MXPA00003675A - Thermoplastic compositions of interpolymers of&agr;-olefin monomers with one or more vinyl or vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers blended with vinyl halide homopolymers and co - Google Patents

Abstract

The present invention relates to blend compositions comprising:(A) of from 1 to 99 weight percent based on the combined weights of Components A, B and C of at least one substantially random interpolymer;and wherein said interpolymer:(1) contains of from 0.5 to 65 mole percent of polymer units derived from:(a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hindered aliphatic vinyl or vinylidene monomer, or (c) a combination of at least one vinyl or vinylidene aromatic monomer and at least one hindered aliphatic vinyl or vinylidene monomer;(2) contains of from 35 to 99.5 mole percent of polymer units derived from at least one aliphatic a-olefin having from 2 to 20 carbon atoms;(3) has a molecular weight (Mn) greater than 1,000;(4) has a melt index (I2) of from 0.01 to 1,000;(5) has a molecular weight distribution (Mw/Mn) of from 1.5 to 20;and (B) of from 99 to 1 weight percent based on the combined weights of Components A, B and C of one or more vinyl halide homopolymer(s) or copolymer(s);and (C) of from 0 to 70 weight percent based on the combined weights of Components A, B and C of one or more plasticizers. The novel blend compositions provide materials with improved processing/property attributes over the unmodified polymers comprising the blends. The blend compositions can exhibit a unique balance of properties including enhanced modulus and barrier properties, improved tensile strength, radio frequency (rf) sealability, solvent bondability, thermal stability and heat resistance depending upon the selection of the individual blend components and their composition ratios. Additionally, the location and the breadth of the glass transition can be controlled by varying the blend compositions and plasticizer level. Surprisingly blends including a plasticizer show a single phase material from glass transition temperature data analysis.

Description

THERMOPLASTIC COMPOSITIONS OF INTERPOLIMEROS DE MONOMERS OF • a-OLEFIN WITH ONE OR MORE AROMATIC MONOMERS OF VINYL OR VINYLIDENE AND / OR ONE OR MORE ALUMINUM OR VINYLIDENE OR VINYLIDENE MONOMERS IMPROVED CYCLES WITH MIXED HOMOPOLYMERS AND COPOL I H EALOGUE OF VINYL HALOGEN DESCRIPTION OF THE INVENTION This invention relates to thermoplastic compositions of interpolymers of α-olefin monomers with one or more vinyl or vinylidene aromatic monomers and / or one or more aliphatic or cycloaliphatic vinylidene or hindered vinylidene monomers blended with homopolymers and vinyl halide copolymers. The generic class of α-olefin / vinyl or hindered vinylidene monomer materials, substantially random interpolymers, including materials such as α-olefin / vinyl aromatic ether copolymers, and their preparation, are known in the art, such as described in EP 416 815 A2. These materials, such as ethylene / styrene interpolymers, offer a wide variety of material structures and properties, which make them useful for varied applications, such as asphalt modifiers or as compatibilizers for blends of polyethylene and polystyrene, as described in US 5,460,818.

The structure, thermal transitions and mechanical properties of the substantially random interpolymers of ethylene and styrene containing up to 50 mol% styrene have been described (Y.W. Cheung, M. J. Guest, Proc. Antee '96, pp. 1634-1637). It has been found that these polymers have glass transitions in the range of -20 ° C to + 35 ° C, and do not show a measurable crystallinity of above 25 mol% in the incorporation of styrene, ie they are essentially amorphous. Although useful in its own right, the industry is constantly seeking to improve the applicability of these interpolymers. In order to perform these applications well, these interpolymers may be desirably improved, for example, in the areas of processing characteristics or glass transition temperature depression or reduced modulus or reduced hardness or lower viscosity or improved final elongation compared to a similar property of the non-modified interpolymer. In relation to this invention, it is also considered advantageous to be able to engineer the glass transition process for materials comprising the interpolymers at a particular temperature scale, so that the energy absorption capacities of the polymer can be better utilized, example, in the damping of sound and vibration. The patent of E.U.A. No. 5,739,200 discloses the improvement in the properties of ether copolymers of aromatic α-olefin / vinyl or vinylidene monomers obtained by the addition of plasticizers.

Similarly, the family of vinyl polymers, such as poly (vinyl chloride) (PVC) have found applications in many markets, in part because of their versatility and good balance. This versatility is easily achieved due to the compatibility of the polymer with a scale of plasticizers, typically used at levels, which improve flexibility and processability. The use of polymeric materials to modify the impact properties of rigid PVC is widely known. For example, the addition of polyacrylic resins, butadiene-containing polymers such as terpolymers of acrylonitrile butadiene-styrene (ABS), and methacrylate-butadiene-styrene terpolymers (MBS), and chlorinated polyethylene (CPE) resins to rigid PVC is known to increase the Impact resistance of PVC products such as house panels, vinyl window frames, electrical conduits, and blow molded PVC bottles. Impact modifiers are typically used in these applications from 5 to 15 parts by weight per 100 parts of the PVC resin. The rigid PVC resins typically used in these applications are typically classified as medium or high molecular weight. EP 0 298282 describes mixtures of homo-, co- or terpolymers of vinyl chloride with random styrene copolymers containing polar groups. The patent of E.U.A. No. 5,250,616 discloses blends of polyvinyl halide polymers and copolymers of styrene, acrylonitrile and butadiene.

In the case of impact modification of low molecular weight or flexible PVC resins, such as those used in injection molding applications, the melt viscosity of the impact modification material is higher than that of the PVC resin. This point can result in poor dispersion and a broad particle size distribution of the impact modifier with the effect of the compounds with a low PVC content having a low impact resistance. Some improvement in the impact resistance can be gained by increasing the amount of impact modifier in the compound, but it usually goes economically against the productive aspect. The purpose of this invention is to provide novel blend compositions comprising one or more vinyl halide polymers and at least one substantially random interpolymer of one or more α-olefin monomers with one or more vinyl or vinylidene aromatic monomers and / or or one or more vinylidene or vinylidene monomers aliphatic or cycloaliphatic hindered. The novel blend compositions provide materials with improved processing / property attributes with respect to the unmodified polymers comprising the blends. The blend compositions can exhibit a unique balance of properties, including modulus and barrier properties, improved tensile strength, toughness, radio frequency (rf) sealing capability, solvent binding capacity, thermal stability, and resistance to ignition, depending on the selection of the individual blend components and their compositional relationships. As a further embodiment, the invention provides novel blend compositions comprising one or more vinyl halide polymers, and at least one substantially random interpolymer of one or more vinyl or vinylidene aromatic monomers and / or aliphatic vinylidene or vinylidene monomers. or hindered cycloaliphatics in combination with one or more plasticizers. These blending compositions allow the manufacture of materials for which the location and respirability of the glass transition can be controlled by varying the composition ratio of the blending component and the level of plasticizer. Surprisingly, certain mixtures including a plasticizer show an individual glass transition temperature (Tg) from thermal analysis data. In other examples, the mixing compositions show multiple Tgs, for example when the level of plasticizer is relatively low. Said mixing compositions further find utility in applications such as sound handling and vibration damping. The present invention relates to blend compositions comprising: (A) from 1 to 99% by weight based on the combined weights of Components A, B and C of at least one substantially random interpolymer; and wherein said interpolymer; (1) contains from 0.5 to 65 mole percent of polymer units derived from: (a) at least one aromatic vinyl or vinylidene monomer, or (b) at least one hindered aliphatic vinylidene vinylidene monomer, or (c) ) a combination of at least one aromatic vinyl or vinylidene monomer and at least one hindered aliphatic vinylidene or vinylidene monomer; (2) contains from 35 to 99.5 mol% of polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; (3) has a molecular weight (Mn) greater than 1,000; (4) has a melt index (12) of 0.01 to 1,000; (5) has a molecular weight distribution (Mw / Mn) of 1.5 to twenty; and (B) from 99 to 1% by weight based on the combined weights of Components A, B and C of one or more vinyl halide copolymer (s); and (C) from 0 to 70% by weight based on the combined weights of Components A, B and C of one or more plasticizers. The compositions of the present invention can be used to produce a wide variety of manufactured articles such as, for example, sheets and films calendered, cast and blown and injection molded parts. The compositions of the present invention can further find utility in flexible molded articles, such as layers in multi-layer film structures, in applications such as automobile instrument panel covers, as building materials such as boards, in forming systems of floor, as coatings on substrates including polymers, paper, leather, cloth and inorganic building materials, such as foams for damping of heat, sound and vibration.

Definitions All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and registered by CRC Press, Inc., 1989. Also any reference to the group or groups must be to the Group or Groups as reflected in this Periodic Table of Elements using the IUPAC system to number groups. Any numerical values presented here include all values from the lowest value to the highest value in increments of one unit as long as 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 process variable such as, for example, temperature, pressure time, is, for example, from 1 to 90, preferably from 20 to 80, very preferably from 30 to 70, it is understood that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc., are expressly listed in this specification.

For values, which are less than one, a unit is considered to be 0.0001, 0.001 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 that will be considered as expressly stated in this application in a similar manner. The term "hydrocarbyl", as used herein, means any aliphatic, cycloaliphatic, aromatic, aliphatic substituted with aryl, cycloaliphatic substituted with aryl, aromatic substituted with aliphatic, or cycloaliphatic substituted with aliphatic group. The term "hydrocarbyloxy" means a hydrocarbyl group having an oxygen bond between it and the carbon atom to which it is attached. The term "copolymer", as used herein, means a polymer, wherein at least two different monomers are polymerized to form the copolymer. The term "interpolymer" is used herein to denote a polymer, wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc. The term "substantially random (a)" in the substantially random interpolymer comprising an α-olefin and an aromatic vinyl or vinylidene monomer or an aliphatic or cycloaliphatic vinylidene or hindered vinylidene monomer, as used herein, means that the The distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a Markovian statistical model of the first or second order, as described by JC Randall in Polymer Sequence Determination, Carbon-13 NMR Method. Academic Press, New York, 1977, p. 71-78. Preferably, the substantially random interpolymer comprising an α-olefin and an aromatic vinyl or vinylidene monomer does not contain more than 15% of the total amount of the vinyl aromatic monomer or vinylidene in aromatic vinyl or vinylidene monomer blocks of more than 3. units. Most preferably, the interpolymer was not characterized by a high degree of both isotacticity and syndiotacticity. This means that in the "13 NMR" carbon spectrum of the substantially random interpolymer, the peak areas corresponding to the methylene carbon and the main chain methine representing sequences of either bivalent meso radical or racemic bivalent radical, should not exceed 75 % of the total peak area of the methylene or main chain methine carbon.

The Impedied Ethylene / Vinylidene Interpolymers The substantially randomized α-olefin / vinyl or vinylidene aromatic interpolymer blend components of the present invention include, but are not limited to, interpolymers prepared by polymerizing one or more α-olefins with one or more monomers vinyl or vinylidene aromatics and / or one or more vinylidene or vinylidene monomers aliphatic or cycloaliphatic hindered. Suitable α-olefins include, for example, α-olefins containing from 2 to 20, preferably from 2 to 12, most preferably from 2 to 8 carbon atoms. Particularly suitable are ethylene, propylene, buten-1,4-methyI-1-pentene, hexene-1 and octene-1. These α-olefins do not contain an aromatic portion. The aromatic vinyl or vinylidene monomers, which can be used to prepare the interpolymers include, for example, those represented by the following formula: Ar I (CH2) n 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 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 halogen, C 1-4 alkyl, and C 1-4 haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero. Aromatic vinyl or vinylidene monomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable of these monomers include styrene and its derivatives substituted with lower alkyl or with halogen. Preferred monomers include styrene, α-methyl styrene, styrene derivatives substituted with lower alkyl (C 1 -C) or phenyl ring, such as, for example, ortho-, meta-, and para-methylstyrene, the halogenated styrenes of ring, para-vinyl toluene or mixtures thereof. A most preferred aromatic vinyl monomer is styrene. By the term "aliphatic or hindered cycloaliphatic vinylidene or vinylidene compounds", it represents addition-polymerizable vinyl or vinylidene monomers corresponding to the formula: A1 I R1 - C = C (R2) 2 wherein A1 is a sterically bulky, aliphatic or cycloaliphatic 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 or 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 bulky" is meant that the monomer bearing this substituent is normally incapable of addition polymerization through Ziegler-Natta polymerization catalysts at a rate comparable with ethylene polymerizations. Aliphatic or hindered cycloaliphatic vinylidene compounds are monomers wherein 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 substituted alkyl or aryl ring derivatives thereof, tert-butyl, norbornyl. Preferred aliphatic or cycloaliphatic hindered vinylidene compounds are the various ring-substituted derivatives with isomeric vinyl of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. Especially suitable are 1-, 3- and 4-vinylcyclohexene. Simple linear α-olefins including, for example, α-olefins containing from 3 to about 20 carbon atoms such as ethylene, propylene, buten-1,4-methyl-1-pentene, hexene-1-or octene-1 are not examples of sterically hindered aliphatic or cycloaliphatic vinylidene or vinylidene compounds. The substantially random interpolymers can be modified through typical grafting, hydrogenation, 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. One method for the preparation of the substantially random interpolymers includes polymerizing a mixture of polymerizable monomers in the presence of one or more catalysts of restricted geometry in combination with several co-catalysts, as described in EP-A-0,416,815 by James C. Stevens and the US patent No. 5, 703,187 by Francis J. Timmers. Preferred operating conditions for such polymerization reactions are atmospheric pressures up to 3000 atmospheres and temperatures from -30 ° C to 200 ° C. Polymerizations and removal of the unreacted monomer at temperatures above the autopolymerization temperature of the respective monomers may result in the formation of some amounts of homopolymer polymerization products, for example, the production of atactic polystyrene. Examples of suitable catalysts and methods for the preparation of substantially random interpolymers are described in the patent application of E.U.A. Series No. 702,475, filed May 20, 1991 (EP-A-514,828); as well as US 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, all of these patents and applications are incorporated herein by reference. The substantially random α-olefin / vinylidene aromatic interpolymers can also be prepared by the methods described in JP 07/278230 using compounds shown by the general formula: / CP1 R1 wherein Cp1 and Cp2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents thereof, independently of one another; R1 and R2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1-12, alkoxy groups, or aryloxy groups, independently of one another; M is a group IV metal, preferably Zr or Hf, most preferably Zr; and R3 is an alkylene group or a silanodiyl group used to crosslink Cp1 and Cp2. The substantially random aromatic α-olefin / vinyl or vinylidene 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, p. 25 (September 1992), all of which are incorporated herein by reference in their entirety. Also suitable are substantially random interpolymers comprising at least one quadrivalent element of α-olefin / vinyl aromatic / vinyl aromatic / α-olefin 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 on the chemical shift scale of 43.70-44.25 ppm and 38.0-38.5 ppm. Specifically, the largest peaks are observed at 44.1, 43.9 and 38.2 ppm. A proton test NMR experiment indicates that signals in the chemical shift region of 43.70-44.25 ppm are methine carbon and signals in the region of 38.0-38.5 ppm are methylene carbons. It is believed that these new signals are due to sequences involving two end-to-end vinyl aromatic monomer insertions preceded and followed by at least one α-olefin insert, eg, a quadrivalent ethylene / styrene / element. styrene / ethylene, wherein the styrene monomer insertions of said quadrivalent elements occur exclusively in a form of 1.2 (head to end). It is understood by those skilled in the art that for such quadrivalent elements involving a vinyl aromatic monomer other than styrene and an α-olefin other than ethylene, that the quadrivalent element of ethylene / vinyl aromatic monomer / vinyl aromatic monomer / ethylene it will give rise to similar peaks of carbon13 NMR, but with slightly different chemical shifts. These interpolymers are prepared by conducting the polymerization at temperatures from -30 ° C to 250 ° C in the presence of said catalysts as those represented by the formula: / wherein: each Cp is independently, from each occurrence, a substituted p-cyclopentadienyl group attached to M; E is C or Si; M is a group IV metal, preferably Zr or Hf, most preferably Zr; each R is independently, of each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbyl, containing up to 30, preferably from 1 to 20, most preferably from 1 to 10 carbon atoms or silicon; each R 'is independently, of each occurrence, H, halogen, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl containing up to 30, preferably 1 to 20, most preferably 1 to 10 carbon atoms or silicon or two R' groups together may be a C1-10 hydrocarbyl substituted with 1,3-butadiene; m is 1 or 2; and optionally, but preferably in the presence of an activating co-catalyst, particularly suitable substituted cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, of each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrobisilyl, containing up to 30, preferably from 1 to 20, most preferably from 1 to 10 carbon atoms or silicon, or two R groups together form a divalent derivative of said group. Preferably R, independently of each occurrence, is (including where all isomers are appropriate) hydrogen, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl, or (where appropriate) two R groups are linked together to form a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl or octahydrofluorenyl. Particularly preferred catalysts include, for example, racemic (dimethylsilandiyl) -bis) - (2-methyl-4-phenylindenyl) zirconium dichloride, 1,4-dif in 1- (dimethylsilandiyl) -bis-1,3-butadiene) - racemic (2-methyl-4-phenylindenyl) zirconium, C 1-4 dialkyl of racemic (dimethylsilandiyl) -bis) - (2-methyl-4-phenyl-indenyl) zirconium, C? .4 dialkoxide of (dimethylsilandiyl) -bis) - racemic (2-methyl-4-phenylindenyl) zirconium, or any combination thereof. It is also possible to use the following catalysts of restricted geometry based on titanium, [N- (1,1-dimethylethyl) -1, 1 -dimethyl-1 - [(1, 2,3,4,5 -?) - 1 , 5,6,7-tetrahydro-s-indacen-1-yl] silanaminate (2 -) - NJtitanium dimethyl; (1-indenyl) (tert-butylamido) dimethylsilane titanium dimethyl; ((3-tert-butyl) (1,2,3,4,5-γ) -1-indenyl) (tert-butylamido) dimethylsilane titanium dimethyl; and ((3-isopropyl) (1, 2,3,4, 5-γ) -1-indenyl) (tert-butylamido) dimethylsilane titanium dimethyl, or any combination thereof.

Other preparation methods for the substantially randomized α-olefin / vinylidene aromatic interpolymer blend components of the present invention have been described in the literature. Longo and Grassi (Makromol, Chem .. Volume 191, pp. 2387 to 2398 [1996]) and D'Anniello et al. (Journal of Applied Polymer Science, Volume 58, pp. 1701-1706 [1995]) reported the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCI3) to prepare an ethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am. Chem. Soc. Div. Polym. Chem.) Volume 35, p. 686, 687 [1994]) have reported the copolymerization of the catalyst using MgCl2 / TiCl4 / NdCI3 / AI (iBu) 3 to give random copolymers of styrene and propylene. Lu et al. (Journal of Applied Polymer Science, Volume 53, pp. 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCl / NdCI3 / MgCl2 / AI (Et) 2 catalyst. The manufacture of α-olefin / vinyl aromatic monomer interpolymers, such as propylene / styrene and butene / styrene are described in the U.S.A. No. 5,244,996, issued to Mitsui Petrochemical Industries Ltd., or the patent of E.U.A. No. 5,652,315 also issued to Mitsui Petrochemical Industries Ltd., or as described in DE 197 11 339 A1 of Denki Kagaku Kogyo KK. Also included as interpolymer mixing components are the isoolefin / para-alkylstyrene, C4-C7 interpolymers, which are random copolymers of a C4-C7 isomonoolefin, such as isobutylene and a para-alkylstyrene comonomer, preferably for methylstyrene containing at least 80%, preferably at least 90% by weight of the para isomer. These interpolymers also include functionalized interpolymers, wherein at least some of the alkyl substituent groups present in the styrene monomer units contain halogen or other functional groups incorporated through nucleophilic substitution of benzyl halogen with other groups such as alkoxide, phenoxide, carboxylate, thiolate, thioether, thiocarbamate, dithiocarbamate, thiourea, xanthate, cyanide, malonate, amine, amide, carbazole, phthalamide, maleimide, cyanate and mixtures thereof. The preferred materials can be characterized as isobutylene interpolymers containing the following monomer units randomly spaced along the polymer chain: these functionalized isomonoolefin interpolymers and their method of preparation are more particularly described in the U.S.A. No. 5,162,445. The most useful of these functionalized materials are elastomeric, random interpolymers of isobutylene and para-methylstyrene containing from 0.5 to 20 mol% para-methylstyrene, wherein up to 60 mol% of the methyl substituent groups present on the benzyl ring contain a bromine or chlorine atom, preferably a bromine atom. These polymers have a substantially homogeneous compositional distribution, so that at least 95% by weight of the polymer has a para-alkylstyrene content of 10% of the average para-alkylstyrene content of the polymer. Most preferred polymers are also characterized by a narrow molecular weight distribution (Mw / Mn) of less than 5, most preferably less than 2.5, a viscosity average molecular weight in the range of 200,000 to 2,000,000, and an average molecular weight in preferred number on the scale of 25,000 to 750,000, as determined by Gel Penetration Chromatography. The interpolymers can be prepared through slurry polymerization of the monomer mixture using a Lewis acid catalyst followed by halogenation, preferably bromination, in solution in the presence of halogen and a radical initiator such as a thermal and / or light initiator. and / or chemical. Also preferred are brominated interpolymers, which generally contain from 0.1 to 5 mol% of bromo-methyl groups, most of which are monobromomethyl, with less than 0.05 mole% of dibromomethyl substituents present in the copolymer. The highly preferred interpolymers contain from 0.05 to 2.5% by weight of bromine based on the weight of the interpolymer, most preferably from 0.05 to 0.75% by weight of bromine, and are substantially free of halogen in the ring or halogen in the structure chain of polymer base. These interpolymers, their method of preparation, their method of curing and grafting, and the functionalized polymers derived therefrom are more particularly described in the U.S. patent. No. 5,162,445 mentioned above. Such etherpolymers are commercially available from Exxon Chemical under the trade name of Exxpro ™ Specialty Elastomers. Homopolymers and Copolymers of Vinyl Halide Vinyl halide homopolymers and copolymers are a group of resins, which use as a development block, the vinyl structure CH2 = CXY, where X is selected from the group consisting of F, Cl, Br and I, and Y is selected from the group consisting of F, Cl, Br, I, and H. The vinyl halide polymer component of the mixtures of the present invention includes, but is not limited to, homopolymers and vinyl halide copolymers with copolymerizable monomers such as α-olefins including, but not limited to, ethylene, propylene, vinyl esters of organic acids containing from 1 to 18 carbon atoms, eg, vinyl acetate, vinyl stearate, etc.; vinyl chloride, vinylidene chloride, symmetrical dichloroethylene; acrylonitrile, methacrylonitrile; alkyl acrylate esters wherein the alkyl group contains from 1 to 8 carbon atoms, for example, methyl acrylate and butyl acrylate; the corresponding alkyl methacrylate esters; dialkyl esters of dibasic organic acids wherein the alkyl groups contain from 1 to 8 carbon atoms, for example, dibutyl fumarate, diethyl maleate, etc. Preferably, the vinyl halide polymers are homopolymers or copolymers of vinyl chloride or vinylidene chloride. Poly (vinyl chloride) (PVC) polymers are further classified into two main types by their degree of rigidity. These are "rigid" PVC and "flexible" PVC. Flexible PVC is distinguished from rigid PVC mainly by the presence of and a quantity of plasticizers in the resin. Flexible PVC typically has improved processability, lower tensile strength and higher elongation than rigid PVC. Of the vinylidene chloride homopolymers and copolymers (PVDC), typically copolymers with vinyl chloride, acrylates or nitriles are commercially used and are highly preferred. The choice of the comonomer significantly affects the properties of the resulting polymer. Perhaps the most notable properties of the various PVDCs are their low permeability to gases and liquids, barrier properties; and chemical resistance. Also included are the various PVC and PVDC formulations containing minor amounts of other materials present to modify the properties of PVC or PVDC, including, but not limited to, polystyrene, styrenic copolymers, polyolefins including homo and copolymers comprising polyethylene, and / or polypropylene, and other ethylene / α-olefin copolymers, polyacrylic resins, butadiene-containing polymers such as acrylonitrile-butadiene-styrene (ABS) terpolymers, and methacrylate-butadiene-styrene (MBS) terpolymers and chlorinated polyethylene resins ( CPE). Also included in the family of vinyl halide polymers for use as the blend components of the present invention are the chlorinated derivatives of PVC, typically prepared by post-chlorination of the base resin and known as chlorinated PVC, (CPVC). Although the CPVC is based on PVC and shares some of its characteristic properties, the CPVC is a unique polymer that has a very high melting temperature scale (410-450 ° C) and a higher glass transition temperature (115 -135 ° C) than PVC.

Plasticizers There is a wide knowledge base on PVC plasticizing, and it is generally known that many thermoplastics can be plasticized. Reference is made, for example, to "Plasticizers" in "Modern Plastics Encvclopedia, broadcast in mid-October 1988, Volume 65, No. 11, p. 180-184, McGraw Hill, 1989) regarding aspects of this type of technology. Depending on the type of polymer, typical families of plasticizers include phosphoric acid derivatives, phthalic acid derivatives, trimellitate esters, benzoates, adipate esters, epoxy compounds, phosphate esters, glutarates and mineral oil. Based on their molecular weight, plasticizers are also classified as "monomeric" or "polymeric". Compared to monomeric plasticizers, polymeric plasticizers generally tend to exhibit higher permanence, lower compatibility, and lower plastification efficiency. Plasticizers are also classified as "primary", and have a high compatibility with a particular polymer, or "secondary", if they have a lower compatibility. Mixtures of the two types of plasticizers can be used to obtain cost / performance balances. Suitable modifiers which may be used herein as the plasticizer component (C) include at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, adipate esters, epoxy components, phosphate esters (triaryl, trialkyl) , alkyl-aryl phosphates compounds), glutarates and oils. Particularly suitable phthalate esters include, for example, C4-C18 dialkyl phthalate esters such as diethyl, dibutyl phthalate, diisobutyl phthalate, butyl 2-ethylhexyl phthalate, dioctyl phthalate, dinonyl phthalate, diisononyl phthalate, phthalate of didecyl, diisodecyl phthalate, diundecyl phthalate, aliphatic esters compounds such as heptyl nonyl phthalate, di (n-hexyl, n-octyl, n-decyl) phthalate (P610), di (n-octyl, n-decyl) phthalate (P810) and phthalate aromatic esters such as phthalate diphenyl ester, or aliphatic-aromatic esters compounds such as benzyl butyl phthalate or any combination thereof.

Additives Additives such as antioxidants (e.g., hindered phenols such as, for example, lrganox®1010), phosphites (e.g., lrgafos®168), (both are registered trademarks of and supplied by Ciba-Geigy Corporation, NY), stabilizers UV, binding additives (eg, polyisobutylene), antiblock additives, colorants, pigments, fillers, may also be included in the ether polymers employed in the blends of and / or employed in the present invention, to the extent that they do not interfere with the improved properties of the present invention. The additives are employed in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant employed is that amount which prevents the polymer or polymer mixture from oxidation at the temperatures and environment employed during the storage and final use of the polymers. Said amount of antioxidants is usually in the range of 0.01 to 10, preferably 0.05 to 5, most preferably 0.1 to 2% by weight based on the weight of the polymer or polymer mixture. Similarly, the amounts of any of the other additives mentioned are the functionally equivalent amounts, such as the amount to make the polymer or polymer mixture anti-blocking, to produce the desired amount of filler charge to produce the desired result, for provide the desired color from the dye or pigment. Said additives can suitably be employed in the range of 0.05 to 50, preferably from 0.1 to 35, most preferably from 0.2 to 20% by weight based on the weight of the polymer or polymer mixture. However, in the case of fillers, these can be employed in an amount of up to 90% by weight based on the weight of the polymer or the polymer mixture. Additives such as fillers also play an important role in the aesthetics of a fine article by providing a glossy or matte finish.

The Final Blend Compositions The compositions of the present invention will be prepared by any conventional method, including dry blending the individual components and subsequently mixing under melting or melt blending, either directly in the extruder or mill used to make the article finished (for example, the part of a car), or pre-mixed under melting in a separate extruder or mill (for example, a Banbury mixer). There are many types of milling operations, which can be used to form articles or fabricated parts useful from the compositions herein, including thermoforming and various injection molding processes (for example, those described in Modern Plastics Encyclopedia / 89 , issued in mid-October 1988, Volume 65, Number 11, page 264-268, "Introduction to Injection Molding" and on pages 270-271, "Injection Molding Thermoplastics", the descriptions of which are incorporated here by reference) and blow molding methods (for example, those described in Modern Plastics Encyclopedia / 89, issued in mid-October 1988, Volume 65, Number 11, page 217-218, "Extrusion-Blow Molding", description of which is incorporated herein by reference) and profile extrusion. Also included are direct mixing and final part formation in an individual melt processing operation to manufacture, for example, sheets and films. Some of the items manufactured include sporting goods, containers such as for food or other household items, footwear and automotive articles, such as soft bands. The compositions of the present invention, in combination with the final part-forming operation, can be selected to control the aesthetics of the part such as a shiny or matt appearance. The compositions of the present invention may also find utility in so-called plastisols or pastes, wherein the polymer components are dispersed in a fluid consisting of the plasticizer. To control the rheology, additional components such as viscosity modifiers, diluents or thickeners are generally employed. The final formulations may also include stabilizers and fillers such as calcium carbonate, clays, fuller's earth, barites, silica, mica and talcum to control the properties and aesthetics. These plastisols find utility in a range of applications including, but not limited to, shaped articles such as toys, joints, films and sheets, such as coatings on polymeric substrates, paper, leather, fabric, and inorganic building materials, and as foams for heat, sound and vibration damping. Plastisols can be applied through procedures such as dip coating, rotary coating, spray systems and hand molding.

Properties of the Individual Mixture Components and the Final Mixture Compositions a) The Ethylene / Vinyl or Vinylidene or Vinyl or Vinylidene Aromatic Interpolymers Prevent the Polymer of one or more α-olefins and one or more vinyl aromatic monomers or Vinylidene and / or one or more aliphatic or hindered cycloaliphatic vinyl or 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, most preferably from 2 to 50 mol% of at least one aromatic vinyl or vinylidene monomer and / or hindered or aliphatic or cycloaliphatic vinylidene or vinylidene monomer. to 99.5, preferably from 45 to 99, most preferably from 50 to 98 mol% of at least one aliphatic α-olefin having from 2 to 20 carbon atoms. The number average molecular weight (Mn) of these ether polymers is usually greater than about 1., 000, preferably around 5,000 to 1,000,000, most preferably around 10,000 to 500,000. The interpolymer (s) applicable to the present invention can have a melt index (12) of 0.01 to 1000, preferably 0.1 to 100, most preferably 0.5 to 30 g / 10 min. The polydispersity ratio of Mw / Mn of the interpolymer (s) applicable to the present invention is 1.5.20, preferably 1.8 to 10, most preferably 2 to 5. While preparing the substantially random interpolymer, one can form a amount of homopolymer, for example, due to the homopolymerization of vinyl aromatic monomer at elevated temperatures. The presence of the aromatic vinyl homopolymer in general is not harmful for the purposes of the present invention and can be tolerated. The aromatic vinyl homopolymer can be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from the solution with a non-solvent for either the interpolymer or the vinyl aromatic homopolymer. For the purpose of the present invention, it is preferred that not more than 20% by weight, preferably less than 15% by weight based on the total weight of atactic vinyl aromatic homopolymer interpolymers be present. b) The Vinyl Halogenide Polymer Mixtures were prepared using both flexible and rigid PVC. For mixtures containing flexible PVC, samples with a hardness of 55 and 80 Shore A were prepared. The molecular weight of PVC is commonly expressed in terms of K value or viscosity number, which generally ranges from 50 to 80. Molecular weight it increases with the increase of the K value. The typical MWD (Mw / Mn) for the PVC is from 2.0 to 2.5. The following table shows the correlation between the value K and Mn. K Mn 50 -28,000 80 -80,000 c) The Final Blend Compositions The blends comprise from 1 to 99% by weight of at least one substantially random interpolymer, preferably from 5 to 95% by weight, most preferably from 10 to 90% by weight. The blends further comprise 1-99% by weight of at least one vinyl chloride polymer, preferably from 5 to 95% by weight, most preferably from 10 to 90% by weight. The blends further comprise 0-70% by weight of at least one plasticizer, preferably 5 to 50% by weight, most preferably 10 to 40% by weight. The following examples are illustrative of the invention, but were not constructed as limiting the scope thereof in any way.

EXAMPLES Test Methods a) Density and Flow Measurements under Fusion: The density of the polymer compositions for use in the present invention was measured in accordance with ASTM D-792. The molecular weight of the polymer compositions for use in the present invention is conveniently indicated using a melt index measurement determined in accordance with ASTM D-1238, Condition 190 ° C / 2.16 kg (formerly known as "Condition (E)"). and also known as l2). b) Chemical Displacements of 13 C-NMR: In order to determine the chemical shifts of "13 NMR" carbon of the interpolymers described, the following procedures and conditions were employed: 5 to 10% by weight of polymer solution in one was prepared. mixture consisting of 50% by volume of 1, 1, 2,2-tetrachloroethane-d2 and 50% by volume of 0.10 molar chromium tris (acetylacetonate) in 1,2,4-trichlorobenzene. NMR spectra were purchased from 130 ° C using a reverse gate decoupling sequence, a pulse width of 90 ° and a pulse delay of 5 seconds or more.The spectra were referenced to the methylene signal isolated from the assigned polymer at 30,000 ppm. c) Part Preparation and Test Procedures: Plasticizer P610 was obtained from C.P. Hall: P610 is a dialkyl phthalate ester (hexyl, octyl, decyl) linear compound having a molecular weight of 400. d) Compression Molding: Samples were melted at 19 °° C for 3 minutes and compression molded at 190 ° C under a pressure of 9080kg for another 2 minutes. Subsequently, the molten materials were extinguished in a press balanced at room temperature. e) Differential Scanning Calorimetry (DSC): DuPont DSC-2210 was used to measure the thermal transition temperatures and transition heat for the samples. In order to eliminate the previous thermal history, the samples were first heated to 160 ° C. Heating and cooling curves were recorded at 10 ° C / min. The melting (tm of the second heat) and crystallization (tc) temperatures were recorded from the peak temperatures of the endotherm and exotherm, respectively. f) Dynamic Mechanical Spectroscopy (DMS): the dynamic mechanical properties of compression molded samples were verified using a Rheometrics 800E mechanical spectrometer. The samples were operated on a rectangular geometry of torsion in solid state and were purged under nitrogen to avoid thermal degradation. Generally, the sample was cooled to -100 ° C and a voltage of 0.05% was applied. The oscillation frequency was set at 10 radios / sec, and the temperature was placed on ramps in increments of 5 ° C. g) Mechanical Test: The tensile properties of the compression molded samples were measured using an Instron 1145 tension machine. Samples of ASTM-D638 (microtension) were tested at a transverse speed of 12.7 cm / min. The given data were the average of four voltage measurements. The standard deviation for the final properties was typically 10% of the average value reported. The elastic limit at the point of inflection of the stress-strain curve (sy, MPa) was measured as the ultimate tensile stress at break (sb, MPa) and the modulus of elasticity (E, MPa). h) Relaxation by Traction Effort: The relaxation of uniaxial tensile stress was evaluated using an Instron 1145 tension machine. The compression molded film (thickness of -508 microns) with a length of 254 microns was deformed to a resistance level 50% at a resistance speed of 20 min'1. The force required to maintain an elongation of 50% was verified for 10 minutes. The magnitude of relaxation by stress is defined as Sr, the percentage = (fj - f f / f ¡) x 100, where f, is the initial force and ff is the final force. il Thermal Mechanical Analysis: After determining the service temperature (TMA (1 mm)) from a thermal mechanical analyzer (Perkin Elmer TMA series 7) scanned at 5 ° C / min., and a load of 1 Newton and defined as the point at which the probe penetrates 1 mm into the sample.

The Individual Blending Components Preparation of ESI # 1 ESI # 1 is a substantially random ethylene-styrene interpolymer containing 74 wt.% Styrene, and 26 wt.% Ethylene (based on the weight of the substantially random ethylene-styrene interpolymer) ) and 9% by weight of atactic polystyrene (based on the combined weight of the substantially random ethylene-styrene interpolymer and atactic polystyrene). The interpolymer was prepared in a stirred, semi-continuous batch reactor of 1512 liters. The reaction mixture consisted of approximately 6660 liters of a solvent comprising a mixture of cyclohexane (85% by weight) and isopentane (15% by weight), and styrene. Before the addition, the solvent, styrene and ethylene were purified to remove water and oxygen. The inhibitor in styrene was also removed. The inert components were removed by purging in a container with ethylene. The vessel was then controlled in the pressure to a fixation point with ethylene. Hydrogen was added to control the molecular weight. The temperature in the container was controlled to a fixing point by varying the water temperature of the jacket in the container. Prior to polymerization, the vessel was heated to the desired operating temperature and catalyst components: titanium: (N-1,1-dimethylethyl) -dimethyl (1- (1,2,3,4,5-eta) -2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl) silanaminate)) (2-) N) -dimethyl, (CAS # 135072-62-7), tris (pentafluorophenyl) boron, ( CAS # 001109-15-5), and modified methylalumoxane type 3A, (CAS # 146905-79-5), were controlled in the flow, (on a molar ratio basis of 1/3/5, respectively), were combined , and they were added to the container. After stirring, the polymerization was allowed to proceed with ethylene supplied to the reactor as required, to maintain the container pressure. In some cases, hydrogen was added to the upper reactor space to maintain a molar ratio to the ethylene concentration. At the end of the operation, the catalyst flow was stopped, the ethylene was removed from the reactor, then 1000 ppm of Irganox * 1010 antioxidant was added to the solution and the polymer was isolated from the solution either by vapor separation in a vessel or through the use of a devolatilization extruder. In the case of the material separated by steam, further processing was required in an equipment similar to the extruder to reduce residual moisture and any unreacted styrene.

Preparation of ESI # 2 ESI # 2 is a substantially random ethylene-styrene interpolymer containing 27% by weight of styrene and 73% by weight of ethylene (based on the weight of the substantially random ethylene-styrene ether polymer) and 1% by weight of atactic polystyrene (based on the combined weight of the substantially random ethylene-styrene interpolymer and atactic polystyrene) prepared essentially as for ESI # 1 using the conditions in Table 1.

TABLE 1 TABLE 1 CONT.

Preparation of ESI # 3 ESI # 3 is a substantially random ethylene-styrene interpolymer containing 73 wt.% Styrene and 27 wt.% Ethylene (based on the weight of the substantially random ethylene-styrene interpolymer) and 9 wt.% of atactic polystyrene (based on substantially random ethylene-styrene interpolymer and atactic polystyrene) prepared as described below, using the conditions set forth in Table 2. Catalyst preparation (dimethyl [N- (1,1-dimethylethyl) -1, 1-dimethyl-1 - [(1, 2,3,4,5-γ) -1,5,6,7-tetrahydro-3-phenyl-s-indacen-1 -yl] silanaminate (2- ) -N] -titanium).

Preparation of 3,5,6,7-tetrahydro-s-hydrindacen-1 (2H) -one. Indan (94.00 g, 0.7954 mole) and 3-chloropropionyl chloride (100.99 g, 0.7954 mole) in CH2Cl2 (300 mL) were stirred at 0 ° C, as AICI3 (130.00 g, 0.9750 mole) was added slowly under a nitrogen flow. The mixture was then allowed to stir at room temperature for 2 hours. The volatiles were removed afterwards. The mixture was then cooled to 0 ° C and concentrated H2SO4 (500 ml) was slowly added. The formation of the solid had to be frequently interrupted with a spatula as the agitation was lost early in this step. The mixture was then left under nitrogen overnight at room temperature. The mixture was then heated until the temperature readings reached 90 ° C. These conditions were maintained for a period of 2 hours, during which periodically a spatula was used to stir the mixture. After the reaction period, crushed ice was placed in the mixture and moved. The mixture was then transferred to a beaker and washed intermittently with H2O and diethyl ether and then the fractions were filtered and combined. The mixture was washed with H2O (2 x 200 'ml). The organic layer was then separated and the volatiles were removed. The desired product was then isolated via crystallization from hexane at 0 ° C as pale yellow crystals (22.36 g, 16.3% yield). 1H NMR (CDCl 3): d2.04-2.19 (m, 2H), 2.65 (t, 3JHH = 5.7 Hz, 2H), 2.84-3.0 (m, 4H), 3.03 (t3JHH = 5.5 Hz, 2H), 7.26 ( s, 1H), 7.53 (s, 1H). 13C NMR (CDCI3): d25.71, 26.01, 32.19, 33.24, 36.93, 118.90, 122.16, 135.88, 144.06, 152.89, 154.36, 206.50. GC-MS: Calculated for: C? 2H12O 172.09, 172.05 was found.

Preparation of 1, 2,3,5-tetrahydro-7-phenyl-s-indacen. 3,5,6,7-Tetrahydro-s-hydrindacen-1 (2H) -one (12.00 g, 0. 06967 moles) in diethyl ether (200 ml) at 0 ° C, as PhMgBr was added slowly (0.105 moles, 35.00 moles of 3.0 M of a solution in diethyl ether). This mixture was then allowed to stir overnight at room temperature. After the reaction mixture period, the mixture was quenched by emptying it on ice. The mixture was then acidified (pH = 1) with HCl and stirred vigorously for 2 hours. The organic layer was then separated and washed with H2O (2 x 100 ml) and then dried over MgSO4. Filtration followed by removal of the volatiles resulted in the isolation of the desired product as a dark oil (14.68 g, 90.3% yield). 1 H NMR (CDCl 3): d 2.0-2.2 (m, 2 H), 2.8-3.1 (m, 4 H), 6.54 (s, 1 H), 7.2- 7.6 (m, 7 H). GC-MS: Calculated for C18H16232.13, 232.05 was found.

Preparation of dilithium salt of 1, 2,3,5-tetrahydro-7-phenyl-s-indacene. 1, 2,3,5-tetrahydro-7-phenyl-s-indacen (14.68 g, 0.06291 mol) was stirred in hexane (150 ml) as slowly added nBuLi (0.080 mol, 40.00 ml of a 2.0 solution). M in cyclohexane). This mixture was then allowed to stir overnight. After the reaction period, the solid was collected via suction filtration as a yellow solid, which was washed with hexane, dried under vacuum, and used without further purification or analysis. (12.2075 g, 81.1% yield).

Preparation of chlorod imeti 1 (1, 5,6,7-tetrah id ro-3-f eni l-s-indecen-1-yl) silane. The dilithium salt of 1,2,3,5-tetrahydro-7-phenyl-s-indacene (12.2075 g, 0.05102 moles) in THF (50 ml) was added dropwise to a solution of Me2SiCl2 (19.5010 g, 0.1511 moles). ) in THF (100 ml) at 0 ° C. This mixture was then allowed to stir at room temperature overnight. After the reaction period, the volatiles were removed and the residue was extracted and filtered using hexane. Removal of the hexane resulted in the isolation of the desired product as a yellow oil (15.1492 g, 91. 1% yield). 1 H NMR (CDCl 3): d? .33 (s, 3 H), 0.38 (s, 3 H), 2.20 (p, 3 J H H = 7.5 Hz, 2H), 2.9-3.1 (m, 4H), 3.84 (s, 1H), 6.69 (d, 3JHH = 2.8 Hz, 1H), 7.3-7.6 (m, 7H), 7.68 (d, 3JHH = 7.4 Hz, 2H). 13C NMR (CDCI3): d? .24, 0.38, 26.28, 33.05, 33.18, 46.13, 116.42, 119. 71, 127.51, 128.33, 128.64, 129.56, 136.51, 141.31, 141.86, 142. 17, 142.41, 144.62. GC-MS: calculated for C20H21CIS¡ 324.11, 324.05 was found.

Preparation of N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-3-phenylis-s-indacen-1-yl) silanamine. Chlorodimethyl (1, 5,6,7-tetrahydro-3-phenyl-s-indecen-1-yl) silane (10.8277 g, 0.03322 mol) was stirred in hexane (150 ml) as NET3 (3.5123 g, 0.03471 moles) and t-butylamine (2.6074 g, 0.03565 moles). This mixture was allowed to stir for 24 hours. After the reaction period, the mixture was filtered and the volatiles were removed resulting in the isolation of the desired product as a thick red-yellow oil (10.6551 g, 88.7% yield). 1H NMR (CDCl 3): d? .02 (s, 3H), 0.04 (s, 3H), 1.27 (s, 9H), 2.16 (p, 3JHH = 7.2 Hz, 2H), 2.9-3.0 (m, 4H) , 3.68 (s, 1H), 6.69 (s, 1H), 7.3-7.5 (m, 4H), 7.63 (d, 3JHH = 7.4 Hz, 2H). 13C NMR (CDCI3): d-0.32, -0.09, 26.28, 33.39, 34.11, 46.46, 47.54, 49.81, 115.80, 119.30, 126.92, 127.89, 128.46, 132.99, 137.30, 140.20, 140.81, 141.64, 142.08, 144.83.

Preparation of dilithium salt of N- (1,1-dimethylethyl) -1,1 -dimethyl-1- (1, 5,6,7-tetrahydro-3-phenyl-s-indecen-1-yl) silanamine. N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1, 5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silanamine (10.6551 g, 0.029947) was stirred. moles) in hexane (100 ml) as nBuLi (0.070 moles, 35. oo ml of a 2.0 M solution in cyclohexane) was added slowly. This mixture was then allowed to stir overnight, during which no salt crashed out of the dark red solution. After the reaction period, the volatiles were removed and the residue was rapidly washed with hexane (2 x 50 ml). The dark red residue was then dried by pumping and used without further purification or analysis (9.6517 g, 87.7% yield).

Preparation of dichloro [N- (1,1-dimethylethyl) -1,1-dimethyl-1 - [(1,2, 3,4, 5 -?) - 1,5,6,7-tetrahydro-3-phenyl -s-indacen-1 -yl] silanaminate (2 -) - NJ titanium. The dilithium salt of N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1, 5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silanamine (4.5355 g , 0.01214 mol) in THF (50 ml) was added dropwise to a slurry of TiCl3 (THF) 3 (4.5005 g, 0.01214 mol) in THF (100 ml). This mixture was allowed to stir for 2 hours. PbCI2 (1.7136 g, 0.006162 mol) was then added and the mixture was allowed to stir for a further 1 hour. After the reaction period, the volatiles were removed and the residue was extracted and filtered using toluene. Removal of toluene resulted in the isolation of a dark residue. This residue was then formed as a slurry in hexane and cooled to 0 ° C. The desired product was then isolated through filtration as a red-brown crystalline solid (2.5280 g, 43.5% yield). 1 H NMR (CDCl 3): d? .71 (s, 3 H), 0.97 (s, 3 H), 1.37, (s, 9 H), 2.0-2.2 (m, 2 H), 2.9-3.2 (m, 4 H), 6.62 (s, 1H), 7.35-7.45 (m, 1H), 7.50 (t3JHH = 7.8 Hz, 2H), 7.57 (s, 1H), 7.70 (d, 3JHH = 7.1 Hz, 2H), 7.78 (s, 1H) . 1 H NMR (CDCl 3): d? .44 (s, 3 H), 0.68 (s, 3 H), 1.35 (s, 9 H), 1.6-1.9 (m, 2 H), 2.5-3.9 (m, 4 H), 6.65 ( s, 1H), 7.1-7.2 (m, 1H), 7.24 (t3JHH = 7.1 Hz, 2H), 7.61 (s, 1H), 7.69 (s, 1H), 7.77-7.8 (m, 2H). 3C NMR (CDCI3): d1.29, 3.89, 26.47, 32.62, 32.84, 32.92, 63.16, 98.25, 118.70, 121.75, 125.62, 128.46, 128.79, 129.01, 134.11, 134.53, 136.04, 146.15, 148.93. 13C NMR (C6D6): d? .90, 3.57, 26.46, 32.56, 32.78, 62.88, 98.14, 119.19, 121.97, 125.84, 127.15, 128.83, 129.03, 129.55, 134.57, 135.04, 136.41, 1136.51, 147.24, 148.96.

Preparation of dimethyl [N- (1,1-dimethyl-ethyl) -1, 1-dimethyl-1 - [(1,2, 3,4, 5 -?) - (1, 5,6,7-tetrahydro- 3-phenyl-s-indacen-1-yl] silanaminate (2 -) - N] titanium. Ro [d - (1,1-dimethyl-ethyl) -1,1-dimethyl-1 - [1, 2,3,4, 5 -?) - (1, 5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl] silanaminate (2 -) - N] titanium (0.4970 g, 0.001039 moles) in diethyl ether (50 ml) as MeMgBr (0.0021 mole, 0.70 ml of a 3M solution in diethyl ether) was slowly added in. This mixture was then stirred for 1 hour.After the reaction period, the volatiles were removed and the residue was extracted and filtered using hexane The removal of the hexane resulted in the isolation of the desired product as a golden yellow solid (0.4546 g, 66.7% yield) .1H NMR (CDCl3): d? .071 ( s, 3H), 0.49 (s, 3H), 0.70 (s, 3H), 0.73 (s, 3H), 1.49 (s, 9H), 1.7-1.8 (m, 2H), 2.5-2.8 (m, 4H) 6.41 (s, 1H), 7.29 (t, 3JHH_7.4 Hz, 2H), 7.48 (s, 1H), 7.72 (d, 3JHH = 7.4 Hz, 2H), 7.92 (s, 1H). 13C NMR (C6D6): d2.19, 4.61, 27.12, 32.86, 33.00, 34.73, 58.68, 58.82, 118.62, 121.98, 124.26, 127.32, 128.63, 128.98, 131.23, 134.39, 136.38, 143.19, 144.85.

Preparation of the Co-catalyst of (bis (hydrogenated tallow alkyl) methylamine) (B-FABA). Methylcyclohexane (1200 ml) was placed in a 2 liter cylindrical flask. While stirring, bis (hydrogenated tallowalkyl) methylamine (ARMEEN® M2HT, 104 g, ground to granulated form) was added to the flask and stirred until completely dissolved. Aqueous HCl (1M, 200 ml) was added to the flask, and the mixture was stirred for 30 minutes. Immediately a white precipitate formed. At the end of this period, L¡B (C6F5) 4 »Et 2 O« 3LiCl (Mw = 887.3, 177.4 g) was added to the flask. The solution began to become white milky. The flask was equipped with a Vigreux column of 15.24 cm, its upper part with a distillation apparatus and the mixture was heated (140 ° C, external wall temperature). A mixture of ether and methylcyclohexane was distilled from the flask. The two-phase solution was now only slightly cloudy. The mixture was allowed to cool to room temperature, and the contents were placed in a 4 liter separatory funnel. The aqueous layer was removed and discarded, and the organic layer was washed twice with H2O and the aqueous layers were discarded again. Methylcyclohexane solutions saturated with H2O were measured to contain 0.48% by weight of diethyl ether (Et2O). The solution (600 ml) was transferred to a 1 liter flask, thoroughly sprayed with nitrogen, and transferred to the drying box. The solution was passed through a column (diameter of 2.54 cm., Height of 15.24 cm) containing 13X of molecular sieves. This reduced the Et2O level from 0.48% by weight to 0.28% by weight. The material was then stirred on fresh 13X sieves (20 g) for 4 hours. The Et2O level was then measured to be 0.19% by weight. The mixture was then stirred overnight, resulting in a further reduction in the Et 2 O level to about 40 ppm. The mixture was filtered using a funnel equipped with a glass frit having a size of 10-15 μm to give a clear solution (the molecular sieves were rinsed with additional dry methylcyclohexane). The concentration was measured through gravimetric analysis producing a value of 16.7% > in weigh.

Polymerization ESI # 3 was prepared in a 22.7 liter, jacketed, oil jacketed (CSTR) continuously stirred tank reactor. A magnetically coupled stirrer with Lightning A-320 propellers provided mixing. The reactor ran the liquid completely at 3,275 kPa. The procedure flow was at the bottom and outside the top. A heat transfer oil was circulated through the reactor jacket to remove some heat from the reaction. At the outlet of the reactor was a micromotion flow meter that measured the flow and density of the solution. All lines of the reactor outlet were traced with 344.7 kPa of steam and were isolated. The ethylbenzene solvent was supplied to the reactor at 207 kPa. Feed to the reactor was measured through a Micro-Motion mass flow meter, A variable speed diaphragm pump controlled the feeding speed. At the time of the discharge of the solvent pump, a side vapor was taken to provide flood flows for the catalyst injection line (0.45 kg / hour) and the reactor agitator (0.34 kg / hour). These flows were measured through differential pressure flow meters and controlled through the manual adjustment of micro-flow needle valves. An uninhibited styrene monomer was supplied to the reactor at 207 kPa. Feed to the reactor was measured through a MicroMotion mass flow meter. A variable speed diaphragm pump controlled the feeding speed. The styrene streams were mixed with the remaining solvent stream. Ethylene was supplied to the reactor at 4,137 kPa. The ethylene stream was measured through a Micro-Motion mass flow meter just before the Search valve controlling the flow. A Brooks flow meter / controller was used to supply hydrogen to 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 as it enters the reactor was dropped to ~ 5 ° C through a glycol-5 ° C exchanger on the jacket. This current was introduced into the bottom of the reactor. The three-component catalyst system and its solvent flood was also introduced into the bottom of the reactor, but through a different port from the monomer stream. The preparation of the catalyst components took place in a handling box with gloves of inert atmosphere. The diluted components were placed in cylinders filled with nitrogen and charged to the catalyst operation tanks in the process area. From these operating tanks, the catalyst was pressurized with piston pumps and the flow was measured with Micro-Motion mass flow meters. These streams were combined with each other and the catalyst flooded with solvent just before entering through the individual injection line into the reactor. The polymerization was stopped with the addition of catalyst annihilator (water mixed with solvent) to the product line of the reactor after the micromotion flow meter measured the density of the solution. Other polymer additives can be added with the catalyst annihilator. A static mixer in the line provided the dispersion of the catalyst annihilator and additives in the reactor effluent stream. This stream then entered the post-reactor heaters that provide additional energy for the flash-off of the solvent. This instantaneous vaporization occurs as the effluent leaves the post-reactor heater and the pressure dropped from 3,275 kPa to -250 nm absolute pressure in the reactor pressure control valve. This vaporized polymer instantly entered a heated oil jacket devolatilizer. Approximately 85% >; of the volatiles were removed from the polymer in the devolatilizer. The volatiles came out of the top of the devolatilizer. The stream was condensed with a glycol jacket exchanger and entered the suction of a vacuum pump and charged to a solvent separation tank of glycol jacket and styrene / ethylene. The solvent and ethylene were removed from the bottom of the vessel and the ethylene from the top. The ethylene stream was measured with a Micro-Motion mass flow r and analyzed for composition. The measurement of the ventilated ethylene plus a calculation of the gases dissolved in the solvent / ethylene stream were used to calculate the ethylene conversion. The polymer separated in the devolatilizer was pumped with a gear pump to a devolatilization vacuum extruder ZSK-30. The dried polymer leaves the extruder as an individual filament. This Filament cooled as it was pulled through a water bath. The excess water was blown from the filament with air and the filament was crumbled into pellets with a filament crusher.

Preparation of ESI # 4 ESI # 4 is a substantially random ethylene-styrene interpolymer containing 72 wt.% Styrene, and 28 wt.% Ethylene (based on the weight of substantially random ethylene-styrene interpolymers) and 3% by weight. atactic polystyrene weight (based on the combined weight of the substantially random ethylene-styrene interpolymer and atactic polystyrene) prepared essentially as for ESI # 3 using the conditions set forth in Table 2.

Preparation of ESI # 5 ESI # 5 is a substantially random ethylene-styrene interpolymer containing 57% by weight of styrene and 43% by weight of ethylene (based on the weight of the substantially random ethylene-styrene interpolymer) and 3% by weight of atactic polystyrene (based on the combined weight of the substantially random ethylene-styrene interpolymer and the atactic polystyrene) prepared essentially as for ESI # 3 using the conditions set out in Table 2.

Preparation of ESI # 6 ESI # 6 is a substantially random ethylene-styrene interpolymer containing 20 wt.% Styrene and 80 wt.% Ethylene (based on the weight of substantially random ethylene-styrene interpolymer) and 8 wt.% of atactic polystyrene (based on the combined weight of the substantially random ethylene-styrene interpolymer and atactic polystyrene) prepared essentially as for ESI # 3 using the conditions set forth in Table 2.

Preparation of ESI # 7 ESI # 7 is a substantially random ethylene-styrene interpolymer containing 20 wt.% Styrene and 80 wt.% Ethylene (based on the weight of the substantially random ethylene-styrene interpolymer) and 8 wt.% of atactic polystyrene (based on the combined weight of the substantially random ethylene-styrene interpolymer and atactic polystyrene) prepared essentially as for ESI # 3 using the conditions set forth in Table 2.

Preparation of ESI # 8 ESI # 8 is a substantially random ethylene-styrene interpolymer containing 57.7 wt% of styrene and 40 wt% of ethylene (based on the weight of the substantially random ethylene-styrene interpolymer) and 3.1 wt% of atactic polystyrene (based on the combined weight of the substantially random ethylene-styrene interpolymer and atactic polystyrene) prepared essentially as for ESI # 3 using the conditions set forth in Table 2.

Preparation of ESI # 9 ESI # 9 is a substantially random ethylene-styrene interpolymer containing 73.3% by weight of styrene and 26.7% by weight of ethylene (based on the weight of the substantially random ethylene-styrene interpolymer) and 8.6% by weight of atactic polystyrene (based on the combined weight of the substantially random ethylene-styrene interpolymer and atactic polystyrene) prepared essentially as for ESI # 3 using the conditions set forth in Table 2.

PVC # 1 PVC # 1 was a flexible PVC obtained from and that has the commercial name of Geon 80 ™ from the supplier, BF Goodrich Company. The Shore A hardness of this material was 80.

PVC # 2 PVC # 2 was also a flexible PVC obtained from, and having the trade name of Geon 55 ™ from the supplier, BF Goodrich Company. The Shore A hardness of this material was 55.

RPVC # 1 RPVC # 1 was also a flexible PVC obtained from, and having the trade name of M1000 ™ from the supplier, BF Goodrich Company.

The various catalysts, co-catalysts and process conditions used to prepare the various individual ethylene interpolymers for use in the blend compositions of the present invention are summarized in Table 2.

TABLE 2 catalyst is dimethyl [N-1, -dimethylethyl) -1, 1-dimethyl - [(1, 2,3,4,5-?) - 1,5,6,7-tetrahyd or -3-phenyl-s- indacen-il] silanaminato (2 -) - N] -titanium. The catalyst is 1,3-pentadiene of (t-butylamido) dimethyl- (tetramethylcyclopentadienyl) silane-titanium (II), prepared as described in the patent of E.U.A. No. 5,556,928, Example 17. c BFABA is tetra-bis (pentafluorophenyl) borate of bis-tallowalkyl hydrogenated methylammonium. d FAB is tris (pentafluorophenyl) borane. e a commercially available methylaluminoxane available from Akzo Nobel as MMAO-33. f CGC-1 is titanium: N-1,1-dimethylethyl) -dimethyl- (1,2,3,4,5 -?) - 2,3,4,5-tetramethyl-2,4-cyclopentadiene-1 -yl) silanaminate)) (2-) N) -dimethyl, CAS # 135072-62-7, prepared as described in the US patent No. 5,380,810, Example 1.

Preparation of the blends Example 1 Example 1 is a mixture containing 25% by weight of ESI # 1 and 75% by weight of PVC # 1. The mixture was prepared by combining under melting mixed components in the specified weight ratios using a Haake mixer equipped with a bowl of Rheomix 3000, operating at 170 ° C and 40 rpm. The capacity of this mixer was 310 ce. The optimum volume for effective mixing was approximately 70% or 220 cc. Calculations were made considering the density and constitution of each component to prepare a dry mix of the materials to obtain a 70% volume filler. The dry mixed materials were then staggered into the preheated calibrated bowl as the rotors rotated at 43 rpm. In order to avoid any decomposition of the flexible PVC, the materials were heated to approximately 160 ° C. After a small residue under melting was established in the mixer, small increments of dry mix were added and allowed to melt and incorporated into the residue before further mixing was added. This was continued for approximately three minutes until the entire mixture was added. A sealing ring was then lowered onto the melting bowl and the molten mixture allowed to combine through the action of a roller blade for a further 10 minutes. At the end of this period, the rotors were stopped, the mixer dismantled and the fusion mixture was removed and allowed to cool for further testing and analysis.

Example 2 Example 2 is a mixture containing 75% by weight of ESI # 1 and 25%) by weight of PVC # 1. The mixture was prepared essentially as in Example 1.

Example 3 Example 3 is a mixture containing 50% by weight of ESI # 2 and 50% by weight of PVC # 1. The mixture was prepared essentially as in Example 1.

Example 4 Example 4 is a mixture containing 75% by weight of ESI # 3 and 25%) by weight of PVC # 2. The mixture was prepared by combining in a HaaKe Rheomix 3000 bowl mixer. The capacity of this mixer was 310 cc. The optimum volume for effective mixing was approximately 70% or 220 cc. Calculations were made considering the density and constitution of each component to prepare a dry mix of the materials to obtain a 70% volume filler. The dry mixed materials were then added stepwise to the preheated calibrated bowl as the rotors rotated at 30 rpm. In order to avoid any decomposition of the flexible PVC, the materials were heated to approximately 150 ° C. After a small residue under melting was established in the mixer, small increments of dry mix were added and allowed to melt and incorporated into the residue before further mixing was added. This was continued for approximately two minutes until the entire mixture was added. A sealing ring was then lowered onto the melting bowl and the molten mixture allowed to combine through the action of a roller blade for a further 10 minutes. At the end of this period, the rotors were stopped, the mixer dismantled and the fusion mixture was removed and allowed to cool for further testing and analysis.

Example 5 Example 5 is a mixture containing 50% by weight of ESI # 3 and 50%) by weight of PVC # 2. The mixture was prepared essentially as Example 4.

Example 6 Example 6 is a mixture containing 15% by weight of ESI # 4 and 25% by weight of RPVC # 1. The mixture was prepared in a Haake Micro18 Extruder. This was a co-rotating twin screw extruder with 18mm screws and an L / D of about 31. A dry mix of the combined materials was fed into the extruder feed throat via a KTRON auger feeder at a speed of approximately 1,816 kilograms per hour. The extruder was preheated for 1 hour under the following Zone conditions: 1-135 ° C, 2-165 ° C, 3-165 ° C, 4-165 ° C, 5-175 ° C and a die temperature of 175 ° C. The extruder was operated at 100 ppm. The extruded product having a melting temperature of 160-178 ° C was extinguished in a water bath dried through an air knife and shredded to pellets.

Example 7 Example 7 is a mixture containing 50% by weight of ESI # 4 and 50% by weight of RPVC # 1. The mixture was prepared essentially as Example 6.

Example 8 Example 8 is a mixture containing 25% or by weight of ESI # 4 and 75% by weight of RPVC # 1. The mixture was prepared essentially as Example 6.

Example 9 Example 9 is a mixture containing 50% by weight of ESI # 6 and 50%) by weight of RPVC # 1. The mixture was prepared essentially as Example 6.

Example 10 Example 10 is a mixture containing 50% by weight of ESI # 5 and 50% by weight of RPVC # 1. The mixture was prepared essentially as in Example 6. The analysis for the various Tg values for these examples in Table 3 shows the surprising result that, although mixtures of ethylene / styrene interpolymers with rigid # 1 PVC (Examples 6- 10) have double wide Tgs due to the immiscible ability of these two components, the flexible PVC and ethylene / styrene interpolymer mixtures can have either a double broad Tg (as in Example 1) or a single narrow Tg ( as in Examples 2-5) simply by varying the relative amounts of the flexible PVC and the ethylene / styrene interpolymer. In addition, the analysis of the E values for the mixtures of Examples 2 and 3 as compared to those of the individual components, demonstrates the synergistic effect of the mixing on the elongation by stress at rupture. In this way, Example 2 had an Eb of 375%, which was greater than the Eb values of the individual blend components, ESI # 1 (282%) or PVC # 1 (198%). A synergistic effect was also observed on the E of the mixing in Example 3, which had an Eb of 481%, which was also higher than the Eb values of the individual blend components, ESI # 2 (397%) or PVC # 1 (198%). Examples 1, 4 and 5 in Table 3 in addition to showing a similar synergistic effect of mixing on E, also show that the percentage of relaxation by tension (percentage SR) observed for the mixtures may also be higher than those observed for the individual blend components, for example, Example 5 had an SR percentage of 95%, which was higher than that of the individual blend component, ESI # 2 (92%) or PVC # 2 (56%). Examples 6-10 in Table 3 were mixtures of rigid PVC with ethylene / styrene interpolymers. PVC # 1 had a very low Eb value (13%) and essentially did not exhibit any stress relaxation. ESI # 4 had an E value of 244% and an SR percentage of 93%. The mixture of Example 6, which contains as much as 25% by weight of RPVC # 1 could have an E of 272% and an SR percentage of 88%. The increase in RPVC # 1 content to 50% as in Example 7, still results in an Eb of 32%.

Examples 11-18 Examples 11-18 in Table 4 were mixtures of ethylene / styrene interpolymers with rigid PVC, all containing the same amount of plasticizer P610 (20% by weight). A mixture of several styrenes containing ESI and RPVC # 1 (stabilized pellet form) was prepared together with a plasticizer in the Haake MicroHd extruder. A mixture of ESI and RPVC was fed to the extruder through a KTRON auger feeder. The plasticizer was injected into Zone 3 as a liquid using a displacement pump and an injector nozzle. The feed rate of the dry mix was verified through a supply load in time at the tip of the auger. The feed rate of the injector system was verified through the time weight loss of the plasticizer container. The calibration curves for each of these were used to establish the appropriate settings for the auger feeder and the displacement pump to produce the desired ratio of plasticizer to solids at a total feed rate of approximately 0.908-1.135 kilograms per hour. The Zone temperature settings in ° C were as follows: 1-137, 2-170, 3-180, 4-180, 5-180, die-170- The extruder was operated at 105 rpm. The resulting extruded product having a melting temperature of 165 ° C was quenched with water, dried by an air knife and crumbled into pellets. Examples 11-13, 14-15 and 16-18 in Table 4, all show how the Tgs of the mixtures can be varied on a wide scale by varying the relative amounts of the ethylene / styrene interpolymer and the rigid # 1 PVC. The magnitude of this variation can best be demonstrated by comparing the Tgs of Examples 16-18 with those measured in Comparative Examples 1 and 2 of the binary mixtures of plasticizer P610 and RPVC # 1, and plasticizer P610 and ESI # 9.

Claims (2)

1. - A mixture of polymeric materials comprising: (A) from 1 to 99% by weight based on the combined weights of Components A, B and C of at least one substantially random interpolymer; and wherein said interpolymer; (1) contains from 0.5 to 65 mole percent of polymer units derived from: (a) at least one aromatic vinyl or vinylidene monomer, or (b) at least one hindered aliphatic vinylidene vinylidene monomer, or (c) ) a combination of at least one aromatic vinyl or vinylidene monomer and at least one hindered aliphatic vinylidene or vinylidene monomer; (2) contains from 35 to 99.5 mol% of polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; (3) has a molecular weight (Mn) greater than 1,000; (4) has a melt index (12) of 0.01 to 1,000; (5) has a molecular weight distribution (Mw / Mn) of 1.5 to 20; and (B) from 99 to 1% by weight based on the combined weights of Components A, B and C of one or more vinyl halide copolymer (s) homopolymer (s); and (C) from 0 to 70% by weight based on the combined weights of Components A, B and C of one or more plasticizers. 2. The mixture according to claim 1, wherein: (i) Component A is present in an amount of 5 to 95%) by weight based on the combined weights of Components A, b and C; (ii) Component A contains from 1 to 55 mol% of polymer units derived from: Ar I (CH2) n R - 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 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 halogen, C 1-4 alkyl, and C? - haloalkyl; and n has a value from zero to 4; or b) at least one of the hindered aliphatic vinyl or vinylidene monomers, Component A (1) (b), represented by the following general formula: A1 R1-C-C (R2); wherein A1 is a sterically bulky, aliphatic or cycloaliphatic 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 or 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 of said vinyl aromatic or vinylidene monomer and at least one of said hindered aliphatic vinylidene or vinylidene monomer; (iii) Component A contains from 45 to 99 mole percent of polymer units derived from at least one of the aliphatic α-olefins selected from the group consisting of ethylene or a combination of ethylene and at least one of propylene, -methyl pentene, butene-1, hexene-1 or octene-1; (iv) Component A has a molecular weight (Mn) of 5,000 to 1,000,000; (v) Component A has a melt index (12) of 0.1 to 100; (vi) Component A has a molecular weight distribution (Mw / Mn) from 1.8 to 10; (vii) Component B is present in an amount of 95% or 5% by weight based on the combined weights A, B and C and is selected from the group consisting of vinyl chloride homopolymers, vinylidene chloride homopolymers and their copolymers with interpolymerizable monomers selected from the group consisting of C2-C20 α-olefins, vinyl esters of organic acids containing from 1 to 18 carbon atoms; vinyl chloride, vinylidene chloride, symmetrical dichloroethylene; acrylonitrile, methacrylonitrile; esters of alkyl acrylate or alkyl methacrylate, wherein the alkyl group contains from 1 to 8 carbon atoms, and dialkyl esters of dibasic organic acids, wherein the alkyl groups contain 1-8 carbon atoms, dibutyl fumarate, and diethyl maleate; and (viii) Component C is present in an amount of 5 to 50% > in weight based on the combined weights of Components A, B and C and is selected from the group consisting of phthalate esters, trimellitate ethers, benzoates, adipate esters, epoxy compounds, phosphates esters, glutarates and oils. 3. The mixture according to claim 2, wherein: (i) Component A is present in an amount of 10 to 90% by weight based on the combined weights of components A, B and C; (ii) Component A contains from 2 to 50 mol% of polymer units derived from: a) the group consisting of styrene, α-methylstyrene, ortho-, meta-, and para-methylstyrene, and the halogenated styrenes in the ring, or b) the group consisting of 5-ethylidene-2-norbornene or 1-vinylcyclohexene, 3-vinylcyclohexene and 4-vinylcyclohexene; or c) a combination of at least one of a) and b); (Ii) Component A contains from 50 to 98 mol% of polymer units derived from ethylene; (iv) Component A has a molecular weight (Mw) of 10,000 to 500,000; (v) Component A has a melt index (l2) of 0.5 to 30; (vi) Component A has a molecular weight distribution (Mw / Mn) of 2 to 5; (vii) Component B is present in an amount of 90 to 10% by weight based on the weights of Components A, b and C and is vinyl chloride, or vinylidene chloride homopolymer or copolymer; and (viii) Component C is present in an amount of 10 to 40% by weight based on the combined weights of Components A, B and C and further is selected from the group consisting of phthalate esters, including dialkyl esters, dialkyl linear compound, aryl and alkylated compound. 4. A mixture according to claim 1, wherein: i) said vinyl aromatic or vinylidene monomer, component A1 (a), is styrene; ii) said aliphatic α-olefin, Component A2, is ethylene; iii) said vinyl halide polymer, Component B, is polyvinyl chloride; and iv) said plasticizer, Component C, selected from the group consisting of phthalate esters, including dialkyl esters, dialkyl linear compound, aryl and alkyl-aryl compound. 5. A mixture according to claim 1, wherein: i) said vinyl aromatic or vinylidene monomer, component A1 (a), is styrene; ii) said aliphatic α-olefin, Component A2, is ethylene; iii) said vinyl halide polymer, Component B, is a homopolymer or copolymer of vinylidene chloride; and iv) said plasticizer, Component C, is selected from the group consisting of phthalate esters, including dialkyl esters, dialkyl linear compound, aryl and alkyl-aryl compound. 6. The mixture according to claim 1, characterized in that it has a single glass transition temperature (Tg) as measured by dynamic mechanical spectroscopy (DMS). The mixture according to claim 1, characterized in that it has more than one glass transition temperature (Tg) as measured by dynamic mechanical spectroscopy (DMS). 8. A mixture according to claim 1, wherein Component A is produced through polymerization in the presence of a metallocene or restricted geometry catalyst and a co-catalyst. 9. A sheet or film resulting from the calendering, casting or blowing of a mixture of claim 1. 10. A sheet or film resulting from the calendering, casting or blowing of a mixture of claim 2. 11.- A sheet or film resulting from the calendering, casting or blowing of a mixture of claim 3. 12. A sheet or film resulting from the calendering, casting or blowing of a mixture of claim 4. 13. A sheet or film that results from calendering, casting or blowing a mixture of claim 5. 14. A sheet or film resulting from calendering, casting or blowing a mixture of claim 6. 15. A sheet or film resulting from calendering, casting or blowing a mixture of claim 7. 16. A sheet or film resulting from the calendering, casting or blowing of a mixture of claim 8. 17. An article resulting from injection molding, by compression, by extrusion or by blowing a mixture of claim 1. 18. An article resulting from the injection, compression, extrusion or blow molding of a mixture of claim 2. 19. An article resulting from injection molding., by compression, by extrusion or by blowing a mixture of claim 3. 20. An article resulting from the injection, compression, extrusion or blow molding of a mixture of claim 4. 21. An article resulting from the injection, compression, extrusion or blow molding of a mixture of claim 5. 22. An article resulting from the injection, compression, extrusion or blow molding of a mixture of claim 6. 23. An article that results from the molding by injection, compression, extrusion or blow molding of a mixture of claim 7. 24.- An article that results from injection molding, compression, extrusion or blow molding. a mixture of claim 8. 25.- An article that results from the coating of a substrate with the mixture of claim 1. 26.- An article that results from the coating of a substrate with the mixture of the claim.

2. An article that results from the coating of a substrate with the mixture of claim 3. 28.- An article that results from the coating of a substrate with the mixture of claim 4.

29. - An article that results from the coating of a substrate with the mixture of claim 5. vinyl halide copolymer (s); and (C) from 0 to 70% by weight based on the combined weights of Components A, B and C of one or more plasticizers. The novel compositions provide the materials with improved processing / property attributes with respect to the unmodified polymers comprising the blends. The blend compositions can exhibit a unique balance of properties including improved modulus and barrier properties, improved tensile strength, radio frequency (rf) sealing capacity, solvent binding capacity, thermal stability and thermal resistance depending on the selection of the individual mixing components and their compositional relationships. In addition, the location and respirability of the glass transition can be controlled by varying the level of mix composition and plasticizer. Surprisingly, blends including a plasticizer show a single phase material from analysis of glass transition temperature data.