the unsaturated carboxylic acid monomers, and to the use of such grafted interpolymers as, for example, impact modifiers, compatibilizers and adhesion promoters. Ref.134060 Background of the Invention Polyolefins are used in numerous applications including, but not limited to, wire and cable insulation, automotive interior linings, modification of the impact characteristics of other polyolefins, foams, and films . Many of these applications demand ever-increasing improvements in heat resistance. A method for improving the heat resistance of the polyolefin involves the crosslinking or curing of the polyolefin using either a radiation source such as electron beam (EB) radiation, gamma radiation or ultraviolet (UV) radiation, or a heat activated chemical crosslinking agent such as a peroxide. Additionally, when the polyolefin contains an unsaturation, the heat-activated chemical crosslinking agent can be sulfur, a phenolate, or a silicon hydride. Cured elastomer parts manufacturers are engaged in current polyolefin research with improved curing characteristics that provide one or more additional benefits such as faster productivity to reduce manufacturing costs. For polyethylene (PE), an increase in the density of the crosslinking typically requires the use of more peroxide or an increased level of exposure to radiation, both of which increase the cost. Those who work with the EP want an effective proposal, but cheaper. The interpolymers of this invention have unsaturated sites that allow the grafting of polar materials onto the backbone of the interpolymer. Skilled artisans recognize that non-polar polyolefins, particularly PE, provide poor substrates for the application of polar coating materials such as paint. For the paint to effectively adhere to the PE, PE surfaces are usually treated to improve compatibility using techniques such as surface treatment with a flame and corona discharge. An alternative technique changes the polymer itself and involves the grafting of the polar materials onto the polymer skeleton.

Brief Description of the Invention One aspect of the present invention is an interpolymer composition comprising a random EAODM interpolymer comprising: (a) ethylene in an amount from 84 to 99 percent by weight (% by weight), (b) ) an α-olefin containing from 3 to 20 carbon atoms (C3-2o) in an amount within a range from greater than (>) O to less than (<) 16% by weight, and (c) a polyene in an amount from > 0 to 15% by weight, all percentages are based on the weight of the interpolymer and selected up to 100 percent by total weight, the interpolymer has a crystallinity >; 16 percent and a vitreous transition temperature (Tg) of -45 ° C (° C) or higher. As an example, a Tg of -40 ° C is > a Tg of -45 ° C. For comparison, an EAODM having 85% by weight of ethylene, 10% by weight of propylene, and 5% by weight of a diene, has an ethylene content of 91.5 mol%. The resulting interpolymers, if desired, can be chemically crosslinked using agents such as peroxides, sulfur, phenolates and silicon hydrides or by radiation using any of the radiation with EB, gamma radiation or UV radiation. When used herein, "interpolymer" refers to a polymer having at least three monomers polymerized therein. The interpolymer includes, without limitation, terpolymers and tetrapolymers. A "copolymer" has two monomers polymerized therein. When crosslinked, the ethylene interpolymers of this invention exhibit improved mechanical strength, heat resistance, and curing properties relative to the crosslinked ethylene interpolymers prepared from the same monomers but with a lower ethylene content.

DETAILED DESCRIPTION OF THE INVENTION Skilled artisans recognize that polyolefins with unsaturation have a greater crosslinking efficiency than those lacking unsaturation. The improved crosslinking efficiency generally results in faster curing, increased mechanical strength, and, for a terminal use manufacturer, increased productivity. The EAODMs of the present invention, when combined with the polyolefins, provide a means for increasing the crosslinking density of the polyolefin without resorting to conventional techniques such as the use of more peroxide or the increase in radiation exposure. The crystallinity of the polymer has an impact on physical properties such as tensile strength, strength before firing, and flexural modulus. Reductions in the crystallinity of the polymer typically lead to a corresponding reduction in tensile strength, strength before firing, and flexural modulus. Commercially available polyolefins, such as high density polyethylene (HDPE), typically have a crystallinity within a range of 45% up to. 95% Conventional EAODM polymers have a crystallinity within a range of 0% to 16%. When such conventional EAODM polymers are mixed with the HDPE or other crystalline polyolefin, the resulting mixture has a reduced crystallinity relative to crystalline polyolefin. By way of contrast, the EAODMs of the present invention have a crystallinity, as measured by Differential Scanning Calorimetry (DSC), within a range of > 16% by weight up to < 75% by weight, preferably from > 19% by weight up to 40% by weight. Unless stated otherwise, a numerical range includes both extreme points. The EAODM interpolymers suitable for this invention include polymers having polymerized thereon to ethylene, at least one α-olefin with C3-2o. preferably C3-10, and at least one polyene. Skillful craftsmen can easily select the appropriate monomer combinations for any desired interpolymer as long as the interpolymer meets the requirements, such as the ethylene content and the crystallinity requirements set forth herein. The EAODM interpolymers of this invention have an ethylene content of at least 84% by weight, preferably at least 88% by weight, and more preferably at least 90% by weight, but in no case more than 99% by weight of ethylene. The ethylene content can vary up or down by a few percentage points depending on the amount and weight of the polyene in the EAODM. In general, selections of the amounts of ethylene, α-olefin and polyene provide a ratio of ethylene to α-olefin of at least 95: 5, preferably > 95: 5. The EAODMs with > 84% by weight of ethylene possess a crystallinity by DSC as described above. It is believed that this crystallinity provides much of the mechanical strength of the polymer. Increases in the polymer's crystallinity lead to proportional increases in the Tg of the polymer. The interpolymers of this invention have a Tg, when measured by DSC, of > -45 ° Centigrade (° C), preferably > -40 ° C. Expert artisans recognize that endothermic fusion makes the Tg uncertain when the polymer's crystallinity increases. As such, there is no significant upper limit for Tg. The α-olefin may be a compound either aliphatic or aromatic and may contain a vinyl unsaturation or a cyclic compound, such as cyclobutene, cyclopentene, or norbornene, including the norbornenes substituted at positions 5 and 6 with a hydrocarbyl group of C? -20. The α-olefin is preferably an aliphatic compound of C3-20, more preferably an aliphatic compound of C3-? 6 and still more preferably an aliphatic compound of C3-? 0 such as propylene, isobutylene, butene-1, pentene-1, hexene-1,3-methyl-1-pentene, 4-methyl-1-pentene, octene-1, decene-1 and dodecene-1. Other preferred ethylenically unsaturated monomers include 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, and mixtures thereof. The most preferred α-olefins are propylene, butene-1, hexene-1, and octene-1. The content of α-olefin is preferably from >; 0 up to < 16 percent by weight, more preferably from 1% by weight to 10% by weight, and even more preferably from 2% by weight to 8% by weight, based on the weight of the total interpolymer. The polyene, sometimes referred to as a diolefin or a diene monomer, is desirably a polyene with C4-40. The polyene is preferably an unconjugated diolefin, but can be a conjugated diolefin. The unconjugated diolefin can be a straight-chain, branched-chain or cyclic hydrocarbon diene of C6-i5. Illustrative non-conjugated dienes are branched chain acyclic dienes such as 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 3,7-dimethyl- 1, 6-octadiene, 3,7-dimethyl-l, 7-octadiene, 5,7-dimethyl-l, 7-octadiene, and the mixed isomers of dihydromyrzene; the single-ring alicyclic dienes such as 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene; the ring-bonded dienes and the fused, alicyclic, multi-ring dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene (DCPD), bicyclo- (2, 2, 1) -hepta-2, 5-diene ( norbornadiene or NBD), methyl norbornadiene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, - (4-cyclopentenyl) -2-norbornene and 5-cyclohexylidene-2-horbornene. When the diolefin is a conjugated diene, it can be 1,3-pentadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 4-methyl-1,3-pentadiene, or 1,3-diene. cyclopentadiene. The diene is preferably a non-conjugated diene selected from ENB and NBD, more preferably, ENB. The content of the EAODM polyene monomer is preferably within a range of > 0 up to < 5 percent mol (mol%), based on the moles of ethylene, α-olefin and, based on weight, the content of the EAODM polyene monomer is equal to the percent limitations in mol and will vary depending on the weight of the polyene. In general terms, the content of the polyene is from > 0 to 15% by weight; more preferably from 0.3 to 12% by weight, and more preferably from 0.5 to 10% by weight based on the weight of the polymer. When the polyene monomer is the ENB, a monomer content from > 0 up to < 11% by weight, based on the weight of the interpolymer, is generally equal to > 0 up to < 3 of the% in mol interval. The molecular weight distribution (MWD) is a well-known variable in polymers. It is sometimes described as the ratio of the weighted average molecular weight (M ") to the numerical average molecular weight (Mn) (ie, Mw / Mn) and can be measured directly or more routinely by measuring the melt index of the polymer (I) using ASTM D-1238 (190 ° C / 10 kilograms (kg)) for lyo and ASTM D-1238 (190 ° C / 2.16 kg) for I2 / and calculate the ratio of I10 / I2. Polymers having a reduced MWD exhibit higher strength, better optical characteristics, and higher crosslinking efficiencies than polymers with the same monomer composition, but a comparatively wider MWD. The MWD values of the interpolymers of this invention, prepared with the metallocene catalysts, particularly the restricted geometry catalysts (GCSs), are from > 1 to 15, preferably from > 1 to 10 and even more preferably from > 1 to 4. The EAODM interpolymers of this invention have a melting point (m.p.) of > 70 ° C. The p.f. it is desirably > 80 ° C, preferably > 85 ° C. The p.f. it is desirably < 135 ° C, preferably < 125 ° C. The p.f. of < 70 ° C effectively excludes certain applications that require a relatively high service temperature (UST) such as the coating materials of cables and wires with a UST >requirement.; 70 ° C. Expert craftsmen recognize that a limit of the theoretical upper melting point is established by the homopolymer of HDPE with a p.f. of about 135 ° C (varies with the molecular weight of the polymer). The EAODM interpolymers of this invention have a heat of fusion > 11 calories per gram (cal / g). The heat of fusion is desirably > 12 cal / g, and preferably > 13 cal / g. The heat of fusion can be as large as 30 cal / g or even higher depending on a variety of factors, one of which is the crystallinity of the interpolymer. The EAODM interpolymers of this invention can be produced using one or more metallocenes or restricted geometry catalysts (CGC) in combination with an activator, in solution, suspension, or gas phase processes. The catalysts are preferably the transition metal catalysts of mono or bis-cyclopentadienyl, indenyl, or fluorenyl (preferably of Group 4), and more preferably the CGCs of mono-cyclopentadienyl, mono-indenyl or mono-fluorenyl. The process in solution is preferred. U.S. Patent No. 5,064,802; WO93 / 19104 (US Serial No. 8,003, filed January 21, 1993), and WO95 / 00526 disclose metal complexes of restricted geometry and methods for their preparation, metal complexes containing indenyl, variously substituted, are taught in WO95 / 14024 and W098 / 49212. The relevant teachings of all of the foregoing patents and their corresponding US patent applications are incorporated herein by reference. In general, the polymerization can be carried out under conditions well known in the art for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type, ie, at temperatures from 0-250 ° C, preferably 30-200 ° C, and pressures from atmospheric to 10,000 atmospheres (1013 megapascals (MPa)). Polymerization in suspension, solution, slurry, gaseous phase, or powder in solid state or other process conditions, may be employed if desired. A support, especially silica, alumina, or a polymer (especially poly (tetrafluoroethylene) or a polyolefin) can be employed, and desirably is employed when the catalysts are used in a gas phase polymerization process. The support is preferably employed in an amount sufficient to provide a weight ratio of the catalyst (based on the metal): support within a range of from 1: 100,000 to 1:10, more preferably from 1: 50,000 to 1:20, and even more preferably from 1: 10,000 to 1:30. In most polymerization reactions, the molar ratio of the polymerizable compounds: catalyst employed is from 10"12: 1 to 10_1: 1, more preferably from 10" 9: 1 to 10"5: 1. Inerts serve as suitable solvents for polymerization Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof: cyclic and alicyclic hydrocarbons such as cyclohexane , cycloheptane, methylcyclohexane, methydecydoheptane, and mixtures thereof, perfluorinated hydrocarbons such as C- or perfluorinated alkanes, and alkyl-substituted aromatic and aromatic compounds such as benzene, toluene, xylene, and ethylbenzene. Suitable also include liquid olefins that can act as monomers or comonomers including butadiene, cyclopentene, 1-hexene, 1-hexane, 4-vinylcyclohexene, vinyl clohexane, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene, and vinyltoluene (including all isomers alone or mixed). Mixtures of the above are also suitable. If desired, normally gaseous olefins can be converted to liquids by the application of pressure and used herein. The catalysts can be used in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same reactor or in separate reactors which are connected in series or in parallel to prepare the polymer blends having desirable properties. An example of such a process is described in WO 94/00500 on page 29 line 4 to page 33 line 17. The process uses a continuously stirred tank reactor (CSTR) connected in series or parallel to at least one other CSTR or reactor. tank. WO 93/13143 (on page 2 lines 19-31) teaches the polymerization of the monomers in a first reactor using a first CGC having a first reactivity and polymerization monomers in a second reactor using a second CGC having a second reactivity and combine the products of the two reactors. Page 3, lines 25-32 of WO 93/13143 provides teachings about the use of two CGCs having different reactivities in a reactor. WO 97/36942 (page 4 line 30 to page 6 line 7) teaches the use of a reactor system of two closed circuits. The relevant teachings of such applications and their U.S. patent applications. corresponding ones are incorporated herein for reference. Additionally, the same catalyst can be used in both reactors operating at different processing conditions. The EAODM interpolymers of this invention can be combined with other natural or synthetic polymers in a mixture containing from 2 to 98% of such EAODM interpolymer (s) based on the weight of the total mixture. The natural and synthetic polymers can be natural rubber, styrene-butadiene rubber (SBR), butadiene rubber, butyl rubber, polyisoprene, polychloroprene (neoprene), or the homopolymers of the monoolefins of a mixture of two or more monoolefins, preferably an α-olefin monomer of C2-2o- The α-olefin monomer is more preferably selected from the group consisting of ethylene, propylene-1, butene-1, hexene-1 and octene-1. Olefin homopolymers or polyolefins include, for example, polyethylene, polypropylene, and polybutene. Exemplary copolymers of two, and the interpolymers of at least three, different monoolefins, include the ethylene / propylene, ethylene / butene, ethylene / hexene and ethylene / octene copolymers, the ethylene / propylene / carbon monoxide polymers, the ethylene / styrene interpolymers; and vinyl acetate / ethylene copolymers. The interpolymers. of EAODM of this invention can also be mixed with conventional ethylene / propylene / diene monomer (EPDM) or EAODM interpolymers having an ethylene content.; 80% by weight. Preferred polyolefins for mixing with the interpolymers of this invention are polyethylene (PE), polypropylene (PP) and mixtures thereof. The term "PE" includes HDPE, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), intermediate density polyethylene (MDPE), and ultra low density polyethylene (ULDPE). The interpolymers of this invention and mixtures thereof can be crosslinked or cured using conventional methods and compounds. Peroxides, suitable for crosslinking or curing include a series of vulcanization and polymerization agents containing a, a'-bis (t-butylperoxy) -diisopropylbenzene and available from Hercules, Inc., under the registered designation VULCUP ™ , a series of such agents containing dicumyl peroxide and available from Hercules, Inc., under the registered Di-cup ™ designation as well as the Lupersol ™ peroxides made by Elf Atochem, North America and the organic peroxides of Trigonox ™ made by Moury Chemical Company. Lupersol ™ peroxides include Lupersol ™ 101 (2,5-dimethyl-2, 5-di (t-butylperoxy) hexane), Lupersol ™ 130 (2,5-dimethyl-2, 5-di (t-butylperoxy) hexin-3) and Lupersol ™ 575 (t-amyl peroxy-2-ethylhexonate). Other suitable peroxides include 2, 5-dimethyl-2, 5-di- (t-butylperoxy) hexane, di-t-butyl peroxide, 2,5-di (t-amyl peroxy) -2,5-dimethylhexane, 2, 5-di- (t-butylperoxy) -2,5-diphenylhexane, bis (alpha-methylbenzyl) peroxide, benzoyl peroxide, t-butyl perbenzoate and bis (t-butylperoxy) -diisopropylbenzene. The peroxide can be added by any conventional means known to skilled artisans. If a processing oil is used in the preparation of the polymer blends and other compositions including an EAODM interpolymer of the invention, the peroxide may be injected during the processing of the mixture or composition as a solution or dispersion in the oil of the invention. processing or other auxiliary for dispersion. The peroxide can also be fed into a processing apparatus at a point where the mixture or polymer composition is in a melting state. The concentrations of the peroxide in a solution or dispersion can vary over a wide range, but at a concentration of 20 to 40% by weight, based on the weight of the solution or dispersion, acceptable results are provided. The solution or dispersion can also be mixed with, and allowed to imbibe or absorb on, the dried polymer microspheres, or mixed dry. If the peroxide is a liquid, it can be used as such without first preparing a solution or dispersion in, for example, a processing oil. In other words, a liquid peroxide can be added to a high-speed mixer together with the dried polymeric microspheres, subject the contents of the mixer to the mixing action for a short period of time and then allow the contents to rest until the action of Imbibition or absorption is considered sufficiently complete. The absence of a discernible, separate liquid peroxide fraction can be considered as being sufficiently complete. On a small scale, mixing occurs in a Welex Papenmeier Type TGAHK20 mixer (Papermier Corporation) for a period of 30-45 seconds, followed by a 30 minute rest period. A more preferred method involves the introduction of the peroxide as a solid in a compositing apparatus together with the microspheres of the polymer when the microspheres are introduced into an apparatus of composition such as in the throat of an extruder. A preferred alternative method includes a step of adding the peroxide to a molten polymer in a composition apparatus such as a Haake apparatus, a Banbury mixer, a continuous Farrel mixer or a Buss kneader. A previously formed dry mixture of a solid peroxide and polymeric microspheres can also be introduced into the apparatus. The peroxide is suitably present in an amount within a range from 0.05 to 10% by weight, based on the total weight of the polymer in the mixture or composition. Low levels of peroxide may not show measurable gel content when measured by boiling xylene extraction, but will still show discernible evidence of improvements in rheology relative to the same composition except for peroxide. In other words, the amount of peroxide should be sufficient to effect at least partial cross-linking of the EAODM interpolymers of this invention. A peroxide content in excess of 10% by weight tends to provide materials that are too brittle for practical use. For efficient crosslinking of the peroxide, a sample needs to be subjected to heating for a sufficient period of time to decompose the peroxide thus generating free radicals for crosslinking. Depending on the peroxide, the crosslinking can be initiated at temperatures ranging from 70 ° C to 80 ° C for a low temperature peroxide, up to as high as 220 ° C up to 230 ° C using a high temperature peroxide. The time of crosslinking can vary from as little as a few minutes to as long as 30 minutes. One skilled in the art can determine the time required and the temperature for the crosslinking with the peroxide based on the temperature data of the known average duration for the different peroxides. Sulfur and phenolates (alkylphenol formaldehyde resins) and silicon hydrides serve as functional alternatives for peroxides. The sulfur produces satisfactory results at levels of 1-8% by weight, based on the total weight of the polymer in the mixture or composition. Phenolates such as 2,6-dihydroxymethyl alkylphenol also produce satisfactory results at levels of 1-15% by weight, based on the total weight of the polymer in the mixture or composition. Silicon hydrides produce satisfactory results at 1-10% levels, based on the total weight of the polymer in the mixture or composition. As noted above, cross-linking can also occur through irradiation with EB. An advantage of using EB irradiation is that, if desired, a cross-linked polymer system with at least partial cross-linking of the EAODM interpolymers of the present invention can be made without using the peroxide or any other crosslinking additives. Suitable doses of the EB irradiation range from 0.1 megarad (Mrad) to 30 Mrad, preferably from 0.1 Mrad to 10 Mrad, more preferably from 0.1 Mrad to 8 Mrad, and even more preferably from 0.1 Mrad to <; 5 Mrad. Although a dosage in excess of 30 Mrad can be used, for example 70 Mrad, doing this simply increases the cost without providing sufficient compensation in the improvements of the physical properties to justify the increased cost. The actual irradiation dose depends on several variables including the source and intensity of the radiation, the polymer to be cross-linked, the thickness of the material or article, and environmental and other factors. The preferred source of irradiation is a high-energy beam from an electron accelerator. The hi-energetic beams provide a suitable curing dosage and processing speeds as high as 1200 meters per minute. Several types of linear high-power electron accelerators are commercially available. Since the radiation levels required to effect cross-linking in the EAODMs of the present invention are relatively low, small power units, such as the Electrocurtain® Processor from Energy Sciences, Inc., Wilmington, Mass., Provide sufficient radiation . As noted above, other sources of high energy radiation, such as gamma rays can also be used.

The crosslinking may additionally occur by means of UV irradiation. In this embodiment, the composition of the interpolymer of this invention, preferably, may contain at least one photoinitiating agent. Suitable photoinitiators include, but are not limited to, - benzophenone, ortho- and para-methoxybenzophenone, dimethylbenzophenone, dimethoxy-benzophenone, diphenoxybenzophenone, acetophenone, o-methoxy-acetophenone, acenaftenquinona, methylethylketone, valerophenone, hexanophenone, (x-phenyl- butyrophenone, p-morpholino-propiophenone, dibenzosuberone, 4-morpholinobenzophenone, benzoin, benzoin methyl ether, 3-o morfolinodesoxibenzoina, p-diacetylbenzene, 4-aminobenzophenone, 4'-metoxiacetofenona, (x-tetralone, 9-acetylphenanthrene, 2- acetyl-phenanthrene, I 0-thioxanthenone, 3-acetyl-phenanthrene, 3-acetylindole, 9-fluorenone, indanone I, 1, 3, 5-triacetylbenzene, thioxanthen-9-one, xanthene-9-one, 7-H- bencfde] anthracene-7-one, benzoin tetrahydropyranyl ether, 4 '-bis (dimethylamino) benzophenone, F-acetonaphthone, 2' acetonaphthone, acetonaphthone and 2, 3-butanedione, benz [alantracen-7, 12-dione, 2, 2-dimethoxy-2-phenylacetophenone, (X, (x-diethoxy-acetophenone, CW- dibutoxiacetofenona, anthraquinone, isopropylthioxanthone and the like. Polymeric initiators include poly (ethylene / carbon monoxide), oligo [2-hydroxy-2-methyl-l- [4- ( 1-methylvinyl) -phenylpropanone], polymethylvinyl ketone, and polyvinylaril ketones.The use of a photoinitiator is preferable in combination with UV irradiation because it generally provides faster and more efficient crosslinking.The preferred photoinitiators that are available commercially they include benzophenone, anthrone, xanthone, and others, the Irgacure ™ series of photoinitiators from Ciba-Geigy Corp., including 2,2-dimethoxy-2-phenylacetophenone (Irgacure 65 1), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) and 2-methyl-l- [4- (methylthio) phenyl-2-morpholino-propan-1-one (Irgacure 907) .The most preferred photoinitiators will have a low migration from the formulated resin, as well as a low vapor pressure at the extru temperatures tion and sufficient solubility in the polymer or polymer blends to give a good cross-linking efficiency. The vapor pressure and solubility, or compatibility of the polymer, of many familiar photoinitiators can be easily improved if the photoinitiator is derived. Derivative photoinitiators include, for example, the higher molecular weight derivatives of the benzophenone, such as 4-phenylbenzophenone, 4-afliloxybenzophenone, 4-dodecyloxybenzophenone and the like. The photoinitiator can be covalently linked to the interpolymer of this invention or to a polymer diluent, as described hereinafter. The most preferred photoinitiators, therefore, will be substantially non-migratory from the polymeric material. The radiation must be emitted from a source capable of emitting radiation of the wavelength from 170 to 400 nanometers (nm). The dosage of the radiation should be at least 0.1 Joules per cm2 (J / cm2) and preferably from 0.5 to 10 (J / cm2) and even more preferably from 0.5 to approximately 5 (J / cm2). The dosage required on a particular application will depend on the configuration of the film layer, the composition of the layer, the temperature of the film that is irradiated and the particular wavelength used. The dosage required to cause cross-linking to occur for any particular set of conditions can be determined by the artisan. European Patent Application 0 490 854 A2 teaches a continuous process for crosslinking polyethylene with UV light. The EAODM interpolymers of this invention can be modified by, or grafted with other monomers. Any unsaturated compound that is organic and contains at least one ethylenic unsaturation (eg, at least one double bond) and at least one carbonyl group (-C = 0) or which can be used. be an unsaturated alkoxysilane, and that will be grafted to the interpolymer of EAODM. The grafted interpolymers can be mixed with other synthetic or natural polymers in the same manner as the non-grafted EAODM interpolymers. Monomers which are suitable for grafting or modification include the unsaturated carboxylic acids, as well as the anhydrides, esters and salts, both metallic and non-metallic, of such acids and unsaturated alkoxysilanes. The unsaturated carboxylic acid monomers preferably contain an ethylenic unsaturation which is conjugated to a carbonyl group. These acids include, for example, maieic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, alpha-methyl crotonic acid, and cinnamic acid. Unsaturated alkoxysilanes include, for example, vinyltrimethoxysilane and vinyltriethoxysilane. The monomer is more preferably maieic anhydride. The grafted EAODM interpolymers have a minimum unsaturated compound or a grafted monomer content of >; 0.01% by weight, and preferably > 0.05% by weight, based on the weight of the grafted EAODM interpolymer. The content of the unsaturated compound may vary upwards from the minimum in the manner that is convenient, but is typically < 10% by weight, and it is preferably < 5% by weight, more preferably < 2% by weight based on the weight of the grafted EAODM interpolymer. The unsaturated compound can be grafted to the EAODM interpolymer by any known technique, such as those taught in U.S. Pat. No. 3,236,917 and U.S. Pat. No. 5,194,509, the relevant teachings of which are incorporated into and become a part of this application, for reference. For example, in the '917 patent, the polymer is introduced into a two-roll mixer and mixed at a temperature of 60 ° C. The unsaturated organic compound is then added in the company of a free radical initiator, such as benzoyl peroxide, and the components are mixed at 30 ° C until the graft complements. In the '509 patent, the procedure is Similar except that the temperature of the reaction is higher, for example, 210 ° C to 300 ° C, and a free radical initiator is not used or is used at a reduced concentration. An alternative and preferred method of grafting is taught in U.S. Pat. No. 4,950,541, the relevant parts of which are incorporated in and form a part of this application for reference. The '541 patent teaches, in column 4, lines 16 to 28, the use of a twin-screw devolatilization extruder as an apparatus for mixed. When such is used. The apparatus, the EAODM interpolymer and the unsaturated compound are suitably mixed together and reacted within the extruder at temperatures above m.p. of the EAODM interpolymer and in the presence of a free radical initiator. The unsaturated compound is preferably injected into the molten EAODM within the zone of the extruder which is maintained under pressure. In another embodiment of this invention the grafted modified EAODM interpolymer is either dry blended or blended in the melt with another thermoplastic polymer, and then molded or extruded into a shaped article. Such other thermoplastic polymers include any polymer with which the EAODM interpolymer is compatible, and include both olefin and non-olefin polymers and industrial or engineering thermoplastics, as well as grafted and non-grafted versions of such polymers. The amount of grafted modified EAODM interpolymer that is mixed with one or more other polymers varies and depends on many factors, including the nature of the other polymer (s), the proposed final use of the mixture. , the presence or absence of additives and, if present, the nature of such additives. In these applications in which the grafted ethylene interpolymer is mixed with other polyolefin polymers, for example an ungrafted ethylene interpolymer or a conventional polyolefin polymer (LLDPE, HDPE, PP), the composition of the blend comprises < 70% by weight of the ethylene interpolymer (s) modified by the graft, preferably < 50% by weight, and even more preferably < 30% by weight, based on the total weight of the mixed polymers. The presence of the EAODM interpolymer modified by grafting in these mixtures, both for industrial or engineering materials and the compositions for cables and wires, provide impact properties and / or resistance to materials and compositions. In other embodiments, the grafted modified EAODM interpolymer comprises from a relatively minor amount (eg, 10% by weight), up to 100% by weight of the finished article. In those applications in which the paintability of a finished article is important, a graft-modified EAODM interpolymer content within a range of 10 to 50% by weight, based on the total weight of the finished article, provides satisfactory results with relation to a molded article that otherwise can not be painted otherwise, for example an article prepared from a polyolefin such as polyethylene, polypropylene, etc. A content of the EAODM interpolymer modified by < 10% by weight provides little or no benefit in terms of improving the polyolefin's painting capacity. On the contrary, although the contents of EAODM modified by > 50% by weight, for example > 70% by weight, can be used, the properties of the finished article such as flexural modulus can be unacceptably low while others such as distortion by heating can be too high compared to articles prepared without the modified EAODM interpolymer by grafting. The EAODM interpolymers of this invention, whether modified by grafting or not, and whether mixed with other polymers or not, may be compounds with any or more of the materials conventionally added to the polymers. These materials include, for example, process oils,. plasticizers, especially additives or pigments. These materials can be compounds with such interpolymers of EAODM or mixtures containing the same either before or after the cross-linking of the EAODM interpolymer occurs. The selection of such materials and the addition thereof to the EAODM interpolymers and the compounds including such interpolymers is considered within the competence of the skilled artisan. Process oils are frequently used to reduce one or more of the following characteristics of a composition: viscosity, hardness, modulus and cost. The most common process oils have particular ASTM designations depending on whether they are classified as paraffinic, naphthenic or aromatic oils. An artisan skilled in the processing of elastomers in general - and EAODM compositions in particular, will recognize which type of oil will be most beneficial. A useful amount of the process oil will be within a range from >; 0 to 200 parts by weight, per 100 parts by weight of the EAODM interpolymer. A variety of special additives can be advantageously mixed with the interpolymers of this invention to prepare the useful compositions of the art. Special additives include antioxidants; the surface tension modifiers; anti-blocking agents; the lubricants; antimicrobial agents such as organometallic substances, isothtazolones, organosulfides and mercaptans; antioxidants such as phenolic substances, secondary amines, phosphites and thioesters, antistatic agents such as quaternary ammonium compounds, amines, and ethoxylated, propoxylated or glycerol compounds; fillers and reinforcing agents such as carbon black, glass, metal carbonates such as calcium carbonate, metal sulfates such as calcium sulfate, talc, clay or graphite fibers; hydrolytic stabilizers; lubricants such as fatty acids, fatty alcohols, esters, fatty amides, metal stearates, paraffin and microcrystalline waxes, silicones and esters of orthophosphoric acid; mold release agents such as pulverized or fine particulate solids, soaps, waxes, silicones, polyglycols and complexing esters such as trimethylolpropanetristearate or pentaerythritoltetrastearate; the pigments, dyes and dyes; plasticizing agents such as esters of dibasic acids (or their anhydrides) with monohydric alcohols such as o-phthalates, adipates and benzoates; thermal stabilizers such as organotin mercaptides, an octyl ester of thioglycolic acid and a barium or cadmium carboxylate; ultraviolet light stabilizers used as a hindered amine, an o-hydroxy-phenylbenzotriazole, a 2-hydroxy, 4-alkoxybenzophenone, a salicylate, a cyanoacrylate, a nickel chelate and a benzylidene malonate and oxalanilide; and the zeolites, molecular sieves and other known deodorants. A preferred hindered phenolic antioxidant is the antioxidant Irganox ™ 1076, available from Ciba-Geigy Corp. Each of the above additives, if used, is present in an amount from > Or up to < 45% by weight, based on the total weight of the composition, desirably from 0.001 to 20% by weight, preferably from 0.01 to 15% by weight and more preferably from 0.1 to 10% by weight. Although more than one special additive may be present, the amounts of each additive are selected to give a total additive content of < 90% by weight, based on the total weight of the composition. The EAODMs of this invention or combinations thereof with other polymers may be compounds with one or more other materials and additives and manufactured in a variety of ways including, without limitation, extruded profiles, parts, sheets, ribbons or bands, insulation for cables and wires, foams, shrinkable tubing and films using any of a number of conventional processes for the processing of thermoplastic or thermosetting elastomers. The EAODMs, the mixtures and the resulting compounds can also be formed, spun or stretched into films, fibers, multilayer laminates or extruded sheets, thin layer coextruded coatings or sheets, or compounds with one or more organic or inorganic substances, or any machine suitable for such purposes. Any of the above forms can be multi-layered.

The following examples illustrate but do not limit, either explicitly or by implication, the present invention. Unless stated otherwise, all parts (pbw) and percentages (% by weight) are by weight, on a basis of total weight. The examples (Ex.) Of the present invention are identified by Arabic numerals and the letters of the alphabet identify the comparative examples (Ex. Comp.).

Experiments Section Ex. 1-4 and Ex. Comp. AD Preparation of the Polymer Examples 1-4, the Interpolymers of this invention and Comparative Example A were prepared using a 3.8 liter stirred reactor (1) providing a continuous addition of the reactants and continuous removal of the polymer solution, devolatilization, and polymer recovery. The catalyst system was a (t-butylamido) -dimethyl (? 5-2-methyl-s-indacen-1-yl) silantitanium (II) 1,3-pentadiene CGC, a cocatalyst of tris (pentafluorophenyl) borane (FAB) ) and a modified methylalumoxane purification compound (MMAO).

Tables ID to 4 show the physical properties for Examples 1-4 and Comparative Example A. Ethylene (C2), propylene (C3), and hydrogen (H2) were combined in a stream before introducing the stream into a stream. diluent mixture comprising a mixed alkane solvent (Isopar-E ™, available from Exxon Chemicals Inc.) and polyene (ENB) to form a mixed feed mixture. The combined feed mixture was injected continuously into a reactor. The catalyst (Cat) and a mixture of the cocatalyst (Cocat) and the scrubbing compound (Scav) were combined in a single stream, which was continuously injected into the reactor. Table IA shows the flow rates for the solvent, C2, C3, and ENB in kilograms per hour (kg / r). Table IB shows the concentrations and flux of Cat, Cocat and Scav in parts per million (ppm) and kilograms per hour (kg / h), respectively. Table IB also shows the Cocat / Cat and Scav / Cat relationships. Table IC shows the hydrogen flow, in standard cubic centimeters per minute (sscm), the amount of the polymer produced in kg / h, the Reactor Temperature (Temp) in ° C, and the Reactor Pressure in megapascals (MPa) . An output stream from the reactor was continuously introduced into a separator to continuously remove the molten polymer from the solvent and from C2, C3, H2 and ENB that did not react. The molten polymer was cooled in a water bath or a microsphere forming apparatus, the cooled polymer was cut into strips or converted into microspheres and the resulting solid microspheres were collected.

* Based only on the content of C2 and C3 * Measured in accordance with ASTM DI646 (MLi + 4 at 125 ° C) Irradiation Tests Using the EB irradiation, (a) the interpolymers of Ex. 1-4 and (b) the polymers of Ex. Comp. B-D were cross-linked. The ej . Comp. B is an elastomeric ethylene / octene copolymer (Engage® 8003 available from DuPont Dow Elastomers LLC) with a density of 0.885 grams per cubic centimeter (g / cc), a melt index (MI) or I2 of 1 decigram per minute ( dg / min), a molecular weight per GPC (MJ of 125,000, and a MWD of 2.0) Comp Example C is a LLPDE (an ethylene / octene copolymer available from The Dow Chemical Company as Dowlex 2045) with a density of 0.92 g / cc, an MI or I2 of 1 dg / min, a molecular weight per GPC (M ") of 110,000, and a MWD of 4.0.Example D is a copolymer of vinyl acetate-ethylene (Elvax ® 460 available from E. I. du Pont de Nemours and Company) with a density of 0.941 g / cc, an MI of 2.5 dg / min, a molecular weight per GPC (M ") of 80,000, a MWD of 5, and a vinyl acetate content of 18% by weight MI measurements employ ASTM D1238 at 190 ° C or a modified version thereof (for EVA copolymers) Two identical sets of plates were prepared two from each of the Ex. 1-4 and the Ex. Comp. B-D The plates were compression molded to a thickness of 0.32 centimeters (cm) (0.125 inches) using the following cycle: heating at 190 ° C for three minutes without pressure; application of a pressure of 18,200 kg while maintaining the temperature at 190 ° C; cooling with water at room temperature (approximately 25 ° C) while maintaining the pressure of 18,200 kg; and the release of pressure. A set of seven plates was used as a control (without irradiation); the other set of seven plates was irradiated with EB at a dosage of 2 Mrad. The data in Table 5 compare irradiated and non-irradiated plates. Deformation with heating was measured as described in the Insulated Cable Engineers Association Publication T-28-562, Published 3/81, revised 1/83. The warpage test involves hanging a weight on a test specimen of a weight to give a tension of 200 kilopascals (kpa) (29 pounds per square inch (psi)) in an oven heated to 200 ° C. At low levels of crosslinking in the specimen, the specimen is stretched up to 600% and then goes to the bottom of the furnace. When used in Table 5 below, "Failed" means that the sample in question went to the bottom of the oven. At higher cross-linking levels, the specimen exhibits a smaller elongation and provides a measurable percentage elongation. The deformation measurements "with heating" provide an indication that the degree of crosslinking when the deformation is measured with heating and the degree of crosslinking vary inversely proportionally. In other words, a reduction in the value of the deformation with heating is equal to an increase in the degree of crosslinking. The fraction of the insoluble gel (gel content) was measured as described in ASTM D 2765 using the hot xylene as the solvent. means not measured The data in Table 5 show that the interpolymers of Examples 1-4 have a higher crosslinking response with respect to the irradiation with EB (i.e. they crosslinked more efficiently as indicated by the% gel) than the polymers of the Ej. Comp. B and C. With one exception (Ex 2), the EAODM polymers provide performance during deformation by acceptable heating.

A theoretical explanation of the differences between Ex. 2 and Ex. 4 is constructed on a basis established by the difference in crystallinity prior to crosslinking. The interpolymer of Ex. 2 has a crystallinity of 20.5% while the interpolymer of Ex. 4 has a crystallinity of 39.9%. As noted in the Radiation Technology Handbook, Richard Bradley, Marcel Dekker, Inc., 1984 on page 106, curing with EB tends to occur in the non-crystalline regions of a polymer, the ENB, due to its large size relative to to C2 and the olefin monomers, it seems to lie in the amorphous or non-crystalline regions of the EAODM polymers. As such, even with equal percentages of the ENB, a more highly crystalline polymer (eg, Ex. 4 relative to Ex. 2) must provide a larger concentration of the ENB in its amorphous regions. This, in turn, produces a higher potential for crosslinking. As noted above, an increase in crosslinking leads to a reduction in elongation in the deformation test with heating. In view of a relatively lower crosslinking potential, a means of improving the deformation test results by heating of interpolymer 2 involves increasing the dosage of the radiation from 2 Mrad to a level of > 4 Mrad.

EXAMPLES 5-8 Four sample compositions, the Ex. 5-8, respectively, were prepared from the interpolymers of Ex. 1 to 4 mixing each EAODM interpolymer with 2% by weight of peroxide Lupersol® 130 (2,5-dimethyl-2,5-dibutylperoxyhexin-3 available from Elf Atochem) using a Haake mixer of 200 grams (g). The mixtures were prepared at a temperature of 130 ° C by mixing for 4 minutes at a rotor speed of 20 revolutions per minute (rpm). After the preparation of the four sample compositions each composition was compressed into a 0.32 cm plate for curing tests using a modified procedure. The modified procedure used the following cycle: heating at 130 ° C for two minutes while applying a force or pressure of 18,200 kg; cooling with water at room temperature (approximately 25 ° C) for a period of three minutes while maintaining the pressure of 18,200 kg; and the release of pressure. A sample of each uncured plate was stored for the oscillating disc rheometer (ODR) test according to the D-2084 test of the American Society for Testing and Materials (ASTM). The plates were cured using the following cycle: heating at 180 ° C under an applied force of 18,200 kg for '20 minutes; cooling to room temperature for a period of three minutes while maintaining the applied force of 18,200 kg; and release of applied force. The analysis of the percentage gel and the elongation by deformation with heating were determined (See Table 6). See Table 7 for ODR data. The plates prepared from the interpolymers of Ex. 1-4, but not the peroxide, they have less than 2% of the gel and failed in the deformation test by heating.

Table 6 Plate Properties The results shown in Tables 6 and 7 confirm that the EAODM polymers of this invention can be cross-linked using peroxides. The ODR data shows that an increase in the ethylene content of the EAODM polymer leads to a higher delta (?) Torque value. The skilled artisans recognize an increase in the degree of crosslinking. This allows one to use a lower level of the peroxide to obtain a desired degree of crosslinking than that required for EAODM polymers with a lower ethylene content. The highest crosslinking can be obtained with less peroxide which is an expensive component, thus allowing the end user to obtain a similar crosslink density at a lower cost. By way of contrast, conventional EAODM polymers prepared from the same monomers, but with an ethylene content of 80% or less, should produce torque values? lower and requires correspondingly higher amounts of peroxide to achieve the same level of crosslinking.

Example 9-10 and Ex. Comp. E The sampled composition of Ex. 9 was prepared from a mixture of 90% by weight of the polymer of Ex.

Comp. C and 10% by weight of Ex. 1. The composition of the sample of Ex. 10 was prepared from a mixture of 70% by weight of the polymer of Ex. Comp. C and 30% by weight of the Ex. 1. 100% by weight of the polymer of Ex. Comp. C was used as a control and designated as Ex. Comp. AND.

The mixtures were prepared by mixing the dry polymer microspheres in a rotating barrel, melt-compounding the dry-mixed microspheres in an 18 mm (mm) co-rotator twin screw extruder with a rheometer pulse device to provide the Haake torque. 9000, to provide an extruded rod.

The conditions of the extrusion are shown in Table 8 given below: The extruder rod was cooled in a water bath and the rod or bar was converted into microspheres. The plates were prepared using the procedure described above in Ex. 1-4. One plate of each sample was irradiated with EB at a dosage of 1 Mrad and a plate of each sample was irradiated with EB at a dosage of 2 Mrad using an EB unit of ten megavolts (MeV). A plate of each sample free of radiation exposure was stored for use as a control. The degree of crosslinking was used as in Examples 1-4.

The results in Table 9 demonstrate that the addition of 10-30% by weight of a representative EAODM interpolymer of the present invention can enhance the gel response (degree of crosslinking) for an irradiation of EB in LLDPE (Ex. Comp. E). The gel levels for the compositions of Ex. 9 and 10 at a dose of 1 Mrad and Ex. 9 at a dose of 2 Mrad fall within a range of the gel content of 20-60% by weight preferred for expansion of free-climbing foam. Gel levels of 30-40% by weight are more preferred. (Reference: Polymeric Foams, D. Klempner and K. Frish, ed., Chapter 9, pp. 201-203, Hanser Publishers, 1991). An increase in gel response at a low EB dosage, such as 1 Mrad, should significantly increase the capacity of existing EB units. Expert artisans can easily determine the optimum levels of EAODM and the radiation dosage for LLDPE and other polymers described herein.

Example 11 and Comparative Examples F-G Ex. Comp. F, which contains 100% by weight of the propylene copolymer (Profax ™ 8623, commercially available from Himont with a melt flow rate (ASTM D 1238) of 2, a density of 0.9 g / cc (ASTM D 792A- 2) and a flexural modulus (ASTM D 790B) of 965 MPa (140,000 psi), was used as a control.The compositions of Ex. Comp.G and Ex.11 each contain 70% by weight of the copolymer of the Ex: Comp.F and 30% by weight of a second polymer (the copolymer of Ex Comp.C for Comp.G.Example and the interpolymer of Ex.1 for Ex.11) The test plates were prepared using the procedure of Ex.1- 4. One set was retained as a control (without irradiation) and the remaining sets were exposed to the respective EB irradiation dosages of 2, 5, and 10 Mrads. determined using the procedure described in Ex.1- 4. Table 10 summarizes the gel test results.

The copolymer of Ex. Comp. F in Table 10 shows no response of the gel to irradiation with e-rays. Polypropylenes are already known to suffer from chain scission instead of cross-linking under irradiation with EB. (Reference: Radiation Technology Handbook, on pages 114-129). The composition of Ex. Comp. G exhibits some irradiation response, but at 5-10 Mrad dosage. On the other hand, the composition of the sample of Ex. 11 exhibits an irradiation response at a dosage of 2 Mrad comparable to that of the composition of Ex. Comp. G to 10 Mrad. Other EAODMs that represent the present invention, when combined with the polypropylene of Ex. li or with other polymers described herein, should provide similar results.

Example 12 and Example Comp. H Table 11 summarizes the flexural modulus (ASTM D-790) and tensile / elongation properties (ASTM D-638) for the interpolymers of Ex. Comp. A and Ex. 3, and the compositions of Ex. Comp. H and Ex. 12. The compositions of the sample for Ex. Comp. H and Ex. 12, respectively, were prepared by mixing 30% by weight of the interpolymer of Ex. Comp. A and the interpolymer of Ex. 3 with 70% by weight of the copolymer of Ex. Comp. C using the apparatus and the process of Ex. 5-8 except to increase the time to 5 minutes, the temperature to 190 ° C and the rotor speed to 40 rpm. The interpolymers of Ex. Comp. A and Ex. 3, and the compositions of Ex. Comp. H and Ex. 12 were converted to test plates using the procedure of Ex. 1-4 and the plates were subjected to the flexural and tension / elongation module tests.

The data in Table 11 show that the interpolymers of Ex. 3 have better mechanical strength than the interpolymer of Ex. Comp. TO, . as indicated by a flexural modulus and higher tensile properties. This superiority remains after mixing with the copolymer of Ex. Comp. C as shown by the comparison of the properties for Ex. Comp. H with those for Ej. 12. " Examples 13-14 and Ex. Comp. I-J The interpolymers of each of the Ex. Comp. A and Example 3 were combined with 2% by weight, based on the weight of the polymer, of the peroxide (Lupersol® 130, a 2,5 Dimethyl-2, 5-di- (t-butylperoxy) hexyne-3 available from Elf Atochem ) to give, respectively, Ex. Comp. I and Ex. 3 using the apparatus and method of Ex. 12, except for the reduction of the temperature to 130 ° C and the rotor speed to 10 rpm. In the same way, the mixtures for Ex. 14 and Ex. Comp. J were prepared from 70% by weight of the copolymer of Ex. Comp. C and, respectively, 30% by weight of the interpolymer of Ex. 3 and the interpolymer of Ex. Comp. A together with 2% by weight of the same peroxide, based on the weight of the combined polymer. The mixtures were converted into test plates and the plates were exposed to curing conditions using the procedure of Ex. 5-8. Table 12 summarizes the flexural modulus and the results of the tensile / elongation test. The data in Table 12 show that the interpolymer cured with the peroxide of Ex. 13 have superior mechanical properties when compared to those of Ex. Comp. I. The mixed composition cured with peroxide (Ex.14) also has superior mechanical properties when compared to the composition of the cured mixture with peroxide of Ex. Comp. J. These superior physical properties are even more surprising considering that the interpolymer of Ex. Comp. A used in these mixtures has a much higher Mw (higher Mooney value) than the EAODMs of this invention. These improved mechanical properties will allow such EAODMs to be used in blends with other polymers described herein where the retention of mechanical properties is important. Examples of such improved blends include more stable crosslinked polyolefin foams, wire linings and crosslinked wires of higher strength, and stiffer and stronger crosslinked articles.

Example 15 and Comparative Example K The interpolymer of Ex. 3 was mixed with a polypropylene homopolymer (PP) (Profax ™ PD-191, available from Himont) in a weight ratio of 70/30 (PP / Ex. 3) to make the composition of Ex. 15 using the apparatus and method of Ex. 9 and 10. The extruded material was compression molded into two sets of the test plates using the procedure described above for the irradiation tests. The PP polymer was compression molded only for two sets of the test plates of Ex. Comp. K. A set of the test plates was subjected to irradiation with EB at a dosage of 2 Mrad. The IZOD bars were cut from all the test plates and the bars were tested to verify the impact resistance of IZOD by notching (ASTM D-256 - Method A) at two different temperatures (23 ° C and 0 ° C). Table 13 summarizes the results of the IZOD test in kilojoules per meter (kJ / rm).

These results clearly show that the interpolymers of the present invention improve the resistance against IZOD impacts of the polypropylene both before and after irradiation. Similar results are expected with this and other EAODMs of this invention when mixed with any of the other polymers described herein.

Ex. 16-18 and Ex. Comp. L-P Three interpolymers (eg Comp.L, M and N) each having an ethylene content below 75% by weight were prepared using the method of Ex. Comp. A and of the Ex. 1-4. The composition and physical properties for the interpolymers of Ex. Comp. L-N are described in Tables 14 and 15. The compositions of Ex. 16, 17 and 18 were prepared from mixtures of variable amounts of the interpolymer of Ex. Comp. N and the interpolymers of Ex. 1, 3 and 4, respectively. The composition of Ex. Comp. P was prepared from a mixture of the interpolymers of Ex. Comp. M and N. The amounts of each polymer were selected such that the ethylene average weight% of the mixture was about 70% by weight. The mixtures were prepared using a Haake mixer. The polymers were added to the mixing apparatus at a temperature of about 120 ° C. The rotor speed was 30 rpm. The polymers were mixed and combined under these conditions for 10 minutes, at which point the temperature of the mixer was reduced to about 100 ° C and the rotor speed was increased to 60 rpm. The compositions of Ex. 16-18 and Ex. Comp. P were prepared by adding Carbon Black and Oil to the mixer and allowing them to mix for about 3 minutes. The sulfur and other curative materials or hardeners were added to the mixer and allowed to mix for about 2 minutes. After a total of 15 minutes, the rotor stops and uncured mixtures are removed from the mixer. A composition containing 100% by weight of the interpolymer of Ex. Comp. L and designated as Ex. Comp. Or it was prepared using the same apparatus and method. Table 16 summarizes the composition of the mixture of Ex. 16-18 and the Ex. Comp. O-P.

The curing (vulcanization) properties of Ex. 16-18 were determined on a curing meter without rotating parts (movable matrix rheometer - MDR) according to ASTM D-5289, at a temperature of 160 ° C. The values of the minimum torque (ML) and the maximum torque (MH), both in Newton-meters (N-M), and the time for 6? reaching 95% of maximum torque (T93) are shown in Table 17. Test specimens for retraction in a low temperature (TR) test were prepared and tested in accordance with ASTM D-1329. The test specimens were cut from vulcanized plates prepared from each composition. Each molded plate was vulcanized at 160 ° C for a total time equal to T95 plus 3 minutes. The temperatures at which the test specimens were retracted 50% (TR50) are shown in Table 18. The results in Tables 17 and 18 show that the interpolymers of this invention can be vulcanized at approximately the same speed as the Comparative EPDM. (Eg Comp.O) and the comparative EPDM mixture (eg Comp.P) with the added benefit of the higher TR50 values. Surprisingly, the retraction temperature data show that the addition of a crystalline EAODM polymer leads to improved operation for the vulcanized mixture. A lower retraction temperature indicates a more elastic or more rubber-like material at a low temperature. Improved operation at low temperature is unexpected since the retraction temperature must be increased because the tendency to crystallize increases.

The interpolymers of Ex. 19-21 were prepared using the method of Ex. 1-4 but at a production speed ten times (10X) greater than that of Ex. 1-4 (that is, the reactor was ten times larger and the flow velocities were ten times larger). Tables 19-22 show the composition and physical properties for Ex. 19-21.

Based solely on the content of C2 and C3.

* Measured in accordance with ASTM Di646 (MLi + 4 at 25 ° C) Ex. 22-30 and Ex. Comp. O-T The interpolymers of Ex. 1, 3, 19 and 20 were combined with various polymers and additives to give the compositions of Ex. 22-30. The various polymers were combined with additives and, in some cases with other polymers, to give the compositions of Ex. Comp. Q, R, S and T. The compositions of Ex. 22-30 and the Ex. Comp. Q- T are shown in Tables 23-25. Low density polyethylene (LDPE), the Petrothene NA 940000, was obtained from the Equistar Corporation. This LDPE polymer has a melt flow rate of 0.25, a polymer density of 0.918 and a crystalline melting point of 104 ° C. The natural rubber, SMR CV-60, was obtained from Akrochem Corporation and is characterized as a Standard Malaysian Rubber (SMR) stabilized with respect to viscosity, of a value of 60 Mooney. The styrene-butadiene rubbers (SBR), Plioflex 1712 and Plioflex 1502, were obtained from Goodyear Tire and Rubber Company. Plioflex 1712 is characterized as a Mooney viscosity SBR polymer of 46 extended with approximately 37.5 parts per hundred (phr) of the aromatic process oil. Plioflex 1502 is characterized as an SBR polymer of Mooney viscosity of 50. The polybutadiene rubber was obtained from Aldrich Chemical. The additives were carbon black, oil, zinc oxide, stearic acid, and sulfur vulcanizing agents, which consist of Butyl Zylate or Methyl Zylate (a dimethyl dithiocarbonate available from RT Vanderbilt), MTB, TMTD and sulfur. The various polymers, the interpolymers of Ex. 1, 3, 19 and 20, if any, carbon black, oil, zinc oxide and stearic acid were added to a Farrel BR Banbury mixer. The temperature of the Banbury was about 120 ° C to 150 ° C. The rotor speed was set at approximately 80 rpm. The mixture was combined for about 5 minutes. The mixture was removed from the Banbury and spread in the form of sheets on a Reliable roller mill. The roller mill was set at a temperature of approximately 110 ° C. The rotor speed was set at approximately 10 rpm. The sheet was cut into strips and added to the Farrel BR Banbury mixer. During this mixing step, the sulfur vulcanizing agents were added at a Banbury temperature of about 100 ° C to about 110 ° C. The rotor speed was set at approximately 30 rpm. The mixture was combined for about 2 minutes. The mixture was removed and placed in sheet form on a Reliable roller mill. The roller mill was set at a temperature of about 100 ° C to 110 ° C. The rotor speed was set at approximately 10 rpm. The prepared sheet of each mixture was allowed to cool and was subsequently subjected to further tests. * m ** ~ * «ua The vulcanization properties of the interpolymers of Ex. 22-30 and the Ex. Comp. Q-T were determined on a curing meter without rotating parts (movable matrix rheometer - MDR) in accordance with ASTM D-5289. These vulcanization properties were determined at a temperature of 160 ° C. The values of the minimum torque (ML), the maximum torque (MH) and the time to reach 90% of the maximum torque (T90) for each mixture are shown in Table 26.

The test specimens for abrasion resistance were prepared and tested in accordance with ISO 4649-1985 (E). The test specimens were cut from vulcanized plates prepared from each mixture. Each molded plate was vulcanized at 160 ° C for a total time equal to T90 plus 5 minutes. The size of the plate was 7.6 cm by 7.6 cm at a thickness of about 6.5 mm. Abrasion data are shown in Table 27 and are reported as volume loss relative to a standard. A lower value is considered to be indicative of a higher resistance to abrasion wear.

Examples 22-30 demonstrate that the addition of the crystalline EAODM of this invention to different rubber formulations (such as natural rubber, styrene-butadiene rubber and polybutadiene rubber) imparts improved performance and resistance against abrasion when compared to those mixtures that do not contain these polymers and do this without affecting the vulcanization performance as shown in the Table 26. Applications where abrasion resistance is necessary and improved resistance against abrasion could be advantageous include pneumatic tires, shoes, and conveyor belts.

Ex. 31-44 and Ex. Comp. U Examples 31-44 demonstrate the utility of the interpolymers of this invention in foam applications. The data has been obtained from different reticulated formulations. Typical methods for crosslinking the foam formulations containing the EAODM polymers include peroxide, sulfur, vinylalkoxysilane, hydrosilation, phenolic substances, electron beams, gamma and ultraviolet radiation. The foam data demonstrates the usefulness and improved foaming ability of crystalline EAODM polymers especially when mixed with other ethylene interpolymers including low density polyethylene (LLDPE), ethylene vinyl acetate (EVA) , ethylene copolymers such as ethylene-octene and ethylene-butene polymers, ethylene-styrene, LLDPE and HDPE. These data also demonstrate the improved foaming ability of crystalline EAODM polymers when mixed with polypropylene polymers including homopolymers and copolymers. Other types of foaming agents (for example carbonates) could be used to cause foams of cells or cells whether open or closed. The low density polyethylene (LDPE) in Ex. 40 was the Petrothene NA 940000, obtained from Equistar Corporation. Typical properties for this LDPE polymer are a melt flow rate of 0.25, a polymer density of 0.918 and a glass melting point of 104 ° C. The ethylene / vinyl acetate copolymer in Ex. 39 was Elvax 460, obtained from E. I. du Pont de Nemours and Company. Typical properties for this EVA polymer are a density of 0.941 g / cc, a melt flow rate of 2.5 dg / min, a molecular weight per GPC (Mw) of 80,000 and a molecular weight distribution of 5.0 and a vinyl acetate content of 18% by weight. The interpolymers of Ex. 19, 20 and 21 were combined as shown in Table 28 on a Farrel BR Banbury mixer. For Examples 31-33, the foaming agent and activators were added to the Farrel BR Banbury mixer at a melt temperature of about 130 ° C. For Examples 34 and 35, and Ex. Comp. U, the polypropylene and the foaming agent were added to the Farrel BR Banbury mixer at a melt temperature of about 175 ° C. After approximately 5 minutes of mixing, each formulation was removed from the Banbury and spread in the form of sheets on a Reliable roller mill. From these sheets, two compression molded test plates were prepared. The size of the plate was 12.7 cm by 12.7 cm at a thickness of approximately 0.3175 cm. One set of the test plates was irradiated with electronic rays at 2 Mrad while the other set of the test plates was irradiated with 5 Mrad electronic rays. After irradiation, the plates were tested to verify the gel content using the Standard Test Method for the Determination of Gel Content as described in the ASTM D-2765 test method. The content of the gel for each plate after irradiation is shown in Table 29.

Table 29 Gel Content Data Ex. And EJ. Comp. Content of the% Content of 5. of Gel at 2 Mrad Gel at 5 Mrad Ex. 31 72 91 Ex. 32 81 91 Ex. 33 38 75 Ex. 34 15 26 Ex. 35 19 29 Ex. Comp. U 0.3 0.5 The bow-shaped foams were prepared from Examples 31-33, irradiated both at 2 Mrad and 5 Mrad. The 5.1 cm by 5.1 cm test samples were cut from the irradiated, compression molded test plates and placed in a mold cavity of the same size and thickness. The mold with the cavity was placed in a hot hydraulic molding press, placed at a temperature of 165 ° C with a molding pressure of 9100 kg (20,000 pounds). The mold with the cavity was left in the press for about 10 minutes and the pressure was then released quickly. The sample was removed from the press and allowed to expand freely. After expansion, the density of the foam of each sample was determined by weighing a known volume. The density data of the foam are shown in Table 30.

Table 30 shows that the interpolymer mixtures of Ex. 31-33 can be foamed after cross-linking by irradiation and there is an optimal irradiation dosage depending on the ethylene content and the amount of gel content. For the polymers of this invention, a low irradiation dosage is preferred to obtain optimum foam densities. The volume-free increase foams, treated in an oven with a hot air stream, were prepared from Ex. 31-35 and Ex. Comp. U and irradiated to 2 Mrad. The test samples, 2.54 cm by 2.54 cm in size, were cut from the irradiated, compression molded test plates. For the Ex. 31-33, the test samples were placed in an oven with a stream of hot air at a temperature of 180 ° C for about 10 minutes. For the Ex. 34-35 and Ex. Comp. U, the test samples were placed in an oven with a stream of hot air at a temperature of 220 ° C for about 10 minutes. The test samples converted to foam were removed from the oven and the foam density of each sample was determined by weighing a known volume. The data of the density of the foam are shown in Table 31.

Table 31 shows the volume-free increase foams treated in a furnace with a stream of hot air that can be prepared from the interpolymers and the interpolymer mixtures of this invention. The density data of the foam shows that the mixtures containing the interpolymers of this invention exhibit a lower foam density. The foam density data for the polypropylene blends show the improved foam conformation of the samples of the mixture containing the interpolymers of the invention (Ex. 34 and 35) when compared to the sample of the polypropylene mixture. (Ex. Comp. U). It could be expected that the polymers of this invention could be blended with other ethylene polymers such as LDPE, EVA, LLDPE, EAODM, copolymers and terpolymers of ethylene alpha-olefin, ethylene-styrene and HDPE and subsequently irradiated to give the foam articles that have lower densities of foam. The formulations shown in Table 32 were prepared using the combination of a Farrel BR Banbury mixer and a Haake Rheocord 9000 mixer. All of the components of the formulation except the peroxide were premixed using a Farrel BR Banbury mixer at a melting temperature of about 130 ° C. After about 5 minutes of mixing, each mixture was removed from the Banbury and spread in the form of sheets on a Reliable roller mill. These sheets were then cut into irregular cubes of approximately 2 cm in size. For the peroxide addition, each pre-mixed sample (such as cubes) was added to a Haake Rheocord mixer, mixed and allowed to melt before the addition of Di-Cup 40 KE, a dicumyl peroxide. The conditions for mixing in the Haake mixer were a melting temperature of 130 ° C and a rotor speed of about 5 rpm. After about 5 minutes of mixing the molten material, each sample was removed from the Haake mixer and allowed to cool.

Each sample of the formulation was compression molded at a pre-cast temperature of 130 ° C using a hot hydraulic press. The mold cavity used for this operation was approximately 10.2 cm by 10.2 cm with a thickness of 1.3 cm. After molding at 130 ° C, the mold cavity containing the sample was then crosslinked at a temperature of 160 ° C using a total pressure of approximately 9,080 kg (20,000 pounds). The mold with the cavity containing the sample was left in the press for a time of approximately 20 minutes. After this time, the pressure was released quickly. The sample was removed from the press and allowed to expand freely. For each foam sample, the values of% gel content and foam density were determined as previously described. These data are shown in Table 33.

The data in Table 33 demonstrate that the foams can be prepared from the examples of this invention using peroxide crosslinking. Optimal amounts of the peroxide can be adjusted depending on the interpolymer added and the density of the desired foam. The formulations shown in Table 34 were prepared using the combination of the Farrel BR Banbury mixer and a Haake Rheocord 9000 mixer. All of the components of the formulation except the sulfur vulcanizing agents were premixed using a Farrel BR Banbury mixer to a melting temperature of approximately 130 ° C. After approximately 5 minutes of mixing, each formulation was removed from the Banbury and spread in the form of sheets on a Reliable roller mill. These sheets were then cut into irregular cubes of approximately 2 cm in size. For the addition of the sulfur vulcanizing agents, each pre-mixed sample (such as cubes) was added to a Haake Rheocord mixer, mixed and allowed to melt before the addition of the sulfur vulcanizing agents. The conditions for mixing on the Haake mixer were a melting temperature of 130 ° C and a rotor speed of about 5 rpm. After about 5 minutes of mixing the molten material, each sample was removed from the Haake and allowed to cool.

Each mixed sample was compression molded into a plate at a pre-molded temperature of 130 ° C using a hot hydraulic press. The size of the plate was approximately 12.7 cm by 12.7 cm at a thickness of approximately 0.3175 mm. From each plate, smaller test samples were cut. These test samples were 2.54 cm by 2.54 cm in size with a thickness of 0.3175 cm. These test samples were placed in an oven with a stream of hot air at a temperature of 200 ° C for about 5 minutes. Foamy test samples were removed from the oven and tested. For each foam sample, the values of gel% content and foam density were determined as previously described. The results are shown in Table 35.

Table 35 demonstrates that sulfur crosslinking of the polymers of this invention can produce acceptable foam articles. The optimum amounts of the sulfur vulcanizing agents can be adjusted depending on the interpolymer and the density of the desired foam. The interpolymers of this invention can be blended with other ethylene polymers such as LDPE and EVA (other ethylene polymers could include LLDPE, ethylene alpha-olefin copolymers, ethylene-styrene and HDPE), other synthetic or natural rubbers that they can be cured with sulfur, and subsequently crosslinked with sulfur to gfoam articles having low foam densities.

Ex. 45-47 An ethylene-butene-ethylidene norbornene terpolymer of this invention was prepared in a similar manner to Ex. 1-4. The composition and properties for the EAODM polymer are shown in Table 36.

The interpolymer of Ex. 45 was combined with sulfur and accelerators / phenolic vulcanizing agents in a Haake Rheocord 9000 mixer to make the formulations of Ex. 46 and 47. The formulation of Ex. 46 was prepared using the interpolymer of Ex. 45, the vulcanizing agent of sulfur and accelerators. The formulation of Ex. 47 was prepared using the interpolymer of Ex. 45, phenolic vulcanizing agents and accelerators. The conditions for mixing on the Haake mixer were a melt temperature of 130 ° C and a rotor speed of about 5 rpm. The polymer was added to the mixer and allowed to melt. After about 3 minutes, the sulfur or phenol vulcanizing agents and the accelerators were added. After about 2 minutes of mixing the molten material, the sample was removed from the mixer and allowed to cool. Sulfur and phenolic formulations are shown in Table 37.

The blends were tested to verify the vulcanization properties using a Standard Test Method to Verify the Properties of the Rubber in the Vulcanization Using a Gauge without Rotating Parts as described in ASTM D-5289 (Movable Matrix Rheometer - MDR). The mixture of Example 46 with the sulfur vulcanizing agent and the accelerators was tested at a temperature of 160 ° C. The mixture of Ex. 47 with phenolic vulcanizing agents and accelerators was tested at a temperature of 200 ° C. The values of the minimum torque (ML), the maximum torque (MH) and the time to reach 95% of the maximum torque (T95) are shown in Table 38.

The data in Table 38 show that the EAODM of Ex. 45 can be vulcanized with sulfur and accelerators / phenolic vulcanizing agents. Other types of crosslinking agents could be used including peroxide, irradiation (E rays, gamma rays, NV radiation), silane, and hydrosilation. Possible end-use applications for these polymers could be in polyolefin foams (footwear, automotive interiors), vulcanized rubber blends (tires, weather stripping provisions), cross-linked polyolefin blends (films, fiber, tubing), and vulcanized Thermoplastics (TPV's).

Ex. 48 The interpolymer of Ex. 20 was vulcanized using a platinum catalyst and vulcanization agents by hydrosilation. First, the interpolymer of Ex. 20 (100 pph) was added to a Haake Rheocord 9000 mixer and allowed to melt at a melting temperature of 130 ° C. After about 3 minutes, the hydrosilation curing agent (3 pph of Dow Corning Silicon Hydride Type 1107 Fluid) and the platinum catalyst (20 ppm SIP 6831.0 from Gelest, Inc.) were added and allowed to mix at a rotor speed of approximately 5 rpm. After about 5 minutes of mixing the molten material, the sample was removed from the mixer and allowed to cool to give the vulcanized interpolymer of Ex. 48 and tested to verify vulcanization properties using the Standard Test Method to Verify Rubber Vulcanization Properties Using a Meter without Rotating Parts as described in ASTM D-5289 (Movable Matrix Rheometer - MDR). The composition of the polymer mixed with the vulcanizing agent by hydrosilation and the catalyst was tested at a temperature of 190 ° C. The minimum torque (ML) was 0.04 N-m, the maximum torque (MH) was 0.1 N-m, and the time to reach 95% of the maximum torque (T95) was 16.50 minutes. This leads to the interpolymers of this invention being able to be cured successfully using the vulcanization by hydrosilation.

Ex. 49 and Ex. Comp. V The following example and comparative example compare the biaxial orientation of the linear low density polyethylene (LLDPE) with a mixture of LLDPE with the interpolymers of this invention. The subsequent utility of both in the applications of a shrinkable film is also compared. The interpolymer of Ex. 19 was mixed with the LLDPE of Ex. Comp. C in a weight ratio of 10/90, respectively, to prepare the mixture of Ex. 49. Mixing was done in a single screw L / D extruder (Length / Diameter) of 36/1 of 64 mm. The following conditions were used on the 64 mm extruder: the Drum Temperature Zones were Zone 1 = 82 ° C, Zone 2 = 127 ° C, Zones 3-5 = 190 ° C with the Temperature of the Sifter Changer = 204 ° C and the Adapter Temperature and Matrix = 218 ° C. The extruder speed was 31 rpm. The filaments were extruded, the temperature was reduced with water, then they were minced into microspheres. These compounds converted into microspheres were extruded into sheets or sheets using a 24/1 50 mm single screw L / D extruder. The temperature zones of the extruder drum were Zone 1 = 216 ° C, zone 2 = 238 ° C, Zone 3 = 249 ° C, Adapter Temperature and Matrix = 218 ° C. The speed of the extruder was 34 rpm at 19.5 amps. The Roller Temperature for the Cast Material was 39 ° C, the width of the die was 30.5 c., The thickness of the sheet was 0.64 mm, and the width of the sheet was 52.4 cm. The sheets or sheets of the mixtures of Ex. 49 and the LLDPE of Ex. Comp. C were rolled onto cardboard cores. These sheets or sheets were then irradiated with electronic beams at a dosage of 4.0 Mrad at a line speed of 6.1 m / min., To produce the irradiated leaves or sheets of the mixture of Ex. 49 and the LLDPE of Ex. Comp. V. The irradiated laminates were then oriented in the machine direction (MDO) at a draw ratio of 5: 1 using a series of hot rollers with a different roller speed. The conditions for stretching with MDO were a preheating temperature of 98.3 ° C, slow drawing rollers operating at 2.4 m / min, and 109 ° C, fast drawing rollers operating at 12.3 m / min., And 109 ° C. C, an annealing roller at 12.3 m / min., And 36 ° C, a cooling roller at 12.3 m / min., And 19.4 ° C. The thickness of the sheet was 0.13 mm. The sheet stretched at the MDO was oriented in the transverse direction using a laying frame device heated by means of a convection oven and equipped with a flexible holding system and horizontal chain for orientation in the transverse direction (TDO). The conditions used for stretching in the TDO for Ex. Comp. V were a preheat temperature of 113 ° C, a draw temperature of 113 ° C, and an annealing temperature of 96 ° C. The conditions used for stretching in the TDO for a mixture of Ex. 49 were a preheat temperature of 116 ° C, a draw temperature of 116 ° C and an annealing temperature of 99 ° C. The films were cooled by means of circulating ambient air prior to finishing. The thickness of the film was 0.025 mm. The films were tested to verify the cross-linked gel according to Method A of ASTM D-2765. The film of Ej. 49 had an average gel content of 25.41%. The film of Ej. comp. V had an average gel content of 0.68%. These results show the great increase in the crosslinking capacity of the mixtures containing the polymers of this invention.

The tensile strength in the breaking of the film of Ex. 49 and Ex. Comp. V was measured at the MDO and TDO addresses in accordance with ASTM D-882. The results are shown in Table 39. The film of Ex. 49 exhibited a tensile strength at the highest break in the directions of both MDO and TDO than Ex. Comp. V.

The tension during the shrinkage was measured in the MDO direction at 125 ° C, in accordance with ASTM D2838, Method A. The film of Ex. 49 had a tension during shrinkage in the MDO direction of 1.73 MPa and Ex. Comp. V had a tension during the shrinkage in the MDO direction of 1.13 MPa. Accordingly, biaxially irradiated films with an electron beam containing the highly crystalline interpolymers of the invention exhibit higher levels of crosslinking, tensile strength at break, and stress during shrinkage, than films lacking interpolymers. of the invention. These interpolymers of the invention can be used as mixed components or alone to exhibit the high response of the gel to irradiation with electron beams for the shrinkable, biaxially oriented films.

Ex. 50-51 and Ex. Comp. W-X The interpolymer of Ex. 20 was mixed with an LDPE, LD 400.09 (available from Exxon Chemical Company), which has a melt index of 2.8 dg / min., And a density of 0.917 g / cc and a high density polyethylene (HDPE), Sclair 59A (available from Nova Chemicals), which has a melt index of 0.7 dg / min., and a density of 0.962 g / cc. The mixture with the LDPE produced the composition designated as Ex. 50 and one with the HDPE produced the composition designated as Ex. 51. 100% by weight of the LDPE was designated as Ex. Comp. W. 100% by weight of HDPE was designated as Ex. X. The mixed compositions were prepared on a co-rotating screw extruder of Werner Pfleiderer ZSK-30 with configurations of the medium-high shear screw. The medal compositions are shown in Table 40 and the mixing conditions are shown in Table 41.

The mixtures converted to microspheres in Table 40, after being mixed and converted into microspheres according to Table 41, were processed by extrusion in sheet form using a Killion single screw extruder of L / D 24/1. of 50 mm equipped with a coating matrix of 15 cm in width. The conditions used to extrude these sheets or sheets are shown in Table 42.

A one millimeter thick coating of Ex. Comp. W-X and mixtures of Ex. 50-51 was produced and used on a block of three rolls of 25 cm width Killion. The leaves were then irradiated by means of an electronic beam at a dosage of 2 Mrad. The irradiated sheets were tested for a gel response as measured according to ASTM D2765, Method A. The results are shown in Table 43. The coating samples containing the polymers of this invention exhibit much higher gel levels than the Ej. Comp. W and X which do not contain the polymers of this invention.

Table 43 Gel Content Data Ex. Comp. X Ex. Comp. W Ex. 50 Ex. 51 Average 2.64 9.37 51.2 59.93 of Gel (%) The irradiated coating was cut into strips of 20 cm x 10 cm. These strips were stretched in the machine direction on a United tension testing machine equipped with an environmental chamber. The tension testing machine was equipped with a multi-head fastener capable of holding the clamp through a width of 10 cm. Prior to stretching, the sample was allowed to preheat in the ambient chamber at the preset temperature for ten minutes. The temperature of the environmental chamber preset for each mixture is shown in Table 44. Different chamber temperatures were used depending on the type of polyethylene used. Different chamber temperatures were used depending on the type of polyethylene used. The temperature of the chamber was set at or near the melting point of the polyethylene. After the ten minute preheat time, the coating samples were drawn at a draw ratio of 2: 1 in the machine direction using a crosshead speed of 50 mm / min. Immediately after reaching a drawing ratio of 2: 1, the crosshead was stopped, the environmental chamber was opened, and the samples, still under tension, were cooled with air from the pressure pipes. The stretched liner samples were tested to verify shrinkage stress at 150 ° C in accordance with ASTM D2838, Method A. Table 45 shows the results of shrinkage stress. The tension in the contraction was four or five times higher for the examples of this invention (Ex. 50-51) than for Ex. Comp. W-X which did not contain the polymers of this invention. The highly crystalline EAODM can be used in blends with either LDPE, HDPE, or other polyethylenes to give shrinkable items, such as shrinkable sleeves, shrink tubing, shrink liners, etc., with a crosslinking and tension at the highest contraction in one orientation and at dosing levels of the same electron rays.

Ex. 52 The interpolymer of Ex. 2 (38.59 kg / hr (85 pph) was mixed on a two-roll mill with 1 part of 4-chlorobenzophenone and 15 parts of hexanediol diacrylate to provide the formulation of Ex. 52. Slices of thickness of 2 mm were pressed Then, from the formulation, the slice was then exposed to a 5 cm long UV radiation lamp of 80 W / cm.The lamp was placed 10 cm from the slice and the exposure time was 4 minutes. of the exposure, the crosslinked interpolymer of Ex. 52 had a compression adjustment (25% deflection) at 125 ° C for 70 hours of 45% .. These results clearly indicate that the highly crystalline EAODM-based compounds of this invention they can be cross-linked using ultraviolet light.

Ex. 53-56 and Ex. Comp. And the interpolymers of Ex. 2, 19, and 20 were grafted with maieic anhydride. 240 grams of each interpolymer were added to a Haake mixer at a temperature of 200 ° C. The rotor speed was set to 50 rpm. The polymer was allowed to melt for about 1 minute, followed by the addition of 7.2 grams of maieic anhydride. This operation was carried out with the metal gate in the closed position. After about 5 minutes, the rotor was stopped and the grafted interpolymer of Ex. 53-55 was removed from Haake's mixer. The amount of maieic anhydride grafted onto each polymer was determined using infrared absorption with the interpolymers of Ex. 53 which is 0.35% by weight, Ex. 54 which is 0.40% by weight and Ex. 55 which is 0.50% by weight of the maieic anhydride. The interpolymers of Ex. 53 and Ex. 2 were mixed with a polyamide polymer (Capron 8200 obtained from Allied Signal). The polyamide polymer was predried at 70 ° C for 24 hours before use. The interpolymers of Ex. 53 and Ex. 2 were granulated in a K-Tron granulator to an average diameter of approximately 0.47 cm (0.1875 inches) before mixing in the extruder. The mixture was prepared on an 18-millimeter Haake co-twin twin screw extruder having an L / D ratio of 30: 1. The speed of the extruder was set at 50 rpm. The temperatures of the area were profiled from 240 ° C to 260 ° C from the feed throat to the matrix. The temperature of the molten material in the matrix was approximately 260 ° C. The extruder was equipped with a two-hole die, water bath, pneumatic blade and filament shredder. The molten polymer filaments were cooled in a water bath and converted into microspheres to an average microsphere size of about 0.317 cm (0.125 inches) to give Ex. Comp. Y (80% by weight of Capron 8200 and 20% by weight of the interpolymer of Ex. 2) and the interpolymer mixture of Ex. 56 (80% by weight of Capron 8200 and 20% by weight of the grafted interpolymer of Ex. 53). The grafted interpolymer of Ex. 56 and Ex. Comp. And they were injection molded onto an Arburg Injection Molding machine using a standard ASTM mold. The IZOD test bars were molded to a standard thickness of 0.317 cm (0.125 inches). The molding conditions were of a melting temperature of 260 ° C with a mold temperature of 80 ° C. The injection molded IZOD test rods were provided with notches and tested to verify the impact properties at room temperature in accordance with ASTM conditions. The impact properties of IZOD at room temperature are shown in Table 46. The interpolymers grafted with maieic anhydride of this invention can modify the impact characteristics of a polyamide polymer (Nylon 6). When the interpolymers of this invention are not grafted with maieic anhydride, the compality is poor and is reflected in poor performance against IZOD impacts.

Ex. 58-61 and Ex. Comp. Z-AA These examples compare the adhesion of the polymers of LDPE, HDPE and EAODM of low density polyethylene of this invention with respect to a substrate of styrene-butadiene rubber (SBR). Styrene-butadiene rubber (SBR), Plioflex 1502, was obtained from Goodyear Tire and Rubber Company. The Plioflex 1502 sample is characterized as a 50-viscosity styrene-butadiene rubber from Mooney. The LDPE, Petrothene NA 940000, was obtained from the Equistar Corporation. Typical properties for this LDPE polymer are a melt flow rate of 0.25, a polymer density of 0.918 and a crystalline melting point of 104 ° C. The HDPE, Petrothene LR 73200, was obtained from Equistar Corporation. Typical properties for this HDPE polymer are a melt flow of 0.30, a polymer density of 0.955 and a crystalline melting point of 125 ° C. The compression molded plates were prepared from each of the styrene-butadiene rubber, LDPE, HDPE and the interpolymers of Ex. 1, 3, 19, and 20. The plates were 15.2 by 15.2 cm having a thickness of approximately 3.17 mm. The specimens for the adhesion test, 2.54 cm (width) by 5.58 cm (length) were cut from the plates. The adhesion of LDPE, HDPE, and the interpolymers of Ex. 1, 3, 19, and 20 to the SBR was evaluated by placing three test specimens of each type of polymer in contact with the styrene-butadiene rubber. The polymer laminates for the styrene-butadiene rubber were placed in an oven set at 150 ° C. After one hour, the polymer laminates for the styrene-butadiene rubber were removed from the oven, allowed to cool and checked manually for adhesion. The adhesion test was carried out using a 90 degree manual pull. The level of adhesion was determined by evidence of cohesive failure between the test polymers and the styrene-butadiene rubber substrate. The LDPE (eg Comp.Z) and HDPE (eg Comp.A.A.) laminates showed no adhesion while the laminates of Ex. 58, 59, 60, and 61 (prepared from the interpolymers of Ex. 1, 3, 19, and 20 < , .. respectively) exhibited adhesion. In addition, better adhesion was obtained when the ethylene content of the crystalline EAODM polymer was increased. The adhesion of crystalline EAODM polymers could be important in a number of different elastomeric applications including tires for example, such as the low permeability internal coating), the provision of automotive linings (for example, in the wear resistant layer and COF (Coefficient of Friction) low), vulcanized rubber composite materials (for example, in windshield wipers and machine engine mounts) and other articles laminated or co-extruded.

Ex. 62 and Ex. Comp. AB 15% by weight of the interpolymer of Ex. 1 (15% by weight) with 85% by weight of the EPDM Nordel IP 4770 which is available from DuPont Dow Elastomers) on a Farral ID Banbury to give the mixture of Ej. 62. The typical properties for Nordel IP 4770 are an ethylene content of 70% by weight and a Mooney Viscosity ML (1 + 4) at 125 ° C of 70. 100% by weight of Nordel IP 4770 was used as a control and it was designated as Ex. Comp. AB. The mixture of Ex. 62 and the polymer of Ex. Comp. AB were each extruded onto a Davis-Standard extruder using a standard rubber screw (the L / D is 20: 1) at a screw speed of 17 rpm using a die for the provision of gaskets. Drum temperatures were 65.5 ° C in zone 1, 71 ° C in zone 2, 82 ° C in zone 3 and a die temperature of 37.8 ° C. The extruder speed was 81.3 mm / sec. The measurements once the matrix was passed were carried out at 15 cm from the matrix. The measurements at the end of the line are taken approximately 6 m from the matrix after the extruded material traveled through the blow chamber with air at room temperature. The mixture of interpolymers of Ex. 62 had a post-matrix height of 4.76 mm and a height of the end of the line of 4.76 mm while the Ex. Comp. AB had a post-matrix height of 5.56 mm and a height of the end of the line of 3.97 mm.

The addition of the interpolymer of Ex. 1 to Ex. Comp. AB improves both the tensile strength of the material before firing (Table 47) and the resistance to collapse or crushing of the material, both of which are a desirable improvement for profile extrusion applications such as hoses and gaskets. Because the profiles need to maintain their matrix shape until the materials can be cured.

Ex. 63-72 and Ex. Comp. AC-AD The blends in Table 48 were prepared using a "right-side up mixing procedure" (loaded polymers and resins before fillers and oils) in a Reliable (size B, chamber volume of 1.7 1 ), internal tangential rotor mixer operating at 70 rpm. The weights of the ingredients were adjusted to provide 70% filling of the mixer volume. Amorphous EPDM interpolymers, Nordel IP 4570 and Nordel IP 4770 were used. Typical properties of Nordel IP 4570 are an ethylene content of 50% by weight and a Mooney Viscosity ML (1 + 4) at 125 ° C of 70. The amorphous interpolymers and crystalline interpolymers of the invention were charged to the mixer first. , followed by the fillers (carbon black, calcium carbonate) and oil. The gate was lowered and the mixtures were combined at 88 ° C. At 88 ° C the gate was raised and the throat and gate were cleaned of loose fillers. The gate was lowered and the compounds discharged at 127 ° C and extended completely as sheets on a 40.6 cm mill. The compounds were conditioned at 23 ° C for 24 hours before the addition of the vulcanizing agents. The compounds were charged to the mixer and mixed at 66 ° C. The gate was raised and cleaned, then the vulcanizing agents were added. The gate was lowered and the compounds were taken at 88 ° C and the throat and gate were cleaned. The gate was lowered and the compounds discharged at 104 ° C and extended completely as sheets on a 40.6 cm mill.

The procedure for determining the strength before firing of the blends in Table 48 was based on ASTM D412 with the following modifications. The mixtures were compressed in a mold for 0.5 minutes at 115 ° C. The mold was then cooled for 2 minutes before the compressed sheets or sheets were removed. The compressed sheets or sheets were 1.91 -21.6 thick. The test samples were cut from the sheet or sheet using a 12.7 mm wide by 114.3 mm long matrix. The samples were subjected to stress at a speed of 127 mm / min. Fatigue at low voltages (10 - 50% of the voltage) provides a good indication of the "resistance before firing" as defined in the extrusion processes. fifteen The formulations of Ex. 63-72 (Table 49) show the increase in hardness, the 100% modulus, and the strength before firing with increasing levels of the interpolymers of the invention. These increases are greater than what could be predicted by the average ethylene level of the mixture, when compared to the results achieved with an ethylene polymer with a purity of 50% or 70%. As a result, higher modulus and hardness levels can be achieved at lower average ethylene levels. Lower ethylene levels provide improved sealing performance at a low temperature as measured by the Retraction Temperature and Compression Adjustment.

Ex. 73-76 and Ex. Comp. AE-AF Some applications require compositions of high hardness (ie Shore D hardness greater than about 40). The Ej. 73-76 and the Ex. Comp. AE-AF demonstrate that the compositions of the invention exhibit properties which are advantageous for high hardness applications. The interpolymer of Ex. Comp. AE is Nodel IP 4725P, an EPDM available from DuPont Dow Elastomers. The interpolymer of Ex. Comp. AF is Nordel IP 4520, another EPDM available from DuPont Dow Elastomers. A comparison of the physical and compositional properties for the interpolymers of Ex. 1, 4 and 20 and the Ex. Comp. AE and AF are shown in Table 50. The interpolymers of Ex. 1, 4, and 20 were mixed with Ex. Comp. AE and AF. The mixtures were prepared in 2 stages in an internal mixer of 1.2 liters (Shaw - Intermix KO). The filling coefficient was 64%. In a first stage, the masterbatch was prepared in a semi-conventional method in which all the ingredients except sulfur, CaCO3 and vulcanizing agents were introduced into the mixer at 40 rpm, then sulfur and CaCO3 were introduced. seconds before the Black (Carbon) Incorporation Time (BIT) and emptied 90 seconds after the BIT or at 120 ° C. The BIT is the time required to incorporate the filler during the mixing operation. However, the BIT is more than just an indication of the mixing cycle time; it also indicates the mixing efficiency and the dispersion speed of the filler. On a graph of the mixing curve with time on the x-axis and the power on the y-axis, the energy consumption reaches a maximum point during the course of the mixing operation. The time in which the maximum point occurs is the BIT. In a second stage, sulfur and vulcanizing agents were added to the master batch in the internal mixer at 30 rpm, then discharged after 2 minutes or at 11 ° C. Table 51 shows the composition of the mixtures and Table 52 shows the mixing ratios for the various polymers used.

The results in Tables 53 and 54 show that the incorporation of the interpolymers of Ex. 1, 4, or 20 in the interpolymers of Ex. Comp. AE and AF increase tensile strength, modulus, tear strength, and hardness of mixtures of Ex. 73-76 over those of the interpolymers of Ex. Comp. Hardness levels above approximately a hardness of 40 (?) Shore D allow such polymers to be used in high hardness building or automobile fitting supply applications. For such applications, the mixing operation has to be fast (productivity) and efficient (a good dispersion of the fillers is required to match the requirements of the surface appearance). Surprisingly, mixtures of the polymers of the invention with Ex. Comp. AE and AF provided rapid incorporation of carbon black (BIT brief) and dispersion in efficient mixing. In contrast, an interpolymer of the pure invention (Ex. 1) had a BIT of about twice that of the mixed products. It could be expected that the adjustment of the compression and the low temperature operation (TR) of Ex. Comp. AE-AF will change disadvantageously with the addition of highly crystalline material. However, as Table 54 shows, the values of both compression adjustment and TR remain essentially unchanged when the interpolymer of Ex. Comp. AE is mixed with the interpolymers of the invention. When an EAODM of lower crystallinity is used (eg AF Comp), but with a higher charge of the highly crystalline material (ex. 76) to obtain the same total crystallinity of the interpolymer mixtures of Ex. 74 and 75, the values of TR and adjustment of the compression at low temperature really improve considerably, even when the interpolymer mixture of Ex. 76 has the highest percent by weight of the highly crystalline material by 50%. Additionally, the processing in a roller mill improved considerably, because the compound provides a better stratification on the equipment. The total crystallinity of the mixtures of Ex. 74-76 remained constant around 19%, which was comparable to that of the interpolymer of Ex. 1 to 20% crystallinity. These types of properties find applications in fields such as profiles, injection molded parts, hoses, and bands where such improvements are often advantageous.

Ex. 77 and Ex. Comp. AG-AH The interpolymer of Ex. 7 was molded by injection into bars of 12.7 mm (0.5 inches) by 6.35 mm (0.25 inches) for the impact test according to ASTM D 4020. These rods were exposed to an irradiation of e rays of 5 Mrads to produce the irradiated interpolymer of Ex. 77 The ej . Comp. AG is a high density polyethylene, melting index of 17.5, density of 0.962 commercially available with Mn of 17,700 and Mw of 58,600 (ALATHON 6017 available from Equistar). The ej . Comp. AG was injection molded under conditions similar to those used to mold the interpolymer of Ex. 7. The Ex. Comp. AH is a 6.35 mm (0.25 inch) thick ultra high molecular weight HDPE sheet obtained from the Laboratory Supply Corporation and cut into 0.5 mm (0.5 inch) bars for the test. The irradiated interpolymer of Ex. 77, in the company of an interpolymer of Ex. 7 which was not irradiated, were tested to verify the impact resistance in the company of Ex. Comp. AG and AH in accordance with ASTM D 4020, with the modification that a falling weight was used instead of a pendulum. The falling weight was 5.42 kg and was dropped at a distance of 73.66 cm. The impact energy was 39.2 Newtons. Table 55 shows that the impact resistance of the interpolymers of this invention is significantly better than that of the interpolymer of Ex. Comp. AG and AH. Table 55 also discloses that irradiation at 5 Mrads produces a vulcanized interpolymer having an operation at impact conditions essentially equivalent to the irradiated interpolymer of Ex. 7 It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims

CLAIMS Having described the invention as above, the content of the following claims is claimed as priority: 1. An interpolymer composition, characterized in that it comprises an interpolymer of ethylene / α-olefin / random polyene monomer comprising: (a) ethylene in an amount of from 84 to 99 weight percent, (b) an α-olefin containing from 3 to 20 carbon atoms in an amount within a range from greater than 0 to less than 16 weight percent, and ( c) a polyene in an amount of greater than 0 to 15 weight percent polyene, all percentages are based on the weight of the interpolymer and selected up to a total of 100 percent, the interpolymer has a crystallinity greater than 16 percent and a glass transition temperature of -45 ° centigrade or greater.
2. The interpolymer composition according to claim 1, characterized in that the interpolymer has a melting point greater than 70 ° C, and a heat of melting greater than 11 calories per gram.
3. The interpolymer composition according to claim 1, characterized in that the interpolymer has a molar ratio of ethylene: α-olefin greater than 95: 5.
4. The interpolymer composition according to claim 1, characterized in that the interpolymer has a molecular weight distribution (Mw / Mn) within a range from greater than 1 to 15.
5. The interpolymer composition according to claim 4, characterized in that the interpolymer has a molecular weight distribution (Mw / Mn) within a range from greater than 1 to 4.
The interpolymer composition according to claim 1, characterized in that the interpolymer is produced by polymerizing the ethylene monomers. , α-olefin and polyene in the presence of at least one metallocene or catalyst of restricted geometry.
The interpolymer composition according to claim 1, characterized in that it further comprises at least one natural or synthetic polymer in an amount sufficient to form a mixture containing from 2 to 98 weight percent of the interpolymer, based on the weight of mix.
8. The interpolymer composition according to claim 7, characterized in that the natural or synthetic polymer is a monoolefin homopolymer or a polymer having at least two different monoolefins polymerized therein.
9. The interpolymer composition according to claim 8, characterized in that the monoolefin is a C2-20 alpha-olefin monomer.
The interpolymer composition according to claim 9, characterized in that the alpha-olefin monomer is selected from the group consisting of ethylene, propylene-1, butene-1, hexene-1 and octene-1.
The interpolymer composition according to claim 8, characterized in that the natural or synthetic polymer is selected from the group consisting of conventional EAODM interpolymers with an ethylene content of 80% by weight or less, polyethylene copolymers, polypropylene , ethylene / propylene, ethylene / butene, ethylene / hexene and ethylene / octene, ethylene / propylene / carbon monoxide interpolymers, ethylene / styrene interpolymers, and ethylene / vinyl acetate copolymers.
12. The interpolymer composition according to claim 11, characterized in that the natural or synthetic polymer is a polyethylene selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, intermediate density polyethylene. , and ultra low density polyethylene.
13. The interpolymer composition according to claim 7, characterized in that the natural or synthetic polymer is a natural rubber, butadiene rubber, styrene-butadiene rubber, polyisoprene, polyisobutylene or polychloroprene.
14. The composition according to claim 1, characterized in that the interpolymer of the ethylene / α-olefin / random polyene monomer further comprises a grafted monomer selected from the group consisting of the unsaturated carboxylic acids, the anhydrides of the unsaturated carboxylic acid, the esters of the unsaturated carboxylic acid and the salts of the unsaturated carboxylic acid, both metallic and non-metallic.
15. The composition according to claim 14, characterized in that the grafted monomer is maieic anhydride.
The composition according to claim 14, characterized in that the grafted monomer is present in an amount within a range from 0.01 to 10 weight percent, based on the weight of the ethylene / alpha-olefin / polyene monomer interpolymer grafted.
17. The composition according to claim 1, characterized in that it also comprises the Í32 less an additive selected from the group consisting of plasticizers, special additives and pigments.
The composition according to claim 17, characterized in that each additive is present in an amount within a range from greater than 0 to not more than 45 weight percent, based on the weight of the total composition, provided that the Total additive content is less than or equal to 90 weight percent, based on the weight of the total composition.
19. The composition according to claim 17, further comprising a process oil in an amount of greater than 0 to 200 parts by weight per 100 parts by weight of the interpolymer of the ethylene / α-olefin / polyene monomer.
20. An interpolymer composition of the crosslinkable ethylene / α-olefin / polyene monomer, characterized in that it comprises the interpolymer composition according to any of claims 1-19 and a chemical crosslinking agent selected from the group consisting of the peroxides, sulfur compounds, phenolates and the silicon hydrides.
The crosslinkable composition according to claim 20, characterized in that the chemical crosslinking agent is a peroxide selected from the group consisting of dicumyl peroxide, a, a'-bis (t-) & ** & & & . butylperoxy) -diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2, 5-di (t-butylperoxy) hexino-3, peroxy-2-ethylhexonate of t -amyl, 2, 5-dimethyl-2, 5-di- (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-di (t-amyl peroxy) -2,5-dimethylhexane, 2, 5- di- (t-butylperoxy) -2,5-diphenylhexane, bis (alpha-methylbenzyl) peroxide, benzoyl peroxide, t-butyl perbenzoate and bis (t-butylperoxy) -diisopropylbenzene.
22. The crosslinkable composition according to claim 21, characterized in that the peroxide is present in an amount within a range from 0.05 to 10 weight percent, based on the total weight of the polymer in said composition.
23. A process for preparing a crosslinked interpolymer composition, the process is characterized in that it comprises: a) providing the crosslinkable composition according to Claim 20 and b) subjecting the crosslinkable composition to conditions of sufficient temperature to activate the chemical crosslinking agent and perform the at least partial crosslinking of the ethylene / α-olefin / polyene monomer interpolymer.
24. A process for preparing a crosslinked interpolymer composition, the process is characterized in that it comprises: a) providing an interpolymer composition according to any of claims 1-19 and b) exposing the interpolymer composition to a sufficient amount of radiation for perform the at least partial crosslinking of the ethylene / α-olefin / polyene monomer interpolymer.
25. The process according to claim 24, characterized in that the ionizing radiation is supplied by electronic rays in a dosage within a range from 0.1 to 30 megarads.
26. The process according to claim 24, characterized in that the ionizing radiation is supplied by ultraviolet irradiation in a dosage of at least 0.1 Joules per square centimeter.
27. A crosslinked interpolymer composition, characterized in that it is prepared by the process according to claim 23.
28. A crosslinked interpolymer composition, characterized in that, it is prepared by the process according to claim 24.
29. An article of manufacture, characterized in that it is prepared from the interpolymer composition according to any of claims 1-19.
30. An article of manufacture, characterized in that it is prepared from the crosslinkable interpolymer composition according to claim 20.
31. An article of manufacture, characterized in that it is prepared from the crosslinkable interpolymer composition according to claim 27.
32. An article of manufacture, characterized in that it is prepared from the crosslinkable interpolymer composition according to claim 28.
33. An article multilayer, characterized in that it comprises at least two contiguous layers, one of said contiguous layers comprises the interpolymer composition according to any of claims 1-6 or 14-19 and the other of the adjacent layers comprises at least one natural polymer or synthetic
34. An article of manufacture, characterized in that it is prepared by exposing the multi-layer article according to claim 33 to a sufficient amount of radiation to effect at least partial cross-linking of the interpolymer of the ethylene / α-olefin / polyene monomer .
35. A multi-layer article, characterized in that it comprises at least two contiguous layers, one of the contiguous layers comprises an interpolymer composition of the crosslinkable ethylene / α-olefin / polyene monomer which 5 comprises the composition of the interpolymer according to any of claims 1-6 or 14-19 and a chemical crosslinking agent selected from the group consisting of peroxides, sulfur compounds, phenolates and silicon hydrides, and the other of the layers contiguous 10 comprises at least one natural or synthetic polymer.
36. A manufacturing article, characterized in that it is prepared by exposing the multi-layer article according to claim 35 to sufficient temperature conditions to activate the The chemical crosslinking agent and at least partial crosslinking of the interpolymer of the ethylene / α-olefin / polyene monomer. twenty 25 ^^^ ájÉi