MXPA99002110A - BLENDS OF&agr;-OLEFIN/VINYLIDENE AROMATIC MONOMER OR HINDERED ALIPHATIC VINYLIDENE MONOMER INTERPOLYMERS WITH POLYOLEFINS - Google Patents

Abstract

Thermoplastic blends are prepared from polymeric materials comprising (A) from 1 to 99 weight percent of at least one interpolymer made from monomer components comprising (1) from 1 to 65 mole percent of (a) at least one aromatic vinylidene monomer, or (b) at least one hindered aliphatic or cycloaliphatic vinylidene monomer, or (c) a combination of at least one aromatic vinylidene monomer and at least one hindered aliphatic or cycloaliphatic vinylidene monomer, and (2) from 99 to 35 mole percent of at least one aliphatic&agr;-olefin having from 2 to 20 carbon atoms;and (B) from 99 to 1 weight percent of at least one polymer made from monomer components comprising (1) from1 to 100 mole percent of at least one&agr;-olefin having from 2 to 20 carbon atoms, and (2) from 0 to 99 mole percent of at least one&agr;-olefin having from 2 to 20 carbon atoms which monomer is different from the monomer of component (B-1). These blends possess improved properties when compared to the properties of the polymers comprising the blend. These blends are useful in the preparation of films, fabricated articles, injection molded parts, bitumen and asphalt modification, hot melt and pressure sensitive adhesive systems.

Description

MIXTURES OF A-OLEFI NAOMERS VI NI LI DENO AROMÁTICO OR MONOMERO DE VI NI LI DENO ALIFATICO OBSTRU IDO WITH POLIOLEFI NAS The present invention pertains to mixtures (A) of interpolymers made of monomer components comprising at least one α-olefin and at least one aromatic vinylidene monomer and / or at least one clogged aliphatic vinylidene monomer and / or at least one monomer of vinylidene cycloaliphatic and (B) olefinic polymers. The generic class of materials covered by substantially random interpolymers of clogged α-olefin / vinylidene monomers and including materials such as α-olefin / aromatic vinyl monomer interpolymers are known in the art, and offer a range of material structures and properties, which makes them useful for varied applications, such as, compatibilizers for blends of polyethylene and polystyrene, as described in US 5,460, 818. A particular aspect described by D'Anniello et al (Journal of Applied Polymer Science, Volume 58, pages 1 701-1 706 (1995)) is that such interpolymers can show good elastic properties and energy dissipation characteristics. In another aspect, the selected interpolymers can find utility in adhesive systems, as illustrated in U.S. Patent No. 5244996, issued to Mitsu i Petrochemical Industries Ltd. Although utilization in its own right, the industry is constantly seeking to improve the applicability of these interpolymers, for example, to extend the application temperature range. Such intensifications can be achieved via additives, but it is desirable to develop technologies to provide improvements in processing capacity or performance without the addition of additives or additional improvements that can be achieved with the addition of additives. Park et al. , in WO 95/27755 discloses a method for increasing the hardness and solvent resistance of a homopolymer or interpolymer of a monovinylidene aromatic monomer, by mixing it with an olefin polymer, such as a polyethylene or ethylene / octene copolymer. However, due to the incompatibility of these two types of resins, a compatibilizer is required, which Park shows may be a pseudo random interpolymer of an aromatic vinylidene monomer and an α-olefin to the ifatic. Bradfute et al. , in WO 95/32095 discloses multilayer films having at least one layer which is an ethylene / styrene copolymer. McKay et al. , in WO 96/07681 describes a thermosetting elastomer comprising a pseudo random or substantially random crosslinked interpolymer of at least one α-olefin, at least one aromatic vinyl idene compound, and at least one diene. The subject invention also provides a thermoplastic vulcanizate comprising the heat set elastomer as provided in a thermoplastic polyolefin matrix. There is a need to provide materials based on interpolymers of α-olefin / aromatic vinylidene monomers with superior performance characteristics for unmodified polymers, which will further extend the usefulness of this interesting class of materials. but are not limited to, low hardness at low temperature, mechanical strength and melt processability The present invention pertains to a manufactured article other than a film comprising a mixture of polymeric materials consisting of (A) from 1 to 99 percent of one or more non-crosslinked substantially random interpolymers of α-olefin / vinylidene monomers, wherein the distribution of the monomers of said interpolymers can be described by the Bernoulli statistical model or by a Markovian statistical model of the first or second order, and made each from composing monomer entities comprising: (1) from 0.5 to 65 percent mole of either (a) at least one aromatic vinylidene monomer, or (b) at least one aliphatic vinylidene monomer clogged, corresponding to the formula: A1 R1 - C = C (R2) 2 wherein A1 is an aliphatic or cycloaliphatic, spherically bulky substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system or (c) a combination of at least one aromatic vinylidene monomer and at least one clogged aliphatic vinylidene monomer; and (2) from 35 to 99.5 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms, or aliphatic α-olefins having from 2 to 20 carbon atoms and containing polar groups. The present invention also pertains to an expandable composition comprising the aforesaid mixture and a foaming or expanding agent. The mixtures and or foams herein may "comprise", "consist essentially of" or "consist of" any of two or more such polymers or interpolymers listed herein. These blends provide an improvement in one or more of the properties of polymers, such as, but not limited to, mechanical properties, low temperature performance, relaxation / damping behavior and melt flow properties compared to a similar property of any of the individual polymers of said mixture. The term "interpolymer" is used herein to mean a polymer, wherein at least two different monomers are polymerized to make the interpolymer. The term "copolymer" as used herein means a polymer wherein at least two different monomers are polymerized to form the copolymer. The term "mer (s)" means the polymerized unit of the polymer derived from the indicated monomer (s). The term "monomer residue" or "polymer units derived therefrom" means that portion of the polymerizable monomer molecule, which resides in the polymer chain as a result of being polymerized with another polymerizable molecule to make the polymer chain . The term "substantially random" in the substantially random interpolymer resulting from polymerizing one or more α-olefin monomers and one or more vinylidene aromatic monomers or blocked cycloaliphatic or aliphatic vinylidene monomers, and optionally, with one or more other polymerizable ethylenically unsaturated monomers , as used herein, means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by JC Randall et? POLYMER SEQUENCE DETERMINATION, Carbon-13 NMR Method. Academic Press, New York, 1977, pp. 71 -78. Preferably, the substantially random interpolymer resulting from polymerizing one or more α-olefin monomers and one or more aromatic vinylidene monomers, and optionally, with one or more polymerizable ethylenically unsaturated monomers does not contain more than 1 5 percent of the amount total of aromatic vinylidene monomer in aromatic vinylidene monomer blocks of more than 3 units. More preferably, the interpolymer was not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the carbon-NMR spectrum of the substantially random interpolymer the peak areas corresponding to the methylene and methylene main chain carbons representing either meso-diadic sequences or sequences of racemic dyads must not exceed 75 percent of the area total peak of the methylene and methylene main chain carbons Any numerical value declared herein includes all values from the lowest value up to the highest value in increments of one unit, provided there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a variable process, such as, for example, temperature, pressure, time, is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 1-5 to 85, 22 to 68, 43 to 51, 30 to 32 are expressly listed in this specification. For values which are less than one, a unit is considered to be 0.0001, 0.001 0.01 or 0. 1, as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value listed to be considered to be expressly declared in this application in a similar manner. Interpolymers suitable as component (A) for the mixtures comprising the present invention include substantially random interpolymers, each having been made from monomer components comprising one or more α-olefin monomers with one or more vinylidene aromatic monomers and / or one or more blocked cycloaliphatic or aliphatic vinylidene monomers, and optionally with one or more other polymerizable ethylenically unsaturated monomers. The interpolymers are also prepared by polymerizing one or more α-olefin monomers with one or more aromatic vinylidene monomers and / or one or more clogged aliphatic or cycloaliphatic vinylidene monomers, and optionally with one or more other polymerizable ethylenically unsaturated monomers. Suitable α-olefin monomers include, for example, α-olefin monomers containing from 2 to 20, preferably from 2 to 1 2, more preferably from 2 to 8 carbon atoms. Such preferred monomers include ethylene, propylene, butene-1,4-methyl-1 -pente, hexene-1 and octene-1. Ethylene or a combination of ethylene with C3.8 α-olefins are highly preferred. These α-olefins do not contain an aromatic portion. Other optionally polymerizable, ethylenically unsaturated monomers include deformed anion olefins, such as norbornene and norborne substituted with C.sub.1.10 alkyl or C.sub.6-? Aryl or >; being an example interpolymer ethylene / styrene / norbornene. Suitable vinylidene aromatic monomers which can be used to prepare the interpolymers used in the mixtures include, for example, those represented by the following formula: Ar (CH2) p R1 - C = C (R2) 2 wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C 1 - alkylene, and C, 4 haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero. Exemplary monovinylidene aromatic monomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Such particularly suitable monomers include styrene and substituted derivatives with lower alkyl or halogen thereof. Preferred monomers include styrene, α-methyl styrene, ring or phenyl substituted derivatives or styrene C C-C 4 lower alkyl, such as, for example, ortho-, meta-, and para-methylstyrene, ring styrenes halogenated, para-vinyl toluene or mixtures thereof. A more preferred aromatic monovinylidene monomer is styrene. By the term "clogged cycloaliphatic or aliphatic vinylidene compounds" is meant the addition polymerizable vinylidene monomers corresponding to the formula: A1 R1 - C = C (R2) 2 wherein A1 is an aliphatic or cycloaliphatic, sterically bulky substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system. By the term "sterically voluminous" it is meant that the monomer bearing this substituent is normally incapable of addition polymerization by standard Ziegler-Natta polymerization catalysts at a rate comparable to ethylene polymerizations. -olefin containing from 2 to 20 carbon atoms and having a linear aliphatic structure, such as propylene, butene-1, hexene-1 and octene-1 are not considered as clogged aliphatic monomers.The aliphatic or cycloaliphatic vinylidene compounds clogged preferred are monomers in which one of the carbon atoms bearing the ethylenic unsaturation is tertiary or substituted quaternary Examples of such substituents include cyclic aliphatic groups, such as cyclohexyl, cyclohexenyl, cyclooctenyl, or derivatives substituted with alkyl or aryl ring of them, tert-butyl, and norbornyl. highly preferred cycloaliphatic or aliphatic vinylidene are the various substituted derivatives of the isomeric vinylidene ring of substituted cyclohexene and cyclohexenes, and 5-ethyleneden-2-norbornene. They are especially 1 -, 3- and 4-vinylcyclohexene.

The interpolymers of one to more α-olefins and one or more monovinylidene aromatic monomers and / or one or more clogged aliphatic or cycloaliphatic vinylidene monomers employed in the present invention are substantially random polymers. These interpolymers usually contain from 0.5 to 65, preferably from 1 to 55, more preferably from 2 to 50 percent mole of at least one aromatic vinylidene monomer and / or blocked cycloaliphatic or aliphatic vinylidene monomer and from 35 to 99.5, preferably from 45 to 99, more preferably from 50 to 98 percent mole of at least one α-olefin to the isatic having from 2 to 20 carbon atoms. Another or other optional polymerizable ethylenically unsaturated monomers include deformed ring olefins, such as norbornene and norbornenes substituted with alkyl of d.1 0 or aryl of C6.o, being an exemplary interpolymer ethylene / styrene / norbornene. The number average molecular weight (Mn) of the polymers and interpolymers is usually greater than 5,000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000.

Polymerizations and removal of unreacted monomer at temperatures above the auto-polymerization temperature of the respective monomers may result in the formation of some amounts of homopolymer polymerization products, resulting from the polymerization of free radicals. For example, in preparing the substantially random interpolymer, an amount of aromatic homopolymer of atactic vinylidene can be formed due to the homopolymerization of the aromatic vinylidene monomer at elevated temperatures. The presence of aromatic vinylidene homopolymer in general is not detrimental to the purposes of the present invention and can be tolerated. The aromatic vinylidene homopolymer can be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation of the solution with a non-solvent either for the etherpolymer or the aromatic homopolymer of vinylidene. For the purposes of the present invention, it is preferred that no more than 20 percent, preferably less than 15 percent by weight, based on the total weight of the aromatic vinylidene homopolymer interpolymers be present.

Substantially random polyterpolymers can be modified by entraining, hydrogenation, typical functionalization, or other reactions well known to those skilled in the art. The polymers can be easily sulfonated or chlorinated to provide functionalized derivatives according to established techniques. Substantially random interpolymers can be produced by polymerization or copolymerization of the appropriate monomers in the presence of a metallocene catalyst and a cocatalyst, as described in EP-A-0,416,815 by James C. Stevens et al., And US Patent No. 5,703,187 by Francis J. Timmers. Preferred operating conditions for such polymerization reactions are pressures from atmospheric to 3,000 atmospheres and temperatures from -30 ° C to 200 ° C. Examples of suitable catalysts and methods for preparing substantially random interpolymers are described in EP-A-514,828; as well as in the U.S. Patents: 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723; 5,374,696; 5,399,635; 5,470,993; 5,703,187; and 5,721,185. The substantially random aromatic α-olefin / vinylidene aromatic interpolymers can also be prepared by the methods described by John G. Bradfute et al. (W.R. Grace &Co.) in WO 95/32095; by R.B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500; and in Plastics Technology, page 25 (September 1992). Also suitable are substantially random interpolymers which comprise at least one a-olefin / vinyl aromatic / vinyl aromatic / α-olefin tetrad described in WO 98/09999 by Francis J. Timmers et al. These interpolymers contain additional signals with intensities greater than three times the peak-to-peak noise. These signals appear in the range of chemical change 43.70-44.25 ppm and 38.0-38.5 ppm. Specifically, the highest peaks are observed at 44. 1, 43.9 and 38.2 ppm. A proton test NMR experiment indicates that the signals in the chemical shift region 43.70-44.25 ppm are methine carbons and the signals in the 38.0-38.5 ppm region are methylene carbons. In order to determine the chemical changes of carbon-13 NMR of the described interpolymers, the following procedures and conditions are employed. A polymer solution of five to ten percent by weight in a mixture consisting of 50 percent by volume of 1,1,1,2-tetrachloroethane-d 2 and 50 percent by volume of chromium tris (acetylacetonate) 0.10 molar in volume is prepared. 1, 2, 4-trichlorobenzene. The N M R spectra are obtained at 130 ° C using a reverse gate decoupling sequence, a pulse width of 90 ° and a pulse delay of five seconds or more. The spectra are referred to as the methylene signal isolated from the polymer assigned at 30,000 ppm. It is believed that these new signals are due to sequences involving two vinyl aromatic monomers from head to tail preceded and segmented by at least one α-olefin insert., for example, an ethylene / styrene / styrene / ethylene tetrad, wherein the styrene monomer insertions of said tetrads occur exclusively in a 1, 2 (head to tail) manner. One skilled in the art understands that for such tetrads involving a vinyl aromatic monomer other than styrene and an α-olefin other than ethylene that the ethylene tetrad / vinyl aromatic monomer / vinyl / ethylene aromatic monomer will give an increase to peaks of carbon-1 3 NMR similar, but with slightly different chemical changes. These interpolymers are prepared by conducting the polymerization at temperatures from about -30 ° C to about 250 ° C in the presence of such catalysts, such as those represented by the formula 'P \ (ER2) r M R'2 v wherein each Cp is independently, each occurrence, a substituted cyclopentadienyl group p-linked to M; E is C or Si, M is a group IV metal, preferably Zr or Hf, most preferably Zr; each R is independently, each occurrence, H, hydrocarbon, silahydrocarbyl or hydrocarbylsilyl, containing up to about 30, preferably from 1 to about 20, more preferably from 1 to about 10 carbon atoms or if licio, each R 'is independently, each occurrence, H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsi containing it up to about 30, preferably from 1 to about 20, more preferably from 1 to about 10 carbon or silicon atoms, or two R 'groups together can a 1, 3-butadiene substituted with C 1 - 1 0 m hydrocarbyl is 1 or 2, and optionally, but preferably in the presence of an activating cocatalyst, such as tr? s (pentafluorophen? lo) borane or methylalumoxane (MAO). Particularly, suitable substituted cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, containing up to about 30, preferably from 1 to about 20, more preferably from 1 to about 10 carbon atoms or silicon, or two R groups together form a divalent derivative of such a group. Preferably, R independently, each occurrence is (including all isomers where appropriate) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl, or (where appropriate) two such R groups are they bind together to form a fused ring system, such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl or octahydrofluorenyl. Particularly preferred catalysts include, for example, racemic (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl)) zirconium dichloride, 1,4-diphenyl-1, 3-butadiene of (dimethylsilanediyl) -bis- ( Racemic 2-methyl-4-phenylindenyl)) zirconium, di-C 1 -4 alkyloxy (dimethylsilanediyl) -bis- (2-methyl-4-phenyl indenyl)) zirconium, di-C 1 -4 alkoxide (racemic dimethylsilaneyl) bis (2-methyl-4-phenylindenyl)) zirconium, or any combination thereof.

Additional preparative methods for the interpolymer in the present invention have been described in the literature. Longo and Grassi (Makromol, Chem., Volume 191, pages 2387 to 2396 [1990]) and D'Anniello et al. (Journal of Applied Polymer Science, Volume 58, pages 1 701 to 1 706 [1,995]) reported the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCI3) to prepare a copolymer of ethylene- styrene Xu and Lin (Polymer Preprints, Am. Chem. Soc, Div. Polym. Chem.) Volume 35, pages 686, 687 [1 994]) have reported copolymerization using a MgCl2 / TiCl / NdCI3 / AI (iBu) catalyst. to give random copolymers of styrene and propylene. Lu et al (Journal of Applied Polymer Science, volume 53, pages 1453 to 1460 [1 994]) have described the copolymerization of ethylene and styrene using a TiCl4 / NdCI3 / MgCl2 / AI (Et) 3 catalyst. Sernetz and Muhaupt, (Macromol. Chem. Phys., V. 1 97, pages 1071-1083, 1997) have described the influence of the polymerization conditions on the copolymerization of styrene with ethylene using Zieg ler-catalysts. Natta from Me2Si (Me4Cp) (N-tert-butyl) TiCl2 / methylaluminoxane. The manufacture of interpolymers of α-olefin / aromatic vinyl monomer, such as propylene / styrene and butene / styrene, is described in U.S. Patent No. 5,244,996, issued to Mitsui Petrochemical Industries Ltd. Olefin polymers suitable for use as component (B) in the mixtures according to the present invention are homopolymers or etherpolymers of aliphatic α-olefins., or interpolymers of one or more aliphatic α-olefins and one or more non-aromatic monomers interpolymerizable therewith, such as, C 2 -C 20 α-olefins or those aliphatic α-olefins having from 2 to 20 carbon atoms and they contain polar groups. Suitable aliphatic α-olefin monomers, which introduce polar groups into the polymer include, for example, ethylenically unsaturated nitriles, such as, acrylonitrile, methacrylonitrile, ethacrylonitrile, etc.; ethylenically unsaturated anhydrides, such as maleic anhydride; ethylenically unsaturated amides such as acrylamide, methacrylamide, etc.; ethylenically unsaturated carboxylic acids (both mono- and difunctional), such as acrylic acid and methacrylic acid, etc.; esters (especially lower alkyl esters, for example, d -Cβ) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, methacrylate or n-butyl acrylate, 2-ethyl-hexylacrylate, etc.; imides of ethylenically unsaturated dicarboxylic acids, such as N-alkynyl or N-aryl maleimides, such as N-phenyl maleimide, etc. Preferably, such monomers containing polar groups are acrylic acid, vinylacetate, maleic anhydride and acrylonitrile. The halogen groups which can be included in the polymers of the aliphatic α-olefin monomers include fluorine, chlorine and bromine; Preferably such polymers are chlorinated polyethylenes (CPEs). Preferred olefinic polymers for use in the present invention are homopolymers or interpolymers of an α-olefin to the atypical, including cycloaliphatic, having from 2 to 1 8 carbon atoms. Suitable examples are ethylene or propylene homo-polymers, and interpolymers of two or more α-olefin monomers. Other preferred olefinic polymers are ethylene polymers and one or more different α-olefins having from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1 -hexene, and 1-ketene. The olefin polymer blend component may also contain, in addition to the α-olefin, one or more non-aromatic monomers interpolymerizable therewith. Such additional interpolymerizable monomers include, for example, C4-C20 dienes, preferably butadiene or ethyleneidene-2-norbronone. The olefinic polymers can be further characterized by their degree of long or short chain branching and the distribution thereof. A class of olefinic polymers is generally produced by a high pressure polymerization process using a free radical initiator, resulting in low density polyethylene with traditional long chain branching (LDPE). The LDPE employed in the present composition usually has a density of less than 0.94 g / cc (ASTM D 792) and a melt index of from 0.01 to 100, and preferably from 0. 1 to 50 grams per 10 minutes (as is determined by ASTM Test Method D 1 238, condition I). Another class is the linear olefin polymers, which have an absence of long chain ramification, such as traditional linear low density polyethylene polymers (heterogeneous LLDPE) or linear high density polyethylene polymers (H DPE). made using Ziegler polymerization processes (e.g., U.S. Patent No. 4, 076, 698 (Anderson et al.), sometimes called heterogeneous polymers.

HDPE consists mainly of long linear polyethylene chains The HDPE employed in the present composition usually has a density of at least 0.94 grams per cubic centimeter (g / cc) as determined by ASTM Test Method D 505, and a melt index (ASTM-1 238, condition I) in the range from 0 01 to 1 00, and preferably from 0 1 to 50 grams per 10 minutes The heterogeneous LLDPE employed in the present composition generally has a density from 0 85 to 0 94 g / cc (ASTM D 792), and a melt index (ASTM-1 238, condition I) in the range from 0 01 to 100, and preferably from 0 1 to 50 grams per 10 minutes Preferably, the LLDPE is a polymer ester of ethylene and one or more different α-olefins having from 3 to 1 8 carbon atoms, more preferably from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl? -1-pentene, 1 -hexene, and 1 -octene An additional class is here of uniformly ramified or homogeneous polymers (homogeneous LLDPE) Homogeneous polymers do not contain long chain branches and have only branches derived from monomers (if they have more than two carbon atoms) Homogeneous polymers include those made as described in US Patent 3, 645, 992 (Elston), and those made using single-site catalysts in a batch reactor having relatively high olefin concentrations [as described in US Pat Nos. 5,026,798 and 5,055, 438 (C-anich)] Uniformly branched / homogeneous polymers are those polymers in which the comonomer is randomly distributed within a given interpolymer molecule, and wherein the interpolymer molecules have a ratio of ethylene / common comonomer within of that interpolymer. The homogeneous LLDPE employed in the present composition generally has a density from 0.85 to 0.94 g / cc (ASTM D 792), and a melt index (ASTM-1 238, condition I) in the range from 0.01 to 100, and preferably from 0. 1 to 50 grams per 10 minutes. Preferably, the LLDPE is an interpolymer of ethylene and one or more different α-olefins having from 3 to 1 8 carbon atoms, more preferably from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1 -hexene and 1-ketene. Additionally, there is the class of substantially linear olefin polymers (SLOP) that can be advantageously used in the component (B) of the mixtures of the present invention. These polymers have a processability similar to LDPE, but the strength and hardness of LLDPE. Similar to traditional homogeneous polymers, the substantially linear ethylene / α-olefin interpolymers have only a single melting peak, as opposed to conventional, heterogeneous linear Ziegler polymerized ethylene / α-olefin interpolymers, which have two or more fusion peaks (determined using differential scanning calorimetry). The substantially linear olefin polymers are described in US Pat. Nos. 5, 272, 236 and 5,278,272, which are incorporated herein by reference.

The density of the SLOP as measured according to ASTM D-792 is generally from 0.85 g / cc to 0.97 g / cc, preferably from 0.85 g / cc to 0.955 g / cc, and especially from 0.85 g / cc to 0.92 g /DC. The melt index, according to ASTM D-1238, Condition of 190 ° C / 2.16 kg (also known as l2), of the SLOP is generally from 0.01 g / 10 min to 1000 g / 10 min., Preferably from 0.01 g / 10 min at 100 g / 10 min., and especially from 0.01 g / 10 min at 10 g / 10 min. Also included are the ultra low molecular weight ethylene polymers and ethylene / α-olefin interpolymers described in the patent application (Application No. 60 / 010,403) entitled Ultra-low Molecular Weight Polymers, provisionally filed on January 22, 1996., in the names of M. L. Finlayson, C.C. Garrison, R.E. Guerra, M.J. Guest, B.W.S. Kolthammer, D.R. Parikh, and S. M. Ueligger. These ethylene / α-olefin interpolymers have l2 melt index greater than 1,000, or a number average molecular weight (Mn) less than 11,000. The SLOP may be a homopolymer of C2-C20 olefins, such as ethylene, propylene, 4-methyl-1-pentene, etc., or it may be an interpolymer of ethylene with at least one C3-C20 α-olefin and / or C2-C20 acetylenically unsaturated monomer and / or C-C18 diolefin. The SLOP may also be an interpolymer of ethylene with at least one of the above C3-C20 α-olefins, diolefins and / or acetylenically unsaturated monomers in combination with other saturated monomers. Especially preferred olefin polymers suitable for use as component (B) comprise LDPE, HDPE, heterogeneous and homogeneous LLDPE, SLOP, polypropylene (PP), especially isotactic polypropylene and hardened polypropylenes of rubber, or ethylene-propylene (EP) interpolymers, or chlorinated polyolefins (CPE), or ethylene-vinyl acetate copolymers, or ethylene-acrylic acid copolymers, or any combination thereof. The blends of the present invention usually comprise from 1 to 99, preferably from 5 to 95 and more preferably from 10 to 90 percent by weight of the interpolymers containing at least one residue of aromatic vinylidene monomer or residue of cycloaliphatic viyl nylidene monomer. or clogged aliphatic, or any combination thereof (component (A)) and from 1 to 99, preferably from 5 to 95, more preferably from 1 to 90 percent by weight of the polymers, which do not contain any residue of aromatic lead vinyl monomer or residue of clogged cycloaliphatic or aliphatic vinylidene monomer (component (B)). The percentages are based on the total amount of the polymers that make up the mixtures. The mixtures of the present invention can be prepared by any suitable means known in the art, such as, but not limited to, dry blending in a pelletized form in the desired proportions, followed by melt mixing in a screw extruder, or mixer. of Banbury. The dry-mixed pellets can be melt processed directly into a final solid state article, for example, injection molding. Alternatively, blends can be made by direct polymerization, without isolation of the components of the mixture, using, for example, one or more catalysts in one reactor or two or more reactors in series or in parallel. The foam structure of the present invention may have any physical configuration known in the art, such as bun base, board or lamp. Other useful forms are foamable or expandable particles, moldable foam particles, or beads, and articles formed by expansion and / or coalescence and welding of those particles. Excellent teachings for processes for making ethylene polymer foam structures and processing them are seen in CP Park, "Polyolefin Foam," Chapter 9, Handbook of Polymer Foams and Technology, edited by D. Klempner and KC Frisch, Hanser Publishers , Munich, Vienna, New York, Barcelona (1991). The present foam structure can be made by a conventional extrusion foaming process. The structure is generally prepared by heating a polymer material to form a fused or plasticized polymer material, incorporating in it a known blowing agent to form a foamable gel, and extruding the gel through a die to form the product. of foam. Before mixing with the blowing agent, the polymer material is heated to a temperature up to or above its glass transition temperature or melting point. The blowing agent can be incorporated or mixed into the fused polymer material by any means known in the art., such as with an extruder, mixer or beater. The blowing agent is mixed with the polymer material fused at a high pressure, sufficient to prevent substantial expansion of the fused polymer material and to generally disperse the blowing agent homogeneously therein. Optionally, a core former in the fused or dry-blended polymer can be mixed with the polymer material before being plasticized or fused. The foamable gel is usually cooled to a lower temperature to optimize the physical characteristics of the foam structure. The gel is extruded or transported through a die of desired shape to a zone of reduced or reduced pressure to form the foam structure. The zone of lower pressure is at a lower pressure than in which the foamable gel is maintained prior to extrusion through the die. The lower pressure can be superatmospheric or subatmospheric (vacuum), but preferably at an atmospheric level. The present foam structure can be formed into a conglutinated filament form by extrusion of the polymeric material through a multi-orifice die. The holes are arranged so that contact between the adjacent streams of the molten extrudate occurs during the foaming process and the contact surfaces adhere to each other with sufficient adhesion to result in a unitary foam structure. The molten extrudate streams emerging from the die take the form of vertical filaments or cuts, which are suitably foamed, conglutinated and adhered to one another to form a unitary structure. Conveniently, the individual conglutinated filaments or vertical cuts should remain adhered in a unitary structure to prevent filament delamination under stresses encountered when preparing, molding and using the foam. Apparatus and methods for producing foam structures in the form of conglutinated filament are seen in US Pat. Nos. 3, 573, 152 and 4,824,720. The present foam structure can also be formed by an accumulation extrusion process as seen in U.S. Pat. 4, 323,528. In this process, low density foam structures having large lateral cross-sectional areas are prepared by: 1) forming under pressure a gel of the ethylene polymer material and a blowing agent at a temperature at which the viscosity of the gel is sufficient to retain the blowing agent, when the gel is allowed to expand; 2) Extrude the gel in a holding zone maintained at a temperature and pressure at which the gel is not allowed to foam, the holding zone having an outlet die which defines an orifice opening in a pressure zone. lower to which foam the gel, and a gate that can be opened by closing the hole of the die; 3) periodically open the gate; 4) Concurrently applying mechanically pressure by a movable ram in the gel to expel it from the support zone through the hole in the die in the zone of least pressure, at a speed greater than that at which the foam occurs. substantial in the die hole and smaller than the one at which substantial irregularities occur in the cross-sectional shape or area; and 5) allowing the ejected gel to expand without restriction at least in one dimension to produce the foam structure.

The foam structure can also be formed into non-crosslinked foam beads suitable for molding into articles. To make the foam beads, the discrete resin particles such as pellets of granular reams are: suspended in a liquid medium, in which they are substantially insoluble, such as water; impregnated with a blowing agent by introducing the blowing agent into the liquid medium at elevated pressure and temperature in an autoclave or other pressure vessel, and discharging rapidly into the atmosphere or a region of reduced pressure to expand to form the beads of foam. This process is taught well in U.S. Patent Nos. 4, 379, 859 and 4,464,484. In a derivative of the above process, the styrene monomer can be impregnated into the suspended pellets prior to impregnation with blowing agent to form a graft interpolymer. ethylene oxide polymer material The polyethylene / polystyrene interpolymer beads are cooled and discharged from the substantially unexpanded container. The beads are then expanded and molded by the conventional expanded polystyrene bead molding process The process for making the polyethylene / polyethylene interpolymer beads is described in the patent state an idense no 4, 1 68.353 Foam beads can be molded then by any means known in the art, such as loading the foam beads into the mold, commuting the mold to compress the beads, and heating the beads, such as by going through to effect the coalescence and welding of the beads to form the article Optionally, the beads can be impregnated with air or with another blowing agent at a high pressure and temperature before being loaded into the mold. In addition, the pearls can be heated before loading. The foam beads can then be molded into blocks or shaped articles by a suitable molding method known in the art. (Some of the methods are shown in U.S. Patent Nos. 3,504,068 and 3,953,558.) Excellent teaching of the above processes and molding methods in C.P. Park, supra, p. 191, pp. 197-198, and pp.227-229. Blowing agents useful in making the present foam structure include inorganic agents, organic blowing agents and chemical blowing agents. Suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, nitrogen, and helium. Organic blowing agents include aliphatic hydrocarbons having 1-6 carbon atoms. The aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane or neopentane. The aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol. The fully or partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons and chlorofluorocarbons. Examples of the fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-152a) 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane ( HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane. Chlorocarbons and partially halogenated chlorofluorocarbons for use in this invention include methyl chloride, methylene chloride, ethyl chloride, 1,1-trichloroethane, 1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1. , 1 difluoroethane (HCFC-142b), 1,1-dichloro-2,2, -trifluoroethane (HCFC-123) and 1-chloro-1,2,2-tetrafluoroethane (HCFC-124). Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1-trifluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chlorheptafluoropropane and dichlorohexafluoropropane. Chemical blowing agents include azodicarbonamide, azodiisobutyro-nitrile, benzenesulfonhydrazide, 4,4-oxybenzenesulfonyl-semicarbazide, p-toluene sulfonayl semi-carbazide, barium azodicarboxylate, N.N'-dimethyl-N.N'-dinitrosoterephthalamide, and trihydrazino triazine. Preferred blowing agents include isobutane, HFC-152a, and mixtures of the foregoing. The amount of blowing agents incorporated in the polymer melt material to make a foam-forming polymer gel is from 0.2 to 5.0, preferably from 0.5 to 3.0, and most preferably from 1.0 to 2.50 gram mol per kilogram of polymer. The foams may be perforated to intensify or accelerate the permeation of blowing agent of the foam and air into the foam. The foams can be perforated to form channels which extend completely through the foam from one surface to another or partially through the foam. The channels can be separated up to 2.5 centimeters apart and preferably up to 1.3 centimeters apart. The channels are present substantially on a complete surface of the foam and preferably are uniformly dispersed on the surface. The foams can employ a stability control agent of the type described above in combination with a perforation to allow accelerated permeation or release of the agent from blown, while maintaining a dimensionally stable foam. Excellent teachings for the perforation of a foam are seen in U.S. Patent Nos. 5,424,016 and 5, 585,058. Various additives may be incorporated in the present foam structure, such as stability control agents, Core Formers, Inorganic Fillers, Pigments, Antioxidants, Acid Cleaners, Ultraviolet Absorbers, Flame Retardants, Processing Aids or Extrusion Aids A stability control agent can be added to the present foam to enhance dimensional stability. Preferred agents include C10 2 fatty acid esters and esters. Such agents are seen in US Pat. Nos. 3,644, 230 and 4, 214, 054. Highly preferred agents include stearate stearamide, glycerol monostearate, glycerol monobehenate, and sodium monostearate. sorbitol Normally such stability control agents are employed in an amount ranging from 0.1 to 1.0 parts per hundred parts of the polymer. The present foam structure exhibits excellent dimensional stability. Preferred foams recover 80 percent or more of the volume Initially within a month the initial volume is measured within 30 nds after the expansion of the foam. The volume is measured by a suitable method, such as, cubic displacement of water. In addition, a core forming agent may be added in order to control the size of the foam cells. Preferred core forming agents include inorganic substances, such as calcium carbonate, talc, clay, titanium oxide, silica, barium sulfate, diatomaceous earth, mixtures of citric acid and sodium bicarbonate. The amount of core forming agent employed can vary from 0.01 to 5 parts by weight per hundred parts by weight of a polymer resin.

The foam structure is substantially non-crosslinked or non-crosslinked. The alkenyl aromatic polymer material comprising the foam structure is substantially free of crosslinking. The foam structure contains no more than 5 percent gel per ASTM D-2765-84 Method A. A slight degree of crosslinking is permissible, which occurs naturally without the use of crosslinking or radiation agents.

The foam structure has a density of less than 250, more preferably less than 1 00 and most preferably from 1 to 70 kilograms per cubic meter. The foam has an average cell size from 0.05 to 5.0, more preferably from 0.2 to 2.0, and most preferably 0.3 to 1.8 millimeters according to ASTM D3576. The foam structure can take any physical configuration known in the art, such as vertical cuts, board, bar and extruded sheet. The foam structure can also be formed by molding expandable beads in any of the above configurations or any other configuration. The foam structure can be closed cell or open cell. A closed cell foam contains 80 percent or more closed cells or less than 20 percent open cells according to ASTM D2856-A. Also additives, such as antioxidants (for example, clogged phenols, such as, for example, Irganox® 1010, a registered trademark of CI BA-GEIGY), phosphites (for example, I rgafos® 168, a registered brand) can be included. of CI BA-GE1GY), stabilizers of U.V. , grip additives (eg, polyisobutylene), antiblock additives, colorants, pigments, fillers, in the interpolymers employed in the blends of and / or employed in the present invention, to the extent that they do not interfere with the intensified properties discovered by the Requesters. The additives are employed in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidants used is the amount that prevents the polymer or polymer blend from experiencing oxidation at the temperatures and environment employed during the storage and final use of the polymers. Such an amount of antioxidants is generally in the range from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0. 1 to 2 weight percent based on the weight of the polymer or mixture of polymers. Similarly, the amounts of any of the other additives listed are functionally equivalent amounts, such as the amount to make the polymer or mixtures of antiblocker polymers, to produce the desired amount of filler loading to produce the result desired, to provide the desired color from the dye or pigment. Such additives can conveniently be used in the range from 0.05 to 50, preferably from 0. 1 to 35, more preferably from 0.2 to 20 percent by weight based on the weight of the polymer or mixture of polymers. However, in the case of fillers, they could be used in amounts up to 90 percent by weight based on the weight of the polymer or polymer mixture. The mixtures of the present invention, in addition to the production of foams, can be used to produce a wide range of manufactured articles, such as, for example, sheets and films calendered, emptied and blown, and injection molded parts. The mixtures also find use in applications such as modifiers of asphalt and bitumen compositions and as components for pressure sensitive and hot melt adhesive systems. The following examples are illustrative of the invention.

Example 1 -22 Preparations and characteristics of interpolymers Preparation of interpolymers (A), (C), (G), (H) and (I) The polymer is prepared in a stirred batch reactor of 1 .51 4 m3. The reaction mixture consisted of approximately 0.95 m 3 of a solvent comprising a mixture of cyclohexane (85% by weight) &; isopentane (15% by weight), and styrene. Before the addition, the solvent, styrene and ethylene are purified to remove water and oxygen. The inhibitor in styrene is also removed. The inerts are removed by purging the container with ethylene. The pressure is then controlled at a set point with ethylene to the container. Hydrogen is added to control the molecular weight. The temperature in the container is controlled to a set point by varying the temperature of the water in the container. Before polymerization, the vessel is heated to the desired run temperature and the catalyst components: titanium: (N-1, 1-dimethyl-ethyl) dimethyl (1 - (1, 2,3,415-eta) -2, 3 , 4,5-tetramethyl-2,4-cyclopentadien-1-yl) silanaminate)) (2-) N) -dimethyl, CAS # 1 35072-62-7, tris (pentafluorophenyl) boron, CAS # 001 1 09- 1-5, modified methylaluminoxane type 3A, CAS # 146905-79-5, are flow controlled, on a molar ratio basis of 1/3/5 respectively, are combined and added to the receiver. After initiation, polymerization with ethylene supplied to the reactor as required to maintain the container pressure is allowed to proceed. In some cases, hydrogen is added to the upper space of the reactor to maintain a molar ratio with respect to the ethylene concentration. At the end of the run, the catalyst flow is stopped, the ethylene is removed from the reactor, then 1 000 ppm of antioxidant lrganoxMR 1 010 (a registered trademark of CI BA-GEIGY) is added to the solution and the polymer is isolated from the solution. The resulting polymers are isolated from the solution either by steam extraction in a vessel or by the use of a devolatilizing extruder. In the case of steam-extracted material, ad-hoc processing is required in an equipment similar to an extruder to reduce residual moisture and any unreacted styrene.

TABLE 1A TABLE 1A cont. 5 The test parts and characterization data for the interpolymers and their mixtures are generated according to the following procedures: Density: The density of the samples is measured according to ASTM-D792. Differential Scanning Calorimetry (DSC): A Dupont DSC-2920 is used to measure the thermal transition temperatures and transition heat for the interpolymers. In order to eliminate the previous thermal history, the samples are first heated to 200 ° C. Heating and cooling curves are recorded at 10 ° C / min. The melting (second heat) and crystallization temperatures are recorded from the peak temperatures of the endotherm and exotherm, respectively. Fusion Cutting Relocation: Osci latory cutting rheology measurements are performed with a Rheometrics RMS-800 rheometer. The rheological properties are monitored at an isothermal set temperature of 1 90 ° C in a frequency sweep mode. ? It is viscosity. ? (100/0.1) is the proportion of viscosities measured at 100 rad / s and 0. 1 rad / s. Mechanical test: The hardness of Cut A was measured at 23 ° C following ASTM-D240. The flexional module was evaluated according to ASTM-D790. The tensile properties of the compression molded samples were measured using an IN STRON R 1 145 tension machine (a registered trademark of Itrontron Corporation, Canton, Massachusetts) equipped with a strain gauge, at 23 ° C unless which is indicated otherwise. Samples of ASTM-D638 are tested at the 5 min. Warpage speed 1. The average of four stress measurements is given.The yield stress and yield strain are recorded at the point of inflection in the stress / strain curve. The energy at break is the area under the stress / strain curve.Tensile stress relaxation: The uniaxial stress stress relaxation was evaluated using an I NSTRONM tension machine (a registered trademark of Instron Corporation, Canton, Massachusetts) The compression molded film (~ 0.5 mm thick) with a gauge length of 2.54 cm was deformed to a 50% deformation level at a deformation rate of 20 min "1. The force required to maintain 505 lengthening was monitored for 10 min. The magnitude of stress relaxation is defined as (f ¡-ff / f¡), where fj is the initial force and ff is the final force. Thermomechanical analysis (TMA): Data were generated using a Perma Elmer TMA7 instrument. Probe penetration is measured at a depth of 1 mm in 2 mm thick compression molded parts using a heating rate of 5 ° C / min and a load of 1 Newton.

Table 1B Components of interpolymer mixtures 1 proportion of? (1.6) /? (0.1). to N.D. = not determined b Amount of monomer residue in the polymer chain.

EXAMPLES 1-3 Mixtures with ethylene / α-olefin copolymers Preparation of the mixtures: Three mixture compositions are prepared, examples 1, 2 and 3 from the above interpolymer (A) and olefin polymer (B) in proportions in weight of 75/25, 50/50 and 25/75 with a Haake mixer equipped with a bowl of Rheomix 3000. The components of the mixture are first mixed dry and then fed to the balanced mixer at 1 90 ° C. The temperature and power balance equals 3-5 minutes. The molten material is mixed at 1 90 ° C and 40 rpm for 10 minutes. The characterization data for these mixtures and the components of the mixture forming the comparative experiments for these data are given in Table 2.

Table 2 * An interpolymer A containing 69.4 percent by weight (38.4 mol) of styrene is not an example of the present invention; l2 of 0.18. 2 Olefin polymer (B) is ENGAGE R EG8100, an ethylene / octene copolymer commercially available from and a registered trademark of The Dow Chemical Company and having a density of 0.87 g / cm 3 and a melt index of 1.0 (190 ° C) C, 2.16 kg). 3 The sample slid during the test.

Table 2 shows that examples 1, 2 and 3 of the mix compositions all have good mechanical integrity and strength performance as evidenced by stress, strain and total energy at break. Of particular merit is the performance of the mixture at -10 ° C, finding high firmness. The effort and total energy to the rupture unexpectedly exceeds or equals those of the component polymers (A) and (B). In addition, all mixtures unexpectedly show high levels of stress relaxation compared to what would be expected from the behavior of the components and proportions of the compositions of the mixtures. This property is desirable for many movie applications. The melting rheology data for the three blending examples show that the lower cut tan d (a lower cut melt elasticity measure) and the viscosity is lower compared to what would be anticipated from the behavior of components and proportions of compositions of the mixtures. This results in improved processing capacity in some applications.

EXAMPLES 4, 5 AND 6 Mixtures with ethylene / α-olefin polymer copolymers Preparation of the mixtures: Three mixture compositions are prepared, examples 4, 5 and 6 from the above interpolymer (C) and olefin polymer (B) ) in proportions by weight of 75/25, 50/50 and 25/75 with a Haake mixer equipped with a Rheomix 3000 bowl. The components of the mixes are dry mixed first and then fed into the balanced mixer 1. 90 ° C. The temperature and power balance takes 3-5 minutes. The molten material is mixed at 1 90 ° C and 40 rpm for 1 0 minutes.

The characterization data for these mixtures and the components of mixtures forming the comparative examples for these experiments are given in Table 3.

Table 3 * It is not an example of the present invention 1 Interpolymer (C) containing 43.4 percent by weight (17.1 mol) of styrene; l2 of 2.62. 2 Olefin polymer (B) is ENGAGE R EG8100, an ethylene / octene copolymer commercially available from and a registered trademark of The Dow Chemical Company and having a density of 0.87 g / cm 3 and a melt index of 1.0 (190 ° C, 2.16 kg). 3 The sample slid during the test.

Table 3 shows that examples 4, 5 and 6 of the mix compositions all have good mechanical integrity and strength performance as evidenced by stress, strain and total energy at break. Of particular merit is the performance of the mixture at -10 ° C, finding high firmness. The effort and total energy at the break exceeds unexpectedly or equals those of the component polymers.

The melting rheology data for the three blending examples show, in particular, that the lower cut tan d (a lower cut melt elasticity measure) and the viscosity is lower compared to what would be expected from the performance of components and proportions of compositions of the mixtures. This translates into improved processing capacity in some applications, compared to component polymers.

EXAMPLE 7 Mixture with ethylene / α-olefin copolymer Preparation of the mixture: A composition of the mixture, Example 7, of interpolymer (A) above and olefin polymer (D) is prepared in a weight ratio of 50/50 with a Haake mixer with a Rheomix 3000 bowl. The components of the mix are first dried dry and then fed into the mixer balanced at 1 90 ° C. The temperature and feeding balance takes 3-5 m inutes. The molten material is mixed at 190 ° C and 40 rpm for 10 minutes. The characterization data for the mixture and the components of the mixture forming the comparative examples for these experiments are given in Table 4.

Table 4 * Not an example of the present invention 1 Interpolymer (A) is an ethylene / styrene interpolymer containing 69.4 weight percent (37.9 mol) of styrene; l2 of 0.18. 2 Olefin polymer (D) is ENGAGEMR EG8100, an ethylene / octene copolymer commercially available from and a registered trademark of The Dow Chemical Company and having a density of 0.87 g / cm 3 and a melt index of 1.0 (190 ° C.; 2.16 kg).

Table 4 shows that the example of the composition of the mixture has good mechanical integrity and strength performance as evidenced by stress, deformation and total energy at the break. Particular merit is the performance of the mixture at -10 ° C, finding high firmness compared to unmodified Interpol (A) content The mix unexpectedly shows a high level of strain relaxation compared to what would be anticipated from the behavior of the component and proportion of the composition of the mixture This property is desirable for many applications The melting rheology data for the example of the mixture shows, in particular, that the tan d and lower cut viscosity (a measure of lower cut melt elasticity) is lower compared to any one component. This translates into Improved processability in some applications, compared to component polymers EXAMPLE 8 Ethylene / α-olefin copolymer mixture Preparation of the mixture A mixture composition, Example 8, is prepared from the above ether polymer (C) and olefin polymer (E) in a weight ratio of 50/50 with a Haake mixer equipped with a Rheom ix 3000 bowl The components of the mixture are first mixed dry and then fed to the balanced mixer at 190 ° C. The temperature and power supply takes 3-5 Minutes "The fumed material was mixed at 1 90 ° C and 40 rpm for 10 minutes The characterization data for the mixture and the components of the mixture forming the comparative examples for these experiments are given in Table 5 Table 5 * It is not an example of the present invention 1 Interpolimer (C) is an ethylene / styrene interpolymer containing 43 4 percent by weight (1 7 1 mol) of styrene, 12 of 2 62 2 Olefin polymer (E) is AFFI N ITYM R PL1880, an ethylene / octene copolymer commercially available from and a registered trademark of The Dow Chemical Company and having a density of 0.903 g / cm3 and a melt index of 1.0 (190 ° C, 2.16 kg). Table 5 shows that the example of the composition of the mixture has good mechanical integrity and stress performance as evidenced by the effort, deformation and total energy at break.

EJ EMPLOYS 9, 10 AND 1 1 Mixtures with ultra low molecular weight ethylene / α-olefin copolymer Preparation of olefin polymer F Preparation of catalyst Part 1: Preparation of TiC (DME)? _? The apparatus (referred to as R-1) is arranged in the lid and purged with nitrogen; It consisted of a 1 0 I glass kettle with mounted bottom discharge valve, 5-neck head, polytetrafluoroethylene packing, clamp, and agitator components (support, arrow and propeller). The collars are equipped as follows: the agitator components are placed in the center neck and the outer collars had a reflux condenser topped with gas inlet / outlet, a solvent inlet, a thermocouple, and a stopper. Dry, deoxygenated dimethoxyethane (DM E) is added to the flask (approximately 5 L). In the dry box, 700 g of TiCl3 were weighed in a funnel of addition of equalization powder; The funnel is covered, removed from the dry box and placed in the reaction kettle instead of the stopper. TiCl3 is added over 10 minutes with stirring. After the addition is completed, additional DME is used to wash the rest of the TiCl3 in the flask. The addition funnel is replaced with a stopper, and the mixture is heated to reflux. The color changed from purple to pale blue. The mixture is heated for 5 hours, cooled to room temperature, the solid is allowed to settle and the supernatant is decanted from the solid. TiC ME is left)! 5 in R-1 as a pale blue solid. Part 2: Preparation of r (Me4Cfi) SiMe? N-t-BuUMqCp? The apparatus (referred to as R-2) is arranged as described for R-1, except that the size of the flask is 30 I. The head is equipped with seven collars; the agitator is in the central neck, and the outer collars containing condenser topped with nitrogen inlet / outlet, vacuum adapter, reagent addition tube, thermocouple and plugs. The flask is charged with 4.5 I of toluene, 1. 14 kg of (Me4C5H) Si Me2NH-t-Bu, and 3.46 kg of i-PrMgCI 2 M in Et2O. The mixture is then heated and the ether is allowed to boil in a trap cooled to -78 ° C. After four hours, the temperature of the mixture has reached 75 ° C. At the end of this moment, the heater is returned and DM E is added to the hot stirring solution, resulting in the formation of a white solids. The solution is allowed to cool to room temperature, the material is allowed to settle, and the supernatant is decanted from the solid. [(Me4C5) SiMe2N-t-Bu] [MgCl] 2 in R-2 is left as an off-white solid. Part 3: P reparation of [(? 5-Me4C.QS i Me? N -tB u1Ti Me? The materials in R-1 and R-2 are made into DME (3 I of DME in R-1 and 5 I in R-2.) The contents of R-1 are transferred to R-2 using a transfer tube connected to the bottom valve of the 10 I flask and one of the head openings in the 30 I flask. The remaining material in R-1 is washed using additional DME.The mixture darkened rapidly to an intense red / brown color and the temperature in R-2 rose from 21 ° C to 32 ° C. After 20 minutes, the add 160 ml of CH2CI2 through a dropping funnel, resulting in a change of color to green / brown.This is followed by the addition of 3.46 kg of 3M MeMgCI in TH F, which caused a temperature increase from 22 ° C up to 52 ° C. The mixture is stirred for 30 minutes, then 6 I of solvent is removed under vacuum, Isopar E (6 I) is added to the flask.This cycle of vacuum / solvent addition is repeated, with 4 I of solvent removed and 5 I of Isopar E added. The material was allowed to settle overnight, then the liquid layer was decanted into another 30 I glass kettle (R-3). The solvent in R-3 is removed under vacuum to leave a brown solids, which is extracted again with Isopar E; This material is transferred into a storage cylinder. The analysis indicated that the solution (1 7.23 I) is 0. 1 534 M in titanium; this is equal to 2,644 moles of [(? 5-Me4C5) SiMe2N-t-Bu] TiMe2. The remaining solids in R-2 were further extracted with I sopar E, the solution was transferred to R-3, then dried under vacuum and re-extracted with Isopar E. This solution was transferred to storage bottles; the analysis indicated a concentration of 0. 1403 M titanium and a volume of 4.3 I (? 6032 moles of [(? 5-Me4C5) S i Me2N-t-Bu] TiMe2). This gives a total yield of 3.2469 moles of [(? 5-Me4C5) SiMe2N-t-Bu] TiMe2, or 1063 g. This is a 72% total yield based on the titanium added as TiCl3.

Polymer preparation The polymer is produced in a solution polymerization process using a continuously stirred reactor. The polymer is stabilized with 1,250 ppm of calcium stearate, 500 ppm of lrganox R 1076 of clogged polyphenol stabilizer (available from and a registered trademark of Ciba-Geigy Corporatio), and 800 ppm of PEPQMR (tetrakis diphosphonite (2,4- di-t-butylphenyl) -4,4'-biphenylene) (available from and a registered trademark of Clariant Corporation). The feed mixture of ethylene (0.91 kg / h) and hydrogen (0.48 mol% proportion to ethylene) are combined in a stream before being introduced into the diluent mixture, a mixture of saturated C8-C10 hydrocarbons, for example, lsoparMR-E hydrocarbon mixture (available from and a trademark of Exxon Chemical Company) employed in a weight ratio to ethylene of 11.10: 1; and the octene comonomer at a molar to ethylene ratio of 12.50: 1 is continuously injected into the reactor. The metal complex at 4 ppm and 0.194 kg / h and the cocatalysts at 88 ppm and 0.209 kg / h are combined in a single stream and are also injected continuously into the reactor. The concentration of aluminum is 10 ppm at a flow rate of 0.199 kg / h. The sufficient residence time for the metal complex and cocatalyst was allowed to react before introduction into the polymerization reactor. The reactor pressure is kept constant at 33.3925 kg / cm2 gauge. The ethylene content of the reactor, after reaching the stable state, is maintained at the specified conditions. The reactor temperature is 110 ° C. The ethylene concentration in the outlet stream is 1.69 percent by weight. After polymerization, the reactor outlet stream is introduced into a separator where the molten polymer is separated from the unreacted comonomer (s), unreacted ethylene, unreacted hydrogen, and diluent mixing stream. Subsequently, the molten polymer is pelletized or cut into filaments, and, after cooling in a water bath or pelletizer, the solid pellets are collected. The resulting polymer is an ultra-low molecular weight ethylene / octene copolymer having a density of 0.871 g / cm3, melt viscosity of 4.200 centipoise (4.2 Pa.s) at 176.7 ° C, and number average molecular weight ( Mn) of 9,100 and Mw / Mn of 1.81.

Preparation of mixtures: Three mixture compositions are prepared, examples 9, 10 and 11 from the above interpolymers (A), (G) and (H) and olefin polymer (F), all in a weight ratio of 90 / 10 Interpolymer / olefin polymer with a Haake mixer equipped with a Rheomix 3000 bowl. The components of the mixture are first mixed dry and then fed to the balanced mixer at 190 ° C. The temperature and power balance takes 3-5 minutes. The molten material is mixed at 190 ° C and 40 rpm for 10 minutes.

The characterization data for these mixtures and the components of the mixture forming the comparative examples for these experiments are given in Table 6 Table 6 * It is not an example of the present invention. 1 Interpolymer (A) containing 69.9 percent by weight (40 mol) of styrene; l2 of 1.83. 2 Olefin Polymer (F) is an ethylene / 1-octene copolymer of ultra low molecular weight having a density of 0.871 g / cm 3, melt viscosity of 4,200 centipoise (4.2 Pa.s) at 176.7 ° C, average molecular weight of number (Mn) of 9,100 and Mw / Mn of 1.81. 3 Interpolymer (G) containing 47.3 percent by weight (19.5 mol) of styrene; l2 of 0.01. 4 Interpolymer (H) containing 29.3 percent by weight (10 mol) of styrene; l2 of 0.03.

First, this low molecular weight olefin (F) polymer has little mechanical strength compared to a high molecular weight analogue. Table 6 shows that the examples of the compositions of the mixtures retain the good mechanical integrity and stress performance of the component polymers as evidenced by the effort, deformation and total energy to the rupture. The mixture shows an unexpectedly high level of stress relaxation compared to that anticipated from the behavior of the components and proportion of the composition of the mixture. This property is desirable for many movie applications. The melt rheology data for the examples of the blends show that the low shear viscosity and tan d (a low shear elasticity measure) can be altered by the incorporation of the olefin polymer (F).

This results in improved processability in some applications, compared to the component polymer, but with retention of convenient mechanical performance.

EXAMPLES 1 2 AND 13 Mixtures with chlorinated polyethylene (CPE) Preparation of the mixture: Two mixture compositions are prepared, examples 1 2 and 1 3 from interpolymers (I) and (C) and olefin polymer (J) both in a 50/50 weight ratio with a Haake mixer equipped with a Rheomix 3000 bowl. The components of the mixture are first mixed dry and then the balanced mixer was fed at 90 ° C. The feeding temperature balance takes 3-5 minutes. The molten material is mixed at 1 90 ° C and 40 rpm for 10 minutes. The characterization data for these two mixtures and the components of the mixture forming the comparative examples for these experiments are given in Table 7.

Table 7 It is not an example of the present invention 1 Interpolymer (C) containing 433 percent by weight (171 mole) of styrene, 12% of 262 2 Olefin polymer (J) is commercially available poethylene (CPE) and a registered trademark of The Dow Chemical Company as TYRINMR 4211P, and having a chlorine content of 42%, a density of 1 22 g / cm3 and < 2% residual stability as measured by heat of fusion 3 Interpohimer (I) containing 699 percent mole (384 mole) of styrene, 12% of 1 83 Table 7 shows that the examples of the mixture compositions have good mechanical integrity and stress performance as evidenced by stress, deformation and total breakdown energy EXAMPLES 14 A 22 Mixtures with polypropylene and propylene copolymers Preparation of the mixtures: All the compositions of the mixtures are prepared with a Haake mixer equipped with a Rheomix 3000 bowl. The components of the mixtures are first mixed dry in the proportions given in Table 8 and then fed to the balanced mixer to 1 90 ° C. The temperature and power balance takes 3-5 minutes. The melted material is mixed at 1 90 ° C and 40 rpm for 10 minutes. The characterization data for the mixtures and components of the mixtures forming the comparative examples for these experiments are given in Table 8.

Table 8 * It is not an example of the present invention. 1 Interpolymer (G) containing 47.3 weight percent (19.5 mole) of styrene; l2 of 0.01. 2 Interpolymer (I) containing 69.9 percent by weight (38.4 mol) of styrene; l2 of 1 .83. 3 Olefin polymer (K) is a polypropylene homopolymer available from Amoco under the code HPP-9433, and has a melt index (12) of 1 2. 4 Temperature at 1 mm probe depth.

* It is not an example of the present invention. 1 Interpolymer (G) containing 47.3 percent by weight (19.5 mol) of styrene; l2 of 0.01. 2 Interpolymer (I) containing 69.9 percent by weight (38.4 mol) of styrene; l2 of 1.83. 3 Olefin Polymer (L) is an amorphous polypropylene available from Rexene under the code FPP-D1810 and has a melt index of 4. 4 Temperature of 1 mm probe depth.

* It is not an example of the present invention. 1 Interpolymer (G) containing 47.3 percent by weight (19.5 mol) of styrene; l2 of 0.01. 2 Interpolymer (I) containing 69.9 percent by weight (38.4 mol) of styrene; l2 of 1.83. 3 Olefin Polymer (M) is an ethylene-propylene copolymer containing 76% ethylene / 24% propylene, produced via catalyst technology I NSITEMR (a registered trademark of The Dow Chemical Co.) and having a melt index ( l2) of 1 .37. 4 Olefin polymer (N) is an ethylene-propylene-diene terpolymer containing 50.9% ethylene / 44.9% propylene / 4.2% norbornene, produced via I NSITEMR catalyst technology (a registered trademark of The Dow Chemical Co. .) and having a melt index (l2) of 0.56. Table 8 shows that the compositions of the mixtures show good mechanical integrity and strength performance as evidenced by stress, deformation and total energy at break.

EXAMPLES 23, 24 AND 25. Mixtures with ethylene / vinyl acetate copolymer Preparation of the mixtures Three compositions of the mixtures are prepared, examples 23, 24 and 25 in a weight ratio of 50/50 interpolymer (H). ) and olefin polymer (O), ElvaxM R 250, (a registered trademark of Du Pont) a 50/50 weight ratio of interpolymer (G) and olefin polymer (O), and a proportion by weight of 50/50 of interpolymer (A) and olefin polymer (O), with a Haake mixer fitted with a Rheomix 3000 bowl. The components of the mixes are first mixed dry and then fed to the balanced mixer at 1 90 ° C. The balance of temperature and maintenance takes 3-5 minutes. The molten material is mixed at 1 90 ° C and 40 rpm for 10 minutes.

The characterization data for these mixtures and the components of the mixtures forming the comparative experiments are given in Table 9.

Table 9 Table 9 (cont) styrene, l2 of 018 2 Interpolymer (G) containing 473 percent by weight (19.5 mol) of styrene, 12 of 001 3 Interpolymer (H) containing 293 percent by weight (10 mol) of styrene, i2 of 003 4 Polymer (O) is an ethylene / vmilo acetate copolymer, ElvaxMR 250 available from and a registered trademark of DuPont Chemical Company Table 9 shows that the examples of compositions of the mixtures have good mechanical integrity and strength performance as evidenced by the stress, deformation and total energy at the breakdown. The melting rheology data for the examples of the mixtures show that the viscosity low cut and tan d (a measure of low cut melt elasticity) can be unexpectedly altered by incorporating the interpolymers. This results in improved processability in some applications, compared to the component polymer, but with retention of desirable mechanical performance.

EXAMPLE 26 LDPE Polymer The LDPE polymer used in this example has a melt index of 1.8 per ASTM 1238 at 190 ° C / 2.16 kg and a density of 0.923 g / cm 3.

Interpolymer ES The interpolymer ES used in this example is interpolymer I (see tables 1A and 1B). The resulting interpolymer contains 69.9 percent by weight (38.4 percent mole) of styrene moiety (residue) and a melt index (12) of 1.83. The equipment used in this example is a 38 mm screw type extruder having additional mixing and cooling zones at the end of the usual sequential zones of feeding, measuring and mixing. An opening for blowing agent is provided in the barrel of the extruder between the measuring and mixing zones. At the end of the cooling zone, a die hole having a rectangular-shaped opening is attached. The height of the opening, hereinafter called the die gap, is adjustable while its width is fixed at 6.35 mm.

In this example, mixtures of 80/20 and 60/40 of a low density polyethylene (LDPE) and an ES-copolymer are blown with isobutane blowing agent. For comparison, a foam is also prepared from the unblended LDPE resin. The granular polyethylene is premixed with a predetermined amount of the granular ES copolymer, a glycerol monostearate concentrate (GMS) so that the effective GMS level could be 1.0 pph, and a small amount (about 0.02 pph) of talc in dust. GMS is added for dimensional stability of the foam and powdered talc is added to control the size of the cell. The solid mixture is then fed into the extruder feed tank and extruded at a uniform speed of 6.8 kg / h. The temperatures maintained in the extruder zones are 160 ° C in the feed zone, 1 77 ° C in the transition zone, 1 88 ° C in the melting zone, 1 93 ° C in the measuring zone and 1 77 ° C in the mixing zone. Isobutane is injected into the injection gate at a uniform speed, so that the level of blowing agent became approximately 1.3 g-mol per kilogram of polymer (mpk). The temperature of the cooling zone is reduced radically to cool the polymer / blowing agent (gel) mixture at the optimum foaming temperature. The optimum frothing temperature varied from 1 08 ° C to 1 1 1 ° C. The die temperature is maintained at 1 08-1 09 ° C throughout the tests in this example. The opening of the die is adjusted to achieve a good filament of free prefoaming foam.

Strength test and processability The data for processability of the tests are summarized in Table 10. Good foams having low densities and substantially closed cell structure are achieved from mixtures of polymers, as well as from of LDPE resin. The blends allow larger die openings and thus larger sizes of cross sections of foams. All the foams have a width of approximately 32 mm. Foams are dimensionally stable during aging at an ambient temperature, while exhibiting little shrinkage. The strength properties of the foams are tested approximately one month after the extrusion. As shown in Table 10, foams made from LDPE / ES blends are stronger and firmer than LDPE foam in both tension and compression tests.

Table 10 Strength and processability properties of the foams of the mixtures * It is not an example of this invention (1) ES = ethylene / styrene copolymer I having 69.9% styrene residue and a melt index (12) of 1.83 (2) The height of the die opening at the threshold of the pre-foamed in millimeters (3) The thickness of the foam body in millimeters. (4) The body density of aged foam for 4 weeks in kilograms per cubic meter. (5) The cell size determined by ASTM D3576 in millimeters. (6) Stress force of the foam body in the direction of extrusion in kilopascals (7) Stress elongation of the foam body in the extrusion direction in percent (8) Compression force of the foam body to 25% deviation determined by ASTM D3575 in kilopascals Damping characteristics Foams prepared before are tested for their damping characteristics. The test specimens are prepared from previously made foam filaments by cutting them into strips approximately 12.7 mm wide, 4.5 mm thick and 51 mm long. The damping tests are conducted in a dynamic mechanical spectrometer operated in an oscillating torsion mode. In practice, a specimen is mounted on a torsion test jig so that the length between the clamps could be approximately 45 mm. At an ambient temperature of about 25 ° C, the specimen is twisted to approximately 0.5% deformation in an oscillatory movement back and forth at a rate of one radian per second at the start. The oscillation speed is gradually increased until 1 00 radians per second are reached, where the test is completed. During the frequency carryover, the storage modulus (G '), the loss modulus (G "), tan 6 and the damping coefficient (C) are recorded.The last two properties are related to the previous properties and the oscillation speed through the following equations: so d = GJ (1) G 'C = GJ (2) ~? ? = 2 p / (3) where, ? is the angular velocity in radians per second and f, the frequency in Hertz (Hz). Two specimens were tested for each foam. In Table 11, the condensed data are presented at one Hz and 10 Hz. The data is the average of values for two runs. In addition, the damping coefficients for the full range of the frequency are shown in Table 1 2. It is evident from the table that the foams of the LDPE / ES blends are superior to the LDPE foam in buffer capacities or energy absorption. That is, the foams have G ', G ", tan dyc greater than the control LDPE foam It is also evident the intensification of the energy absorption capacity with the level of the ES copolymer The 60/40 LDPE / ES blend foam is remarkable with its capacity buffer five times better than LDPE foam.

Table 1 1 Damping characteristics for various foams of acoustic mixtures * It is not an example of this invention. (1) Storage module in E + 9 dyne per square centimeter. (2) Loss module in E + 9 dyne per square centimeter. (3) Tan delta = G'7G '. (4) Damping coefficient at E + 9 dyne per square centimeter / radians per second.

Table 1 2 Frequency effect on damping coefficients of several Dynamic cushioning test As shown in the tests of this example, the foams of the LDPE / ES blends show their superior energy absorption capabilities also in dynamic cushioning. In this example, the foams made above are prepared in approximately 5.08 cm cube drop test specimens. The foam filaments are cut and soldered together by heat to prepare the test specimens. A specimen is fixed on a board so that its vertical direction (of the foam filament) is aligned vertically. A weight is dropped on the specimens from approximately a height of 61 cm. An accelerometer attached to the top of the weight records the deceleration of the weight by the foam specimen. Four additional falls are made in the same specimen with a given minute interval between falls. The tests are repeated with another weight with a nine specimen. The weights are selected to exert a static force varying from approximately 1.8 kPa to 1 3.4 kPa. The thicknesses of the foam specimen before and after the fall tests are recorded. The data is summarized in Table 1 3. In general, the foams of the LDPE / ES blends show to be better materials that mitigate the blow than the LDPE foam. The foam in the mixtures gives a lower peak deceleration. The ability to mitigate the shock of the 60/40 LDPE / ES blend foam is especially remarkable as the foam registers a low peak deceleration in a static load range. All foams recovered well after the drop tests as indicated by the recovery data for a heavyweight in Table 13.

Table 13 Dynamic cushioning properties * It is not an example of this invention. 1 The average of peak decelerations for one second through five falls in Gs. 2 The thickness as a percentage of an initial hour after the fall tests with the load of 9.3 kPa. 3 Not determined.

EXAMPLE 27 LDPE polymer The LDPE polymer used in this example has a melt index of 1.8 per ASTM 1238 at 190 ° C / 2.16 kg and a density of 0.923 g / cm 3.

ES Interpolymer The interpolymer used in this example is prepared in a manner similar to that of interpolymer C and contains 45.9 weight percent (1 8.3 mole) of styrene moiety and a melt index (12) of 0.43. The apparatus and the method of preparing the foam are essentially the same as in Example 26. A good quality foam of a substantially closed cell structure is made from the mixture. The foam has a thickness of 19 mm, width of 34.5 mm, density of 29 kg / m3 and cell size of 1.2 mm. The dynamic mechanical properties of the foam are determined using a forced ventilation device (MTS 831 Elastomer Test System). In the test, a rectangular specimen with a predetermined dynamic load at a certain frequency is cyclically compressed and the dynamic deformation induced in the specimen is monitored. In practice, a rectangular specimen of 32 9 mm in width, 34.6 mm in depth and 6 5 mm in height of the extruded foam filament is cut and subjected to a dynamic mechanical test in a temperature controlled chamber. The temperature of the chamber is maintained at -10 ° C. The average load is set to -20 Newtons and the dynamic load is set to 1 5 Newtons. The frequency (f) of the cyclic compression is traveled from 1 Hz to 1 01 Hz in a 2 Hz step. dynamic stiffness (K *), the phase angle (d) and shape factor, modulus of elasticity storage (E '), modulus of elastic loss (E ") and damping coefficient of the specimen are calculated. foam by the following equations Form factor = width x depth (A1) Height E '= K "x cos d (A2) Form factor E" = K "x without d (A3) Form factor C = K" without d = E "x form factor (A4) 2pf 2pf The foam made in Test 1.1 of Example 23 is tested similarly for comparison. The test foam specimen 1.1 has a width of 32 mm, depth of 35.2 mm and height of 6.8 mm. The data for these two foam specimens at selected frequencies of 1, 11 and 101 Hz are shown in Table 13.

Table 14 * There is an example of this invention (1) storage module in N / mm2. (2) Loss module in N / mm2. (3) E-VE "(4) Damping coefficient in N-s / mm.

From Table 14, it is evident that the foam of the LDPE / ES blend (465) has the best damping capacity than a LDPE foam at -1 0 ° C.

EXAMPLE 28 In this example, 10 grams of an ethylene-styrene copolymer (ES) which is used in Example 23 (ethylene-styrene copolymer (I), see Table 1 A &B) are mixed by melting with 10 grams of an ethylene-acrylic acid copolymer (EAA) available from and a trademark of The Dow Chemical Company as Primacor ™ 3340 (6.5 wt.% acrylic acid and 9 melt index) using a Brabender mixer. The mixing is done at 1 80 ° C for 1 5 minutes at a rotor rotation speed of 30 rpm. The polymer mixture is molded on a steel bar maintained at 1 80 ° C using a hot press, in order to determine its damping capacity according to the SAE J 1637 test. The steel bar has the dimensions of 0.8 mm thick, 1 2.7 mm wide and 225 mm long. Approximately 200 μm of length of the steel bar is covered with the polymer layer of uniform thickness of about 1.2 mm. The adhesion between the steel bar and the polymer layer is excellent. For comparison, a steel bar specimen coated with PMP resin R 3340, approximately 1.2 mm thick, is also prepared. 7 The specimens are tested according to the SAE J 1637 test for their damping capabilities at an ambient temperature of 23 ° C. The specimen coated with a layer of EAA / ES recorded a damping ratio (factor) of 0.79%. This damping ratio is compared with the damping ratio of an uncovered steel bar (0.1 3%) and that of a steel bar adhered with a pure EAA layer (0.59%).

Example 29-31 Resins were used in Table 1 in the following Examples 29-31. The LDPE used was that used in Example 26 and had a melt index, 12, of 1.8 g / 10 min and a density of 0.923 g / cm 3. The ethylene styrene interpolymers ESI # 's 1 to 4 were prepared as follows: Description of the reactor The simple reactor used was a continuously stirred tank reactor Autoclave, oil jacketed, of 22.7 I (CSTR). A magnetically coupled stirrer with Lightning A-320 propellers provides mixing. The reactor ran full liquid at 3,275 kPa. The process flow was in the background and outside the top. A heat transfer oil was circulated through the reactor socket to remove some of the heat of reaction. After the exit from the reactor was a micromotion flow meter that measured the density of sol ution and fl ux. All the lines of the reactor outlet were traced with a current of 344.7 kPa and were isolated.

Solvent of ethylbenzene or toluene was supplied to the mini-plant at 207 kPa. The feed to the reactor was measured by a Micro-Motion mass flow meter. The variable speed diaphragm pump controlled the feeding speed. At the discharge of the solvent pump a side stream is taken to provide discharge flows for the catalyst injection line (0.45 kg / h) and the reactor stirrer (0.34 kg / h). These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves. An uninhibited styrene monomer was supplied to the mini-plant at 207 kPa. The feed of the reactor was measured by means of a mass flow meter M icro-Motion. A variable speed diaphragm pump controlled the feeding speed. The styrene streams were mixed with the remaining solvent stream. Ethylene was supplied to the mini-plant at 4, 1 37 kPa. The ethylene stream was measured by a MiMotion mass flow meter just before the Research valve controlling the flow. A Brooks flow meter / controllers was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve. The ethylene / hydrogen mixture is combined with the solvent / styrene stream at room temperature. The temperature of the solvent / monomer was allowed to fall as it enters the reactor at ~ 5 ° C by a exchanger with glycol at -5 ° C in the jacket. This current entered the bottom of the reactor. The three-component catalyst system and its solvent discharge also enters the reactor at the bottom, but through a gate different from the monomer stream. The preparation of the catalyst components took place in an inert atmosphere glove box. diluents were placed in nitrogen padded cylinders and charged to the catalyst run tanks in the process area. From these run tanks, the catalyst was pressed with piston pumps and the flow was measured with mimass flow meters. Motion These currents are combined with each other and the catalyst discharge solvent just before entering through a simple injection line to the reactor. The polymerization was stopped with the addition of catalyst neutralizer (water mixed with solvent) in the reactor. Line of product of the reactor after the miotion flow meter measuring the density of the solution Other additives d The polymer can be added with the catalyst neutralizer. A static mixer in the line provides the dispersion of the catalyst neutralizer and additives in the reactor effluent stream. This current then entered the post reactor heaters that provide additional energy for evaporation. instantaneous solvent removal This instantaneous evaporation occurs as the effluent from the post reactor reboiler came out and the pressure drops from 3.275 kPa to -250 mm absolute pressure in the reactor pressure control valve. This evaporated polymer instantly entered a devolatilizer jacketed with alley oil Approximately 85 percent of the volatiles were removed from the polymer in the devolatilizer The volatile salen from the upper part of the hollow devolati The stream was coded with a glycol-enriched exchanger, entered the suction a vacuum pump and it was discharged to a styrene / ethylene separation container and glycol jacket solvent The solvent and styrene were removed from the bottom of the container and ethylene from the top The ethylene stream was measured with a MiMotion mass flow meter and analyzed for the composition The dewaxed ethylene measurement plus a calculation of dissolved gases in the solvent / styrene stream were used to calculate the ethylene conversion. The polymer separated in the devolatilizer was pumped out with a gear pump to a devolatilization vacuum extruder. ZSK-30 The dried polymer leaves the extruder as a simple filament This filament was cooled as it was pulled through a water bath The excess water was blown from the filament with air and the filament was cut into pellets with a filament cutter In In all cases, the three-component modified methylaluminoxane type 3A catalyst stream, CAS # 146905-79-5, was used. To prepare ESI # 1 was 1, 3-pentadiene from (f-but? lam? do) d? met? l (tetramet? lc? clopentad? in? l) s? la-t? tan? o (II ), and the cocatalyst was tetrak? s (pentafluorophen?) seboalkyl bis-hydrogenated methylammonium borate The catalyst used to prepare ESI # 's 2, 3 and 4 was d? met? l [N- (1,1-d ? met? let?) -1,1-d? met? l-1 [(1,2,3,4-5-eta) -1, 5,6,7-tetrahydro-3-phen? ls-? ndacen-1-? l] s? lanamnate (2 -) - N] -t? tan? o and the cocatalyst was tr? s (pentafluorophen? l) boron, CAS # 001109-15-5 The various Process conditions and resulting interpolymer properties are summarized in Table 1 5.

Table 1 5 The weight percent of styrene in the interpolymer is the percent of styrene incorporated in the interpolymer based on the total weight of the ESI resin. The percent mole of styrene in the interpolymer is the percent of styrene incorporated in the interpolymer based on the total moles of ESI The percentage of aPS is the percentage of atactic polystyrene based on the total weight of the resin ESI l 2 is the melting index measured at 1 90 ° C using a weight of 2.1 6 kg.

EJ EM P LO 29 The foams of the LDPE / ESI resin blends of the present invention were made to demonstrate the effect of ES I on the expansion of the foaming temperature window observed against that normally observed for LDPE foams. conventional The foams of LDPE / ESI resin blends were made in an apparatus comprising an extruder, a mixer, a cooler, and a series extrusion die. The LDPE and ESI resin granules were mixed by dry stirring and fed via a feed tank to the extruder. The ESI resin contained a small amount of the talc. The granules were melted and mixed to form a polymer melt. The polymer melt was fed to the mixer where isobutane, a blowing agent, was incorporated to form a polymer gel. The polymer gel was transported through the cooler to lower the temperature of the gel to a desirable foaming temperature. The cooled polymer gel is transported through the extrusion die in a zone of lower pressure to form the expanded foam product. The use of LDPE / ESI resin blends provided a significant increase in the foaming temperature window at 3-4 ° C. This increase is significant since the foaming window is normally only 1 ° C for foams containing only LDPE resin. The expansion of the foaming window reduces the incidence of "freezing" (solidification of the resin before leaving the extrusion die) and generation of production pieces. Low density, high quality closed cell foams were produced without encountering freezing. Based on the results, the useful ES I resins include those which have a total styrene content of 30-75 percent in-weight, melting index of 0 5-20 and up to 20 percent by weight of aPS (polystyrene). atactic) and preferably less than 2 percent by weight of aPS. The total styrene content in the ESI resin is the weight of styrene incorporated in the ethylene / styrene interpolymer plus the weight of the aPS free constituent divided by the total weight of the ESI resin. The results are shown in Table 1 6 below.

Table 16 oo aPS is the atactic polystyrene Tf is the temperature of foaming in degrees Celsius kg / m3 is the density in kilograms per cubic meter% interpolymer ESI is the weight percentage of interpolymer ES I based on the total weight of ESI, aPS and LDPE % aPS is the percentage by weight of aPS based on the total weight of ESI, aPS, and LDPE phr is the parts per half parts by weight of resin (polymer) EXAMPLE 30 Foams of closed cell LDPE / ESI resin mixtures were made in accordance with the present invention. A comparative example of a conventional closed-cell LDPE foam (Sample # 1) was also made. The present foams were made with the apparatus and techniques described in Example 29 The present foams were closed cell and exhibited smaller cell size, better outer layer quality, better firmness, better folding / formability, and better smoothness compared to those of closed cell LDPE foam The results are shown in the Table 1 7. ? c4 is isobutane in parts per hundred parts by weight of resin aPS is the non-atactic polystyrene Tf is the temperature of foaming in grams centigrade kg / m3 is the density in kilograms per cubic meter% ESI interpolymer is the weight percentage of interpolymer of ESI based on the total weight of ESI, aPS and LDPE% of aPS is the percentage by weight based on the total weight of ESI, aPS, and LDPE phr is parts per hundred parts by weight of resin (polymer) * is not an example of the present invention EXAMPLE 31 The foams of the closed cell LDPE / ESI resin blends were made which exhibited excellent dimensional stability without the use of permeability modifiers according to the present invention. A comparative example of a closed cell LDPE was also made. , conventional without the use of permeability modifiers The present foams and the foam of the comparative example were made with the apparatus and technique described in Example 29 Two different ESI resins were employed The foams were made with LDPE / ESI resin blends and the foam of the comparative example were kept at room temperature and were measured for volume change over time. The maximum or maximum volume was noted, whichever existed the greatest deviation. The change in volume was measured by displacement. of water A maximum dimensional change of no more than 1 5 percent was considered desirable (compared to the initial volume measured 60 seconds after extrusion) Foams made with LDPE / ESI # 3 resin exhibited superior dimensional stability as compared to the LDPE foam of the comparative example and the foams made with LDPE / ESI Resin # 2. The results are shown in Table 1 8 below. The excellent dimensional stability can allow the foams to be made with fast permeating blowing agents, such as carbon dioxide and isobutane without the need to use permeability modifiers such as glycerol monostearate. The use of rapid permeate blowing agents without permeation modifiers can provide faster cure times (ie, at very low levels of residual blowing agents and / or replacement of blowing agent in cell gas with ambient air) .

Table 1 8 ic4 is isobutane in parts per hundred parts by weight of resin aPS is atactic polystyrene Tf is the temperature of foaming in degrees centigrade kg / m3 is the density in kilograms per cubic meter% ESI interpolymer is the weight percentage of interpolymer from ESI based on the total weight of ESI, aPS and LDPE. % of aPS is the percentage by weight based on the total weight of ESI, aPS, and LDPE phr is parts per hundred parts by weight of resin (polymer) * is not an example of the present invention

Claims (27)

1. REIVI NDI CATIONS 1 . An article manufactured other than a film, comprising a blend of polymeric materials consisting of (A) from 1 to 99 percent of one or more substantially non-crosslinked interpolymers of α-olefin / vinylidene monomers, wherein the distribution of the monomers of said interpolymers can be described by Bernoulli's statistical model or by a Markovian statistical model of first or second order, and each having been made from monomer components comprising: (1) from 0.5 to 65 percent mol of either (c) at least one aromatic vinylidene monomer, or (d) at least one clogged aliphatic vinylidene monomer corresponding to the formula: A1 I R1 - C = C (R2) 2 wherein A1 is an aliphatic or cycloaliphatic, sterically voluminous bitumen thereof of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkali radicals containing from 1 to 4 carbon atoms, preferably hydrogenous or methyl; each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system or (c) a combination of at least one aromatic vinylidene monomer and at least one clogged aliphatic vinylidene monomer; and (2) from 35 to 99.5 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms, or aliphatic α-olefins having from 2 to 20 carbon atoms and containing polar groups.
2. 2. A manufactured article of claim 1, wherein (i) said mixture comprises from 5 to 95 percent by weight of component (A) and from 95 to 5 percent by weight of component (B); (ii) component (A) contains from 1 to 55 percent mole of component waste (A-1) and from 45 to 99 percent mole of component waste (A-2); and (iii) component (B) comprises a homopolymer or copolymer of monomer components comprising two or more α-olefins having from 2 to 1 2 carbon atoms.
3. 3. A manufactured article of claim 1, wherein (i) said mixture comprises from 1 to 90 percent by weight of component (A) and from 90 to 1 percent by weight of component (B); (II) component (A) contains from 2 to 50 percent mole of component waste (A-1) and from 98 to 50 percent mole of component waste (A-2) 4 A manufactured article of claim 1, in where (i) component (A) is a substantially random ether of styrene and ethylene or a combination of styrene and ethylene and at least one C3 8 al-olefm, and (n) component (B) is an ethylene homopolymer or propylene, or a copolymer of ethylene or propylene and at least one other α-olefin containing from 4 to 8 carbon atoms, or a copolymer of ethylene or propylene and at least one acrylic acid, vinyl acetate, maleic anhydride or acrylic acid, or a terpolymer made of ethylene, propylene and a diene A manufactured article of claim 2, wherein (i) component (A) is a substantially random interpolymer of styrene and ethylene, or styrene, ethylene and at least another α-olefma containing from 3 to 8 carb atoms or, (ii) component (B) is a homopolymer of ethylene or propylene, or a copolymer of ethylene and / or propylene and at least one other olefin containing from 4 to 8 carbon atoms, or an ethylene terpolymer, propylene and at least one of 4-metho pentene, butene-1, hexene-1 or octene-1 A manufactured article of claim 3, wherein (i) the component (A) is an interpol Substantially random number of styrene and ethylene or styrene and a combination of ethylene and at least one of propylene 4-methene pentene, butene-2, hexene-1, octene-1 or norbornene, (ii) component (B) is an ethylene or propylene homopolymer; or a copolymer of ethylene or propylene and at least one other α-olefin containing from 4 to 8 carbon atoms; or a terpolymer of ethylene, propylene and a diene. 7. A manufactured article of claim 1, wherein (1) component (A) is a substantially random interpolymer of styrene and ethylene or styrene and a combination of ethylene and at least one of propylene, 4-methyl pentene, butene- 1, hexene-1, octene-1 or norbornene; (2) component (B) is a homopolymer of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1 or octene-1. 8. A manufactured article of claim 1, wherein (i) component (A) is a substantially random interpolymer of styrene and ethylene; and (ii) component (B) is selected from: (1) one or more ethylene homopolymers, (2) one or more propylene homopolymers, (3) one or more chlorinated polyethylene, (4) one or more copolymers of ethylene and propylene, (5) one or more copolymers of ethylene, propylene and a diene, (6) one or more copolymers of ethylene and octene-1, (7) one or more copolymers of ethylene, propylene and norbornene, (8) one or more copolymers of ethylene and acrylic acid, (9) one or more copolymers of ethylene and vinyl acetate, or (10) any combination of any two or more polymers (1) - (9). 9. A manufactured article of claim 1, wherein (1) component (A) is a substantially random interpolymer made from 1-10 mol percent styrene and 90-99 mol percent ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; and (2) component (B) is selected from: (1) one or more ethylene homopolymers, (2) one or more propylene homopolymers, (3) one or more chlorinated polyethylene, (4) one or more copolymers of ethylene and propylene, (5) one or more copolymers of ethylene, propylene and a diene, (6) one or more copolymers of ethylene and octene-1, (7) one or more copolymers of ethylene, propylene and norbornene, (8) one or more copolymers of ethylene and acrylic acid, (9) one or more copolymers of ethylene and vinyl acetate, or (10) any combination of any two or more polymers (1) - (9). 10. A manufactured article of claim 1, wherein (1) component (A) is a substantially random interpolymer made of 10-25 percent mol of styrene and 75 to 90 percent mol of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; and (2) component (B) is selected from: (1) one or more ethylene homopolymers, (2) one or more propylene homopolymers, (3) one or more chlorinated polyethylene, (4) one or more copolymers of ethylene and propylene, (5) one or more copolymers of ethylene, propylene and a diene, (6) one or more copolymers of ethylene and octene-1, (7) one or more copolymers of ethylene, propylene and norbornene, (8) one or more copolymers of ethylene and acrylic acid, (9) one or more copolymers of ethylene and vinyl acetate, or (10) any combination of any two or more polymers (1) - (9). 11. A manufactured article of claim 1, wherein (1) component (A) is a substantially random interpolymer made from 25-50 percent mol of styrene and 50 to 70 percent mol of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; and (2) component (B) is selected from: (1) one or more homopolymers of ethylene, (2) one or more homopolymers of propylene, (3) one or more chlorinated polyethylene, (4) one or more copolymers of ethylene and propylene, (5) one or more copolymers of ethylene, propylene and a diene, (6) one or more copolymers of ethylene and octene-1, (7) one or more copolymers of ethylene, propylene and norbornene, (8) one or more copolymers of ethylene and acrylic acid, (9) one or more copolymers of ethylene and vinyl acetate, or (10) any combination of any two or more polymers (1) - (9). 12. A fabricated article of claim 1 consisting of (A) from 25 to 99 percent by weight of a substantially random interpolymer made of monomer components comprising 1-10 mole percent styrene and 90-99 percent mole of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; and (B) from 1 to 75 weight percent of a polymer component selected from: (1) one or more ethylene homopolymers, (2) one or more propylene homopolymers, (3) one or more chlorinated polyethylene, (4) one or more copolymers of ethylene and propylene, (5) one or more copolymers of ethylene, propylene and a diene, (6) one or more copolymers of ethylene and octene-1, (7) one or more copolymers of ethylene, propylene and norbornene, (8) one or more copolymers of ethylene and acrylic acid, (9) one or more copolymers of ethylene and acetate vinyl, or (10) any combination of any two or more polymers (1) - (9). 13. A manufactured article of claim 1 consisting of (A) from 1 to 50 weight percent of an interpolymer made of monomer components comprising 1-10 mole percent styrene and 90-99 percent mole of ethylene or a combination of ethylene and minus one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; and (B) from 50 to 99 percent by weight of a polymer component selected from: (1) one or more ethylene homopolymers, (2) one or more propylene homopolymers, (3) one or more chlorinated polyethylene, ( 4) one or more copolymers of ethylene and propylene, (5) one or more copolymers of ethylene, propylene and a diene, (6) one or more copolymers of ethylene and octene-1, (7) one or more ethylene copolymers, propylene and norbornene, (8) one or more copolymers of ethylene and acrylic acid, (9) one or more copolymers of ethylene and vinyl acetate, or (10) any combination of any two or more polymers (1) - (9) . 14. A manufactured article of claim 1 consisting of (A) from 50 to 99 weight percent of an interpolymer made of monomer components comprising 1-10 mole percent styrene and 90-99 percent mole of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; and (B) from 1 to 50 weight percent of a polymer component selected from: (1) one or more ethylene homopolymers, (2) one or more propylene homopolymers, (3) one or more chlorinated polyethylene, (4) ) one or more copolymers of ethylene and propylene, (5) one or more copolymers of ethylene, propylene and a diene, (6) one or more copolymers of ethylene and octene-1, (7) one or more copolymers of ethylene, propylene and norbornene, (8) one or more copolymers of ethylene and acrylic acid, (9) one or more copolymers of ethylene and vinyl acetate, or (10) any combination of any two or more polymers (1) - (9). 15. A manufactured article of claim 1 consisting of (A) from 25 to 99 weight percent of an interpolymer made of monomer components comprising 10-25 percent mol of styrene and 75 to 90 percent mol of ethylene or a combination of ethylene and minus one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; and (B) from 1 to 75 weight percent of a polymer component selected from: (1) one or more ethylene homopolymers, (2) one or more propylene homopolymers, (3) one or more chlorinated polyethylene, (4) ) one or more copolymers of ethylene and propylene, (5) one or more copolymers of ethylene, propylene and a diene, (6) one or more copolymers of ethylene and octene-1, (7) one or more copolymers of ethylene, propylene and norbornene, (8) one or more copolymers of ethylene and acrylic acid, (9) one or more copolymers of ethylene and vinyl acetate, or (10) any combination of any two or more polymers (1) - (9). 16. A manufactured article of claim 1 wherein each of the components (A) and (B) is produced by polymerization or copolymerization of the appropriate monomers in the presence of a metallocene catalyst and a co-catalyst. 1 7. An adhesive system comprising a mixture of polymeric materials comprising (A) from 1 to 99 percent by weight of one or more substantially random interpolymers of blocked α-olefin / vinylidene monomers, made of monomer components comprising: (1) from 0.5 to 65 percent mole of either (a) at least one aromatic vinylidene monomer, or (b) at least one clogged aliphatic vinylidene monomer, or (c) a combination of at least one monomer of aromatic vinylidene and at least one aliphatic vinylidene monomer clogged; Y (2) from 35 to 99.5 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms, or aliphatic α-olefins having from 2 to 20 atoms of carbon and containing polar groups. The adhesive system of claim 1, wherein (1) the component (A) is a substantially random polymer of styrene and ethylene or styrene and a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; (2) Component (B) is a homopolymer of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1 or octene-1. 19. A manufactured article of any of claims 1-16 in the form of an injection molded, compressed, extruded or blown part. 20. The article of any of claims 1-16 in the form of a foam. twenty-one . A foam comprising (I) a mixture of polymeric materials consisting of (A) from 1 to 80 percent of one or more substantially non-crosslinked interpolymers of α-olefin / vinylidene monomers, wherein the distribution of the Such interpolymers can be described by Bernoulli's statistical model or by a Markovian statistical model of first or second order, and each one having been made: (1) from 10 to 65 percent mole of either (a) at least one vinylidene aromatic monomer, or (b) at least one aliphatic vinylidene monomer clogged, corresponding to the formula: A1 R1 C = C (R2) 2 wherein A1 is an aliphatic or cycloaliphatic, sterically bulky substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is selected irrespective of the radical group consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system or (c) a combination of at least one aromatic vinylidene monomer and at least one clogged aliphatic vinylidene monomer; and (2) from 90 to 35 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 85 to 20 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms; and (I I) a blowing agent. 22. A foam of claim 21, wherein (i) the component (I-A) is a copolymer made of monomer components comprising 1 5 - 65 percent mol of styrene and 35 to 85 percent mol of ethylene; (ii) Component (1-B) is a homopolymer of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1 or octene-1. 23. A foam having at least 80 percent of closed cells as determined by ASTM D2856-A, comprising a mixture of polymeric materials comprising (A) from 1 to 99 percent of one or more substantially random interpolymers not cross-linking of α-olefin / nylidene monomers or, where the monomer distribution of such interpolymers can be described by the Bernoulli statistical model or by a Markovian statistical model of the first or second order, and each having been made from monomer components comprising: (1) from 0.5 to 65 percent mole of either (a) at least one aromatic vinylidene monomer, or (b) at least one aliphatic vinylidene monomer clogged, corresponding to the formula: A1 I R1 - C = C (R2) 2 wherein A1 is an aliphatic or cycloaliphatic, sterically bulky substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system; or (c) a combination of at least one aromatic vinylidene monomer and at least one clogged aliphatic vinylidene monomer; and (2) from 35 to 99.5 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms, or aliphatic α-olefins having from 2 to 20 carbon atoms and containing polar groups. 24. A foam having a density of less than 250 kilograms per cubic meter, comprising a blend of polymeric materials comprising (A) from 1 to 99 percent of one or more substantially non-crosslinked interpolymers of α-olefin / vinylidene monomers, wherein the distribution of the monomers of said interpolymers can be described by the Bernoulli statistical model or by a Markovian statistical model of the first or second order, and each having been made from monomer components comprising: (1) from 0.5 to 65 percent mole of either (a) at least one aromatic vinylidene monomer, or (b) at least one aliphatic vinylidene monomer clogged, corresponding to the formula: A1 R1 C = C (R2) 2 wherein A1 is an aliphatic or cycloaliphatic substituent, sterically volumin bear of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system; or (c) a combination of at least one aromatic vinylidene monomer and at least one clogged aliphatic vinylidene monomer; and (2) from 35 to 99.5 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms, or aliphatic α-olefins having from 2 to 20 carbon atoms and containing polar groups. 25. A foam of claim 24 having a density of less than 1000 kilograms per cubic meter. 26. A foam of claim 24 having a density from 10 to 70 kilograms per cubic meter. 27. A foam having an average cell size from 0.05 to 5.0 mil, comprising a blend of polymeric materials comprising (A) from 1 to 99 percent of one or more substantially random non-crosslinked interpolymers of monomers of α-olefin / vi n ilidene. wherein the distribution of the monomers of said interpolymers can be described by the statistical model of Bernoulli or by a Markovian statistical model of the first or second order, and each having been made from monomer components comprising: ( 1) from 0.5 to 65 percent mole of either (a) at least one aromatic vinylidene monomer, or (b) at least one aliphatic vinylidene monomer clogged, corresponding to the formula: A1 R1 - C = C (R2): wherein A1 is an aliphatic or cycloaliphatic, sterically voluminous substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and radical is alkyl containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system; or (c) a combination of at least one aromatic vinylidene monomer and at least one clogged aliphatic vinylidene monomer; and (2) from 35 to 99.5 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms, or aliphatic α-olefins having from 2 to 20 carbon atoms and containing polar groups 28 A foam of claim 27 having an average cell size from 02 to 20 millimeters 29 A foam of claim 28 having an average cell size from 03 to 1 8 millimeters 30 A foam having a maximum volume change of less than plus or minus 5 percent, comprising a mixture of polymeric materials comprising (A) from 1 to 99 percent of one or more substantially non-crosslinked, randomized ether-to-olefin / vmylidene monomer polymers, wherein the distribution of the monomers of said interpolymers can be described by the Bernoulli statistical model or by a Markovian statistical model of first or second order, and each having been made from monomer components comprising (1) from 5 to 65 percent mole of either (a) at least one aromatic vmihdene monomer, or (b) at least one vinylidene monomer aliphatic clogged, corresponding to formula A1 R1 C = C (R2) 2 wherein A1 is a fatically or cycloaliphatic, sterically bulky substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1, together form a ring system; or (c) a combination of at least one aromatic vinylidene monomer and at least one clogged aliphatic vinylidene monomer; and (2) from 35 to 99.5 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms, or aliphatic α-olefins having from 2 to 20 carbon atoms and containing polar groups. 31 A latex or fiber comprising a mixture of polymeric materials comprising (A) from 1 to 99 percent of one or more substantially non-crosslinked interpolymers of α-olefin / vi nidene monomers, wherein the distribution of the monomers of said The variables can be described by Bernoulli's statistical model or by a first-order or second-order Markovian statistical model, and each has been made from monomer components comprising: (1) from 0. 5 has at least one percent of either (a) at least one aromatic vinylidene monomer, or (b) at least one aliphatic vinylidene monomer clogged, corresponding to the formula: A1 R1 - C = C (R2): wherein A1 is an aliphatic or cycloal ifatic, sterically bulky substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system; or (c) a combination of at least one aromatic vinylidene monomer and at least one clogged aliphatic vinylidene monomer; and (2) from 35 to 99.5 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) from 99 to 1 weight percent of one or more homopolymers or copolymers of monomer components comprising aliphatic α-olefins having from 2 to 20 carbon atoms, or aliphatic α-olefins having from 2 to 20 carbon atoms and containing polysubstances 32. The latex or fi ber of claim 31, wherein (1) component (A) is a substantially random ether of styrene and ethylene or styrene and a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; (2) component (B) is a homopolymer of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1 or octene-1. SUMMARY The thermoplastic mixtures are prepared from polymeric materials comprising (A) from 1 to 99 weight percent of at least one polymeric material made of monomer components comprising (1) from 1 to 65 percent mole of (a) at least one monomer of aromatic vinylidene, or (b) at least one blocked cycloaliphatic or aliphatic vinylenide monomer, or (c) a combination of at least one aromatic vinylidene monomer and at least one blocked cycloaliphatic or aliphatic vinylene monomer, and (2) from 99 up to 35 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms, and (B) from 99 to 1 weight percent of at least one polymer made of monomer components comprising (1) from 1 to 1 00 mole percent of at least one α-olefin having from 2 to 20 carbon atoms, and (2) from 0 to 99 percent mole of at least one α-olefin having from 2 to 20 carbon atoms, said monomer being different from the monomer of the component (B-1) These mixtures possess improved properties when compared with the properties of the polymers comprising the mixture These mixtures are useful for the preparation of films, manufactured articles, injection molded parts, modification of asphalt and bitumen, pressure sensitive and hot melt adhesive systems.