MXPA99005680A - Plasticized alpha-olefin/vinylidene aromatic monomer or hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers - Google Patents

Abstract

Properties of interpolymers of&agr;-olefin/vinylidene aromatic monomer are enhanced with plasticizers selected from phthalate esters, trimellitate esters, benzoates, aliphatic diesters, epoxy compounds, phosphate esters, glutarates, polymeric plasticizers (polyesters of glycols and aliphatic dicarboxylic acids) and oils. These plasticized interpolymers are useful in a wide range of applications including films, sheet, adhesives, sealants and molded parts.

Description

I NTERPOLI MEROS OF AROMATIC VINYLIDENE MONOMER / ALPINE OLEFIN OR MONOMER OF VI N I LI DENO CYCLAL ALITIC OR ALIPHATIC OBSTRUI DO The present invention corresponds to the modification of the compositions containing ether polymers of aromatic vinylidene monomer / -olefin and / or cycloaliphatic and / or aliphatic vinylidene clogged by the use of a plasticizer. The generic class of substantially random copolymer materials of clogged vinylidene / α-olefin monomers include materials such as vinyl / α-olefin aromatic monomer interpolymers, and their preparation, are known in the art, as described in US Pat. EP 41 6 815 A2. These materials offer a wide range of properties and material structures, which makes them useful for varied applications, such as asphalt modifiers or as compatibilizers for polyethylene and polystyrene blends, as described in US 5,460.81 8. The structure, transitions Thermal and mechanical properties of substantially random interpolymers of ethylene and styrene containing up to 50 percent mol of styrene have been described (see YW Cheung, MJ Guest, Proc. Antee '96, pages 1634-1637). It has been found that these polymers have glass transitions in the range -20 ° C to + 35 ° C, and show unmeasurable crystallinity above 25 percent mole of styrene incorporation, ie they are essentially amorphous.

Despite the utility in its own right, the Industry is constantly seeking to improve the applicability of these interpolymers. To perform well in certain applications, it would be desirable for these ether polymers to be improved, for example, in the areas of processing characteristics or transition temperature depression of intensified glass or reduced modules, or reduced hardness, or lower viscosity, or ultimate prolongation improved compared to a property similar to the unmodified interpolymer. In relation to this invention, it is also considered advantageous to be able to design the glass transition process for the interpolymers at a particular temperature range, so that the energy absorption capacities of the polymer can be used to the maximum, for example, in the sound and vibration damping. This invention describes the utility of plasticizers to achieve modification of the substantially random ether copolymers of clogged α-olefin / vinylidene monomer. There is extensive knowledge based on the plasticization of polyvinyl chloride (PVC), and it is generally known that many thermoplastics can be plasticized. Reference can be made, for example to "Plasticizer" in "The Encyclopedia of Polymer Science and Engineering" (Supplemental volume, Wiley Interscience, 1989) with respect to this type of technology. Depending on the type of polymer, typical plasticizer families include phosphoric acid derivatives, phthalic acid derivatives, trimellitate esters, benzoates, adipate esters, epoxy compounds, phosphate esters, glutarates and mineral oils.

Based on their molecular weight, plasticizers are also classified as "monomeric" or polymeric. "Compared to monomeric plasticizers, polymeric plasticizers generally tend to show greater permanence, less compatibility and lower plasticizing efficiency. as "primary", and that have high compatibility with a particular polymer, or "secondary" if they have less compatibility.Mixes of the different types of plasticizers can be used to achieve cost / performance balances.A well-known effect of the addition of Small amounts of plasticizer is that many polymers, including polystyrene, polycarbonate, and Nylon 66 show "antiplasticization" in which significant increases in modulus and tensile strength and hardness loss are observed.This effect is also found for PVC when plasticizers are used at relatively low concentrations Ajas up to 1 0-17 percent by weight, depending on the nature of plasticizer. Due to the effects of antiplastification, compositions that include less than about 20 parts per cent of PVC are seldom found. Based on the available background information, combinations of substantially random interpolymers of clogged vinylidene monomer / α-olefin, and especially ethylene / styrene interpolymers, with typical plasticizers associated with PVC modification, would not appear to offer an effective route to modify their performance. It is well known that polymers Amorphous thermoplastics, such as atactic polystyrene, will accept large amounts of plasticizers, and although they decrease the glass transition temperature, they quickly form gums or liquids, that is, they have no function as solid state polymers. The addition of a little (less than 3 percent by weight) of dibutyl phthalate (DBP) has been used in latex formulations used for polishing based on thermoplastics including polystyrene. The compatibility of vinyl type plasticizers with low density polyethylene (LDPE) is usually 0 to 2 percent by weight, although some hydrocarbons such as certain mineral oils can be compatible up to 20 percent by weight. U.S. Patent No. 3,821,149 which describes "Plasticized thermoplastic semi-crystals block copolymers" teaches that random copolymers of ethylene and t-butylstyrene are not crystalline, and when plasticized with 50 to 100 parts of dibutyl phthalate provide a product of little physical properties desirable Random and statistical copolymers are specifically excluded from U.S. Patent No. 3,821, 149. WO-A-9607681 relates to thermosetting elastomers well-balanced in rupture tension, elongation at rupture, which are resistant to oils comprising a copolymer of ethylene / styrene and plasticizer. JP-A-6271764 discloses plasticized compositions comprising cycloaliphatic vinylidene monomers for sound damping applications. An additional approach to be considered with respect to plasticization is the relative compatibility of the plasticizer molecule with the polymer. The Buszard reference ("Theoretical Aspects of Plasticization" in "PVC Technology, Fouth Edition "ed WV Titow, Applied Science Publishers 1984) summarizes the theoretical techniques for assessing compatibility, and hence the utility of plasticizers with PVC through the use of the solubility parameter. Effective polymerization and plasticizers is a guide to defining nominal compatibility Although there are some assumptions and limitations in adopting this approach, it is generally clear that effective plasticizers will have good compatibility or miscibility with the polymer.The reference to the "Polymer Handbook" (Third edition, ed J. Brandrup, EH Immergut, Wiley Interscience, 1989) provides the PVC solubility parameter as approximately 1 9.8 (MPa) 0 5, and the appropriate plasticizers having solubility parameters which fall within the limits of 17.2 (MPa) 0 5 and 23.3 (MPa) 0 5. The reported solubility parameters of polyethylene and polystyrene are 16.2 (MPa) 0'5 and 1 8.6 (MPa) 0 5 respectively. Based on the group's additivity theories, it is expected that substantially random copolymers of ethylene and styrene will have solubility parameters that fall somewhere between these values. It is not anticipated that the interpolymers, which are rich in ethylene, will be effectively modified by many typical plasticizers used for vinyl modification, due to differences in the solubility parameters between the polymer and the plasticizer. Additionally, interpolymers, which are relatively rich in styrene (approximately 25-60 mole percent), are not anticipated, and amorphous in nature, are effectively modified by many typical plasticizers used for vinyl modification. Based on the available background information, it would not be anticipated that the substantially random interpolymers of clogged α-olefin / vinylidene monomer, and especially ethylene / styrene interpolymers would be effectively modified by many typical plasticizers associated with PVC modification, and particularly in the plasticizer incorporation ranges described in this invention. One aspect of the present invention corresponds to a composition comprising (A) from 50 to 99 percent by weight of at least one substantially random interpolymer resulting from polymerizing a monomer composition comprising (1) from 1 to 65 percent mol of ( a) at least one aromatic vinylidene monomer, or (b) at least one cycloaliphatic or aliphatic vinylidene monomer or clogged, or (c) a combination of at least one aromatic vinylidene monomer, and at least one cycloaliphatic or aliphatic vinylidene monomer clogged, and (2) from 35 to 99 percent mole of at least one C2-2 o-olefin; Y (B) from 1 to 50 weight percent of at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, aliphatic diesters (including adipates, azelates and sebacates), epoxy compounds, phosphate esters, glutarates, polymeric plasticizers (polyesters of glycols and aliphatic decarboxylic acids) and oils. Another aspect of the present invention corresponds to such interpolymers modified in the form of a film or sheet, or as a component of a multilayer structure resulting from calendering, blowing, pouring or (co-) extrusion operations. Another aspect of the present invention corresponds to such modified etherpolymers and their utility in the form of foams, fibers or emulsions. Another aspect of the present invention corresponds to the use of such modified interpolymers in adhesives, adhesive formulations and adhesive / sealant applications. Another aspect of the present invention pertains to injection, compression, blow molded or extruded parts prepared from such modified etherpolymers. The compositions of the present invention may "comprise", "consist essentially of" or "consist of" any of two or more such polymers or interpolymers or plasticizers listed herein. These compositions provide an improvement in one or more of the properties such as, but not limited to, processing characteristics or transition temperature depression of intensified glass, or reduced modulus, or reduced hardness, or lower viscosity, or improved last prolongation compared to a similar property of the unmodified interpolymer. 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 terminated monomer (s). When the references are made herein to a polymer containing monomer (s) or polymer units derived from, it actually means that the polymer contains monomer residues (s) resulting from polymerizing the monomer (s) indicated for make the polymer. The term "substantially random" in the substantially random interpolymer comprising an α-olefin and an aromatic vinylidene monomer or clogged aliphatic or cycloaliphatic vinylidene monomer as used herein means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by means of a statistical model of Markovian of first or second order, as described by J. C. Randall in POLYMER SEQUENCE DETERMI NATION. Carbon-1 3 NMR Method.

Academic Press New York, 1 977, pp. 71 -78. Preferably, the substantially random interpolymer comprises an α-olefin and an aromatic vinylidene monomer that contains no more than 1 5 percent of the total amount of vinylidene aromatic monomer in aromatic vinylidene monomer blocks other than 3 units. More preferably, the interpolymer was not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the NMR spectrum of carbon-1 3 of the substantially random interpolymer the peak areas corresponding to the methylene and methylene main chain carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the peak area total of the methine and methylene carbons of the main chain. Any of the numerical values quoted herein include all values of the value less than the greatest value in increments of one unit so 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 and the like 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 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, 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 are considered to be expressly declared in this application in a similar manner.

Interpolymers suitable for mixing to make the blends comprising the present invention include, but are not limited to, interpolymers prepared by the polymerization of one or more α-olefins with one or more vinylidene aromatic monomers and / or one or more monomers of cylindrical or aliphatic vinylidene clogged. Suitable α-olefins include, for example, α-olefins containing from 2 to 20, preferably from 2 to 12 and most preferably from 2 to 12. 8 carbon atoms. Particularly suitable are ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 and octene-1. These α-olefins do not contain an aromatic portion. 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 I (CH2) n R 11-C '= C (R2) 2 wherein R1 is selected from the group of radicals consisting of hydrogens 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 1-4 alkyl, and C 4 -4 haloalkyl; and n has a value from zero to 4, preferably from zero to 2, very preferably zero. Examples of monovinylidene aromatic monomers include styrene, vinyltoluene, α-methylstyrene, t-butylstyrene, chlorostyrene, including all isomers of these compounds. Such particularly suitable monomers include styrene and minor alkyl derivatives or substituted by halogen thereof. Preferred monomers include styrene, α-methylstyrene, styrene derivatives of lower (C 1 -C 4) alkyl or substituted phenyl ring, such as, for example, ortho-, meta- and para-methylstyrene, halogenated ring styrenes, para-vinyl toluene or mixtures thereof. A more preferred aromatic monovinylidene monomer is styrene. By the term "clogged aliphatic or cycloaliphatic vinylidene compounds", it is meant addition-polymerizable vinylidene monomers corresponding to the formula: A1 | R1 - C = C (R2) 2 wherein A1 is a spatially bulky aliphatic or cycloalfatic 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 "spatially bulky" is meant that the monomer bearing this substituent is normally incapable of addition polymerization by catalysts of Ziegler-Natta polymerization standards at a comparable ratio with ethylene polymerizations. The preferred cycloaliphatic or clogged aliphatic vinylidene compounds are monomers in which one of the carbon atoms bearing the ethylenic unsaturation is substituted tertiary or quaternary. Examples of such substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or substituted aryl or ring alkyl derivatives thereof, tert-butyl, norbornyl. The most preferred cycloaliphatic or aliphatic vinylidene clogged compounds are the various isomeric vinyl ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. Particularly suitable are 1 -, 3-, and 4-vinylcyclohexene. The interpolymers of one or more α-olefins and one or more monovinylidene aromatic monomers and / or one or more clogged aliphatic or cycloaliphatic vinylidene monomers used in the present invention are substantially random polymers. These interpolymers usually contain 5 to 65, preferably from 5 to 50, more preferably from 10 to 50 percent mole of at least one aromatic vinylidene monomer and / or clogged aliphatic cycloaliphatic or vinylidene monomer and from 35 to 95, preferably from 50 to 95, more preferably from 50 to 90 percent mole of at least one aliphatic α-olefin having from 2 to 20 carbon atoms. The average molecular weight number of the polymers and interpolymers is generally greater than 10,000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000.

While preparing the substantially random interpolymer, an amount of atactic vinylidene aromatic homopolymer can be formed due to the homopolymerization of the aromatic vinylidene monomer at elevated temperatures. The presence of aromatic vinylidene homopolymer is generally 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 for either the interpolymer or the aromatic vinylidene homopolymer. For the purpose of the present invention, it is preferred that not more than 20 percent by weight, preferably less than 1 5 percent by weight based on the total weight of vinylidene aromatic homopolymer interpolymers be present. The substantially random interpolymers can be modified by typical insertion, hydrogenation, functionalization, or other reactions well known to those skilled in the art. The polymers can easily be sulfonated or chlorinated to provide derivatives functionalized according to established techniques. Substantially random interpolymers can be prepared as described in EP-A-0,416,815 by James C. Stevens et al. , and in U.S. Patent 5,703, 187,438. The preferred operating conditions for such polymerization reactions are pressures of atmospheric to 3,000 atmospheres and temperatures of -30 ° C to 200 ° C. Polymerizations and unreacted monomer removal at temperatures above the temperature of Autopolymerization of the respective monomers may result in the formation of some amounts of homopolymer polymerization products resulting from the polymerization of the free radical. Examples of suitable catalysts and methods for preparing substantially random interpolymers are described in EP-A-41 6, 815; EP-A-514,828; U.S. Patent No. 5,470,993 corresponding to EP-A-520,732; U.S. Patent No. 5,721,185, as well as 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 and 5,556,928 all patents and applications are incorporated herein by reference in their entirety. The substantially random vinylidene / α-olefin 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, p. 25 (September 1 992), all of which are incorporated herein by reference in their entirety. Also suitable are substantially random interpolymers which comprise at least one tetrad of α-olefin / vinyl aromatic / vinyl aromatic / α-olefin described in WO 98/09999. These interpolymers contain additional signals with intensities greater than three times the peak-to-peak noise. These signals appear in the chemical shift range 43.75-44.25 ppm and 38.0-38-5 ppm. Specifically, the main peaks are observed at 44.1, 43.9 and 38.2 ppm. An NMR Proton Test Experiment indicates that the signals in the chemical shift region 43.75-44.25 ppm are methine carbons and the signals in the 38.0-38.5 ppm region are methylene carbons. In order to determine the chemical shifts 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, 2,2-tetrachloroethane-d2 and 50 percent by volume of chromium 0.1 molar tris (acetylacetonate) is prepared. in 1, 2,4-trichlorobenzene. The NMR spectra are acquired at 1 30 ° C using a reverse input decoupling sequence, at a pulse width of 90 ° and a pulse delay of five seconds or more. The spectra are referenced to the methylene signal isolated from the assigned polymer 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 followed by, at least one α-olefin insert, for example, a tetrad of ethylene / styrene / styrene / ethylene where the styrene monomer insertions of said tetrads occur exlusively 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 tetrad ethylene / vinyl aromatic monomer / vinyl aromatic monomer / ethylene will give an increase to the peaks of carbon NMR 1 3 similar but with slightly different chemical shifts.

These interpolymers are prepared by conducting the polymerization at temperatures from -3 ° C to 250 ° C in the presence of such catalysts as those represented by the formula 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, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms or silicon; each R 'is independently, each occurrence, H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl containing up to 3, preferably 1 to 20, more preferably 1 to 10 carbon atoms or silicon or two R' groups together can be 1, 3-butadiene substituted hydrocarbyl C ^ o; m is 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst. Particularly, suitable substituted cyclopendanyl groups include those illustrated by the formula: wherein each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30, preferably 1 to 20, more preferably 1 to 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 where appropriate all isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two such R groups are linked together forming 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 (dimethylsilanediyl) -bis- (2- racemic methyl-4-phenylindenyl) zirconium, di-C 1-4 alkyl of racemic (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium, di-C 1-4 alkoxy (dimethylsilanediyl) -bis- (2-methyl- Racemic 4-phenylindenyl) zirconium, or any combination thereof. Additional preparation methods for the interpolymer component (A) of the present invention have been described in the literature. Longo and Grassi (Makromol, Chem .. volume 191, pages 2387 to 2396 [1 990]) and D'Anniello et al. , (Journal of Applied Polymer Science, volume 58, pages 1 701 -1 706 [1,995]) 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. Polvm. Chem.) Volume 35, pages 686,687 [1 994]) have reported copolymerization using a MgCl 2 / TiCl 4 / NdCl 3 / AI (iBu) 3 catalyst to give random copolymers of styrene and propylene. Lu et al (Journal of Applied Polymer Science, Volume 53, pages 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a MgCl2 / TiCl4 / NdCI3 / MgCl2 / AI (Et) 3 catalyst. The manufacture of vinyl aromatic monomer / α-olefin interpolymers such as propylene / styrene and butene / styrene is described in U.S. Patent No. 5,244,996, issued to Mitsui Petrochemical Industries Ltd. All the above described methods for preparing the interpolymer component they are incorporated herein by reference. Suitable modifiers that can be employed herein as the plasticizer component (B) include at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, aliphatic diesters (including adipates, azelates and sebacates) ), epoxy compounds, phosphate esters, glutarates, polymeric plasticizers (polyesters of glycols and aliphatic dicarboxylic acids) and oils. Particularly suitable phthalate esters include, for example, dialkyl C4-C1-phthalate esters such as diethyl, dibutyl phthalate, diisobutyl phthalate, butyl 2-ethylhexyl phthalate, dioctyl phthalate, diisooctyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, diundecyl phthalate, mixed aliphatic esters such as heptyl nonyl phthalate, di ( n-hexyl, n-octyl, n-decyl) phthalate (P61 0), di (n-octyl, n-decyl) phthalate (P81 0), and esters of aromatic phthalate such as diphenyl phthalate ester, or aliphatic-aromatic esters mixtures such as benzyl butyl phthalate or any combination thereof.

Particularly suitable trimellitate esters include, for example, tri (2-ethylhexyl) trimellitate, tri (heptyl, nonyl) trimellitate, tri isooctyl trimellitate, tri isodecyl trimellitate, tri (octyl, decyl) trimellitate. Particularly suitable benzoates include, for example, diethylene glycol dibenzoate and dipropylene glycol dibenzoate. Particularly suitable epoxy compounds include, for example, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil. Particularly suitable phosphate esters include, for example, triaryl, trialkyl, mixed alkyl aryl phosphates such as tributyl phosphate, trioctyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, isopropylphenyl diphenyl phosphate, t- butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate and isodecyl diphenyl phosphate. Particularly suitable oils include, for example, mineral oils, natural oils, naphthenic oils, paraffinic oils and aromatic oils. The most preferred oils are those having an aromatic content from 12 to 28.5 percent by weight; a flash point from 31 5 ° C to 420 ° C and an ASTM viscosity D445 at 40 ° C from 9 to 85 centistokes (9 x 10"6 to 85 x 1 0" 6 m2 / sec). The compositions of the present invention suitably comprise from 50 to 99, preferably from 55 to 95, most preferably from 60 to 90, percent by weight based on the combined weight of components (A) and (B) of the ) interpolymer (s) of aromatic vinylidene monomer / α-olefin and / or cycloaliphatic and / or aliphatic vinylidene monomer clogged as component (A); and from 1 to 50, of preferably from 5 to 45, most preferably from 10 to 40, percent by weight based on the combined weight of the components (A) and (B) of the plasticizer (s) as component (B). Preferably, the composition comprises; (A) from 40 to 85 percent by weight of at least one substantially random interpolymer comprising (1) from 6.3 to 15.2 percent mole of polymer units derived from styrene; and (2) from 84.8 to 93.7 mole percent of polymer units derived from ethylene, or a combination of ethylene with propylene; (B) from 15 to 60 weight percent of at least one naphthenic oil or a mixture of at least one naphthenic oil and at least one paraffinic oil; and wherein (i) component (A) has a melt index from 0.1 to 10 g / 10 min; and (ii) said composition has a flexural modulus (2 percent secant) from 4, 137 kPa to 48,953 kPa, a process index from 0.1 to 2.0 kpoise, and a thermomechanical analysis (TMA) from 60 ° C to 1 00 ° C . More preferably, the composition comprises; (A) from 55 to 85 weight percent of at least one substantially random interpolymer comprising (1) from 6.3 to 1 0.3 mole percent of polymer units derived from styrene, and (2) from 89.7 to 93.7 mole percent of units of polymer derived from ethylene, or a combination of ethylene with propylene; (B) from 1-5% to 45% by weight of at least one naphthenic oil and aromatic oils; and wherein (i) component (A) has a melt index from 0.1 to 2 g / 10 min; and (ii) said composition has a flexural modulus (2 percent secant) from 4, 137 kPa to 27,579 kPa, a process index from 0.1 to 1.0 kpoise, and a thermomechanical analysis (TMA) from 65 ° C to 1 00 ° C. Even more preferably, the composition comprises; (A) from 60 to 65 weight percent of at least one substantially random interpolymer comprising (1) from 7.8 to 1 0.3 mole percent of polymer units derived from styrene, and (2) from 89.7 to 92.2 mole percent of units of polymer derived from ethylene; (B) from 35 to 40 weight percent of at least one naphthenic oil; and wherein (i) component (A) has a melt index of from about 0.5 to about 0.9 g / 1 0 min; and (ii) said composition has an inflectional modulus (2 percent secant from 4, 1 37 kPa to 13,790 kPa, a process index from 0.1 to 0.3 kpoise, and a thermomechanical analysis (TMA) from 70 ° C to 1 00 ° C. The compositions of the present invention may be prepared by any suitable method known in the art such as, but not limited to, dry blending in a pelletized form in the proportions desired followed by a casting mix in a screw extruder, an internal batch mixer for example, a Banbury mixer, a calender or roller mill, or the like. Alternatively, the processing oil or plasticizer may be added to a solution of the interpolymer, followed by devolatilization of the solvent by any suitable means such as in a steam separator, flash devolatilizer, slide film evaporator, or devolatilization extruder. . For example, the plasticizer or oil may be added to the ether polymer solution after it leaves the polymerization reactor of the polymer. This can be achieved by mixing the two liquid streams for example with a static in-line mixer. Additives such as antioxidants (e.g., clogged phenols such as, for example I RGANOXMR 1 01 0), phosphites (e.g., IRGAFOS® 168), U .V stabilizers. , adhesion additives (eg, PI B), antiblock additives, slip agents, colorants, pigments, fillers, and the like may also be included in the interpolymers employed in the mixtures of the present invention, to the extent that they do not interfere with the Intensifying properties discovered by the Requesters. Minor amounts, up to 50 weight percent of other polymers including polystyrene, syndiotactic polystyrene, styrenic copolymers such as styrene / acrylonitrile, homo and copolymers of polyolefin, polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, urethane and oxide polymers of polyphenylene, can also be included in the interpolymers used in the mixtures of the present invention, to the extent that they do not interfere with the enhanced properties discovered by the Applicants. 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 undergoing oxidation at the temperatures and environment employed during the storage and final use of the polymers. Such amounts of antioxidants are generally in the range of 0.01 to 1.0, preferably 0.05 to 5, more preferably 0.1 to 2 percent by weight based on the weight of the polymer or polymer blend. Similarly, the amounts of any of the other additives listed are functionally equivalent amounts such as the amount to yield the anti-blocking of the polymer or polymer mixture, to produce the desired amount of filler loading to produce the desired result, to provide the desired color from the dye or pigment. Such additives can be suitably employed 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 polymer mixture. However, in the case of fillers, they may be employed in amounts up to 90 percent by weight based on the weight of the polymer or polymer blend.

The compositions of the present invention can be used to produce, but not limited to, a wide range of manufactured articles such as calendered sheet, blown films and injection molded parts. The compositions can also be used in the manufacture of fibers, foams and latex. The compositions of the present invention can also be used in formulations of adhesives and sealants. The following examples are illustrative of the invention, but should not be considered to limit the scope of the invention in any way.

Preparation of interpolymers (A), (B), (C), and (D) The polymer is prepared in a stirred semi-continuous batch reactor of 1514.16 I. The reaction mixture consisted of approximately 946.35 I of a solvent that it comprises a mixture of cyclohexane (85 weight percent) and isopentane (15 weight percent), and styrene. Before the addition, the solvent, styrene and ethylene were purified to remove water and oxygen. The inhibitor in styrene is also removed. The inerts are removed by purging the container with ethylene. The container is then controlled by pressure to a set point with ethylene. Hydrogen is added to control the molecular weight. The temperature in the container is controlled to the set point by varying the water temperature of the jacket in the container. Before polymerization, the vessel is heated to the desired run temperature and catalyst components: Titanium: (N-1, 1-dimethylethyl) -dimethyl (1 - (1, 2,3,4,5-eta) -2,3,4,5-tetramethyl-2,4-cyclopentad-en-1-yl) silanaminate)) (2- (N) -dimethyl, CAS # 135072-62-7, tris (penta-fluorophenyl) boron , CAS # 001 1 09-15-5, Modified methylaluminoxane Type 3a, CAS # 146905-79-5, are controlled by flow, on a proportion basis molar of 1/3/5 respectively, combined and added to the container. After the start, the polymerization is allowed to proceed with ethyline supplied to the reactor as required to maintain the container pressure. In some cases, the hydrogen is added in the head 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, ethylene is removed from the reactor, then 1000 ppm of antioxidant lrganoxM R 1 010 is added to the solution and the polymer is isolated from the solution. The resulting polymers are isolated from the solution either by steam stripping in a vessel or by the use of a devolatilization extruder. In the case of steam-separated material, additional processing is required in equipment similar to an extruder to reduce residual moisture and any unreacted styrene. Table 1 provides a summary of the process conditions used to produce the polymers, together with the characterization data.

Table 1 Table 1 (cont) * styrene content measured by FTI R technique Preparation of interpolymers (E) - (T) Reactor description A continuously stirred autoclave tank reactor, jacketed with oil, of 22.7 I (CSTR) was employed as the reactor. A magnetically coupled stirrer with Lightining A-320 impellers provides mixing. The reactor ran full of liquid at 3,275 kPa. The process flow entered the bottom and came out at the top. A heat transfer oil was circulated through the jacket of the reactor to remove some heat from the reaction. After the reactor outlet there was a Micromotion flow meter that measured the flow and density of the solution. All lines at the reactor outlet were planned with steam at 344.7 kPa and isolated.

Procedure The toluene solvent was supplied at 207 kPa. The feed to the reactor was measured by a deluxe Micro-Motion mass meter.

A variable speed diaphragm pump controlled the feeding speed. At the discharge of the solvent pump a side stream was taken to provide jet streams for the catalyst injection line (0.45 kg / h) and the reactor agitator (0.34 kg / h). These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves. Styrene monomer was supplied without inhibiting the mini-plant at 207 kPa. The feed to the reactor was measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controlled the feeding speed. The styrene stream was mixed with the remaining solvent stream. The ethylene was supplied to the mini-plant at 4, 1 37 kPa. The ethylene stream was measured by a Micro-Motion mass flow meter just before the development valve controlling the flow. A Brooks flow meter / controller 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 as it enters the reactor was dropped at -5 ° C by means of a glycol exchanger at -5 ° C in the jacket. This current entered the bottom of the reactor. The three-component catalyst system and its sudden flow of solvent also entered the reactor at the bottom but through a different gate to the monomer stream. The preparation of the catalyst components took place in an inert glove compartment type box. The diluted components were placed in nitrogen-filled cylinders and charged to the tanks.

Catalyst run in the process area. From these run-off tanks, the catalyst was pressurized with piston pumps and the flow was measured with Micro-Motion mass flow meters. These streams combine with each other and the catalyst flash flow solvent just before entry through a simple injection line to the reactor. The polymerization was stopped with the addition of the catalyst mat (water mixed with solvent) in the product line of the reactor after the Micromotion luxury meter measures the density of the solution. Other additives of the polymer can be added with the catalyst matte. The catalyst / additive kiln tank was a recycled and stirred tank of 189.27 I. The tank had toluene solvent added. The catalyst matte and the additives were added through a flange on the top of the tank to the solvent of toluene mixture. The tank was sealed and purged with nitrogen to remove any oxygen. The concentrations of the catalyst matte and additives were determined by the polymer production rate and the desired concentration in the polymer. The stirred and recycled tank allowed the use of both soluble and insoluble solid oils and additives. A sidestream was taken from the tank recycle pipe to feed a pulse feed pump that pumped the catalyst kill solution / additives into the reactor product line. A static mixer in the line provided dispersion of the catalyst matte and additives in the stream of the reactor effluent. This current then enters the post-reactor heaters that provide additional power for the "flash" removal of the solvent. This flash occurred as the effluent left the heater after the reactor and the pressure was dropped from 3,275 kPa to -250 mm absolute pressure in the pressure control valve of the reactor. This flashed polymer went into a hot oil jacket devolatilizer. Approximately 85 percent of the volatiles were removed from the polymer in the devolatilizer. The volatiles came out through the top of the devolatilizer. The stream was condensed and with a glycol-enriched exchanger, the suction of a vacuum pump entered and was discharged into a styrene / ethylene separation vessel and glycol jacket solvent. The solvent and styrene were removed from the bottom of the container and the ethylene from the top. The ethylene stream was measured with a Micro-Motion mass flow meter and the composition was analyzed. The measurement of ethylene vented 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 ZSK-30 vacuum devolatory extruder. The dried polymer leaves the extruder as a single 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 cut into pellets with a filament cutter.

Catalysts used a modified methylaluminoxane comperially available from Akzo Nobel as MMAO-3A. dimethyl [N- (1,1-dimethylethyl) -1,1-dimetii-1 - [(1,2,3,4,5-.eta.) - 1,5,6,7-tetrahydro-3-phenyl] -s-indacen-1-yl] silanaminato (2 -) - N] -thiatanium bis-hydrogenated alkyl fatty acid ammonium tetrakis (pentaf luoref in i I) borate tris (pentafluorophenyl) borane.

Reactor data The parts of the test and the characterization data for the interpolymers and mixtures are generated according to the following procedures: Preparation of parts and test procedures: The plasticizers used were: P61 0, a dialkyl ester (hexyl, octyl, decyl) mixed linear phthalate having a molecular weight (MW) of 400 available from CP Hall Co.; G57 is a "polymeric" glutarate (MW -5,700) available from C. P. Hall co. and Sunpar 2280, a paraffinic oil available from Sun Company, I ne and having a molecular weight of 690 and a specific gravity at 1 5.56 ° C of 0.891 1. compression lolded: The samples were melted at 90 ° C for 3 min and were compression molded at 90 ° C under 9,072 kg pressure for another 2 min. Subsequently, the molten materials were cooled in a press equilibrated at room temperature.

Density: The density was determined by ASTM D-792.

Fusion Index: The melt index was determined by ASTM D1238 (1 90 ° C / 21 60g).

Differential Scanning Calorimetry (DSC): A 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. The heating and cooling curves were recorded at 10 ° C / min. The melting temperatures (Tm of the second heating) and crystallization (Tc) were recorded from the peak temperatures of the endotherm and the exotherm, respectively.

Dynamic mechanical spectroscopy (DMB) Dynamic mechanical data were generated using a Rheometrics RSA-I I solid-state analyzer, and melt-pressed film test specimens (~ 0.0508 cm thick). The DMS measurements were conducted at a step speed of 5 ° C / min and a fixed frequency of 10 rad / sec. The glass transition temperature (Tg) of the samples was determined from the maximum peak tan d.

Cutting rheology: oscillatory cut rheology measurements were made with a Rheometrics RMS-800 rheometer. The rheological fusion properties were monitored at an isothermal temperature set at 1 90 ° C in a frequency sweep mode, using parallel plate test geometry.

Thermomechanical Analysis (TMA): The thermomechanical analysis was determined using a Perkin Elmer TMA-7 instrument with a diameter of one millimeter probe. A sample of three millimeters thick five millimeters in diameter was penetrated with a force of one newton (1 02.4 g) as the temperature was increased at a rate of 5 ° C / minute. The temperature at 1 mm of penetration is recorded.

Processing index The rheological processing index (Pl) is the apparent viscosity in kpoises) of a polymer measured by a gas extrusion rheometer (GER). The gas extrusion rheometer is described by M. Shida, R. N. Shroff and L.V. Cancio in polymer Engineering Science, Vol. 17, no. 1 1, p. 770 (1 977), and in "Rheometers for Molten Plastics" by John Dealy, published by Van Nostrand Reinhold Co. (1 982) on page 77, both publications being incorporated by reference herein in their entirety. All GER experiments are performed at a temperature of 190 ° C, at nitrogen pressures between 36.197 kPa to 3.447 kPa using a diameter of 0.0752 cm, 20: 1 l / D.dic. A graph of apparent shear stress versus apparent shear rate is used to identify the melting fracture phenomenon. According to Ramamurthy in Journal of Rheology 30 (2), 337-357, 1986, over a certain critical flow velocity, the observed extrudate irregularities can be broadly classified into two main types: surface fusion fracture and fusion fracture gross. For the polymers described herein, Pl is the apparent viscosity (in kpoise) of a material measured by GER at a temperature of 190 ° C, at a nitrogen pressure of 1 7.237 kPa using a diameter of 0.752 cm, given 20: 1 L / D, or corresponding apparent cutoff voltage of 2.15 x 1 06 dyne / cm2.

Mechanical test: The tensile properties of the compression molded samples were measured using an Instron 1 145 tension machine equipped with a strain gauge. Samples ASTM-D638 were tested at a strain rate of 5 min "1. The micro-tension samples were tested at a rate of 12.7 cm / min at -1 0 ° C. The average is given for four voltage measurements. The deviation The standard for the last properties is typically 1 0 percent of the average value reported.

Tension stress relaxation: The uniaxial tensile stress relaxation was evaluated using an Instron 1 145 tension machine. The compression molded film (-0.0508 cm thick) with a measurement length of 2.54 cm was deformed at a level of deformation of 50 percent at a deformation rate of 20 min. "1 The force required to maintain 50 percent elongation was monitored for 10 min.The magnitude of the stress relaxation is defined as ((f¡-ff) / f ) Where fi is the initial force and ff is the final force.

Flexional module (2% secant) The flexural module was determined by ASTM D-790.

Hardness The hardness of Shore A was determined by ASTM D-2240.

EXAMPLES 1 TO 6 AND COMPARATIVE EXPERIMENT A Six mixing compositions, examples 1, 2, 3, 4, 5 and 6, are prepared from interpolymer (A) above and either a dialkyl ester (hexyl, octyl, decyl ) mixed linear phthalate (P61 0, available from CP Hall Company, and having a molecular weight (MW) of 400) or mineral oil (Sunpar 2280, a paraffinic oil available from Sun Company.

Inc. And having a molecular weight of 690 and a specific gravity at 15.56 ° C of 0.891 1) or polymeric glutarate (G57 available from CP Hall Company) in weight proportions given in Table 2 with a Haake mixer equipped with a bowl Rheomix 3000. 180 grams of the materials of the dry mixed components were fed to the balanced mixer at 50 ° C. The temperature and power balance took 3-5 minutes. The molten material was mixed at 150 ° C and 40 rpm for 10 minutes. The characterization data for the examples and the component interpolymer are given in Table 2. It was possible to modify the interpolymers and produce materials with structural integrity and good mechanical properties. The analysis of examples 4 and 5 of modification with the phthalate ester P610 shows the good plasticization achieved. There is no significant expansion of the tan d of the peak loss associated with the glass transition process of the interpolymer. These modified interpolymers show good performances of low temperature and important retention of stress relaxation behavior. The level of hardness can be controlled by appropriate selection of the plasticizer. The combination of mechanical properties, relaxation behavior, hardness and processability is particularly desirable, for example in many film applications.

Table 2 * It is not an example of the present invention. ** Interpolymer (A) is an ethylene / styrene interpolymer containing 69.4 percent by weight (37.9 mol percent) of styrene (measured by NMR technique), which has a melt flow index of 0.18 and contains 8.4 percent in weight of atactic polystyrene. The polymer showed no measurable crystallinity by DSC techniques.

As a further comparative experiment, a mixture of polystyrene (PS; StyronM R 685D, a polystyrene having an index of Melt flow (200 ° C / 5.0 kg) of 1.5 g / 1 0 min and a specific gravity of 1.04, commercially available from The Dow Chemical Company) and plasticizer P61 0 was produced in a weight ratio PS / P61 0 of 80/20. This produced a material which had a Tg of 37 ° C compared to 106 ° C for the unmodified PS. The properties could not be measured due to the shape of this composition, confirming past experience that the phthalate esters do not function as effective plasticizers in PS.

EXAMPLES 7 AND 8 and COMPARATIVE EXPERIMENT B The two compositions of the mixture, examples 7 and 8, are prepared from the above interpolymer (B) and a mixed linear dialkyl (hexyl, octyl, decyl) phthalate ester (P61 0, available from CP Hall Company, and having a molecular weight (MW) of 400) in weight proportions given in Table 3 with a Haake mixer equipped with a Rheomix 3000 bowl. 1 80 grams of the dry blended components materials were fed to the balanced mixer at 50 ° C. The temperature and power balance took 3-5 minutes. The molten material was mixed at 150 ° C and 40 rpm for 10 minutes. The characterization data for the examples and the component interpolymer are given in Table 3. It was possible to modify the interpolymers, and the materials produced with structural integrity and good mechanical properties. The analysis of examples 7 and 8 of the modification with the phthalate ester P610 shows the good plasticization achieved. There is no significant expansion of the tan d of the peak loss associated with the glass transition process of the interpolymer. These modified interpolymers show good low temperature performance and surprising retention of stress relaxation behavior. The combination of mechanical properties, relaxation behavior, hardness and processability is particularly desirable, for example in many film applications. Table 3 It is not an example of the present invention.

** Interpolymer (B) is an ethylene / styrene interpolymer containing 69.9 percent by weight (37.4 percent mole) of styrene (measured by NMR technique), which has an I2 melt flow index of 1.83 and which contains 8.2 percent by weight of atactic polystyrene. The polymer showed no measurable crystallinity by DSC techniques.

EXAMPLE 9 and COMPARATIVE EXPERIMENT C Example 9 is prepared from the above interpolymer (C) and a mixed linear dialkyl (hexyl, octyl, decyl) phthalate ester (P61 0, available from CP Hall Company, and having a weight molecular weight (MW) of 400) in weight proportions given in Table 4 with a Haake mixer equipped with a Rheomix 3000 bowl. 180 grams of the dry mixed component materials were fed to the balanced mixer at 50 ° C. The temperature and power balance took 3-5 minutes. The molten material was mixed at 150 ° C and 40 rpm for 10 minutes. The characterization data for the example and the component interpolymer are given in Table 4. The modified interpolymer has structural integrity and good mechanical properties. The solid materials show increased crystallinity compared to the unmodified interpolymer. There is some significant expansion of the tan d of the peak loss associated with the interpolymer glass transition process, which may have found utility in some energy absorption applications. Modified ether polymers show good low temperature performance and retention of stress relaxation behavior. The combination of mechanical properties, relaxation behavior, hardness and processability is again desirable, for example in many film applications.

Table 4 * It is not an example of the present invention. ** Interpolymer (C) is an ethylene / styrene ether polymer containing 47.3 percent by weight (19.5 percent mole) of styrene, which has a melt flow index of 0.01 and contains 3.7 percent by weight of atactic polystyrene.

EXAMPLES 1 0 AND 1 1 AND COMPARATIVE EXPERIMENT D The two compositions of the mixture, examples 1 0 and 1 1, are prepared from the above interpolymer (D) and a dialkyl ester. (hexyl, octyl, decyl) mixed linear phthalate (P61 0, available from C. P. Hall company, and having a molecular weight (MW) of 400) or mineral oil (Sunpar 2280, a paraffinic oil available from Sun Company, Ine and it has a molecular weight of 690 and a specific gravity at 15.56 ° C of 0.891 1) in weight proportions given in Table 5 with a Haake mixer equipped with a Rheomix 3000 bowl. 180 grams of the components of the dry-mixed components were fed to the balanced mixer at 1 50 ° C. The temperature and power balance took 3-5 minutes. The molten material was mixed at 150 ° C and 40 rpm for 10 minutes. The characterization data for the examples and the component interpolymer are given in Table 5. The modified interpolymers have structural integrity and good mechanical properties. The oil is a more effective modifier for lowering Tg in this interpolymer compared to the ether polymer (A). The solid materials show small changes in the level of crystallinity compared to the unmodified interpolymer. Both modifiers produce significant expansion of the tan d of the peak loss associated with the glass transition process of the interpolymer, which could find utility in some energy absorption applications. Modified interpolymers show good low temperature performance and retention of stress relaxation behavior.

In addition, the viscosity of the modified interpolymers is significantly reduced, which results in improved processability in some manufacturing processes.

Table 5 * It is not an example of the present invention. ** Interpolymer (D) is an ethylene / styrene interpolymer containing 29.3 percent by weight (10 mole percent) of styrene, which has a melt flow index of 0.02 and contains 1 percent by weight of atactic polystyrene.

Example 12 A. Preparation of the mixture The mixtures were prepared in a Haake mixer equipped with a Rheomix 3000 bowl. The bowl, when fully loaded, contains 220 grams of polymer and oil. The polymer portion of this mixture was fed to the mixer and equilibrated at 90 ° C. The balance of Temperature and power took approximately 3 to 5 minutes. The molten polymer material was mixed at 90 ° C at a mixer speed of 20 rpm for 5 minutes. The oil (Deer Park Naphtenic Oil 3131 having an aromatic content of 28.1 percent by weight, a flash point of 31 5 ° C and an ASTM D445 viscosity of 9.1 8 centistokes (9.18 x 1 0"6 m2 / sec) at 40 ° C available from Shell Lubricants in Deep Park, Texas) was then added and mixed with the polymer at 90 rpm for 5 minutes at 190 ° C.

B. Molded polymer + oil mixture The polymer and oil mixture prepared in A above was compression molded into 0.317 cm x 12.7 cm x 12.7 cm test plates for physical evaluation by subjecting the polymer and oil mixture in the mold at a temperature of 190 ° C and a pressure of 34,474 kPa for 5 minutes followed by a pressure of 137,895 kPa at 1 90 ° C for 3 minutes. The plates were then removed from the mold and allowed to cool to 32 ° C at 34,474 kPa. The composition and properties of the interpolymers used to mix with the oil are given in Table 6 and the properties of the interpolymer and oil mixture are given in Table 7.

Table 6 Table 7 CND = can not be determined

Claims (10)

REIVI NDI CATIONS

1 . A thermoplastic composition comprising (A) from 50 to 99 percent by weight of at least one substantially random interpolymer comprising (1) from 5 to 65 percent mole of (a) at least one aromatic vinylidene monomer, or (b) by at least one cycloaliphatic or aliphatic vinylidene monomer clogged, or (c) a combination of at least one aromatic vinylidene monomer and at least one cylindrical or aliphatic cycloaliphatic vinylidene monomer, and (2) from 35 to 95 mol percent of polymer units derived from ethylene, or a combination of ethylene with propylene; and (B) from 1 to 50 weight percent of at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, aliphatic diesters, epoxies, phosphate esters, glutarates, polymeric plasticizers and oils.

2. A composition of claim 1 wherein the component (A) comprises from 5 to 50 percent mole of polymer units derived from at least one aromatic vinylidene monomer and from 50 to 95 mole percent of polymer units derived from ethylene , or a combination of ethylene with propylene.

3. A composition of claim 1 wherein component (A) comprises from 5 to 50 percent mol of polymer units derived from styrene and from 50 to 95 percent of polymer units derived from ethylene, or a combination of ethylene with propylene.

4. A composition of claim 1 comprising (A) from 60 to 95 percent by weight of at least one substantially random interpolymer comprising (1) from 5 to 50 percent mole of polymer units derived from at least one aromatic monomer of vinylidene, and (2) from 50 to 95 percent mol of polymer units derived from ethylene, or a combination of ethylene with propylene; (B) from 5 to 40 weight percent of at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, aliphatic diesters, epoxy compounds, phosphate esters, glutarates, polymeric plasticizers and oils.

5. A composition of claim 1 comprising (A) from 60 to 95 percent by weight of at least one substantially random interpolymer comprising (1) from 5 to 50 percent mole of polymer units derived from styrene, and (2) from 50 to 95 percent mol of polymer units derived from ethylene, or a combination of ethylene with propylene; (B) from 5 to 40 weight percent of at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, aliphatic diesters, epoxy compounds, phosphate esters, glutarates, polymeric plasticizers and oils.

6. A composition of claim 1 comprising (A) from 60 to 95 weight percent of at least one substantially random polymer comprising (1) from 5 to 50 percent mole of polymer units derived from styrene, and (2) from 50 to 95 percent mol of polymer units derived from ethylene, or a combination of ethylene with propylene; (B) from 5 to 40 weight percent of at least one plasticizer selected from the group consisting of phthalate esters, including mixed dialkyl, mixed linear dialkyl, aryl, and alkyl aryl esters.

7. A composition of claim 1 comprising (A) from 60 to 95 percent by weight of at least one substantially random interpolymer comprising (1) from 5 to 50 percent mole of polymer units derived from styrene, and (2) from 50 to 95 percent mol of polymer units derived from ethylene, or a combination of ethylene with propylene; (B) from 5 to 40 weight percent of at least one oil selected from mineral oils, natural oils, naphthenic oils, paraffinic oils and aromatic oils.

8. A composition of claim 1 comprising (A) from 40 to 85 percent by weight of at least one substantially random interpolymer comprising (1) from 6.3 to 15.2 mole percent of polymer units derived from styrene, and (2) from 84.8 to 93.7 mole percent of polymer units derived from ethylene, or a combination of ethylene with propylene; (B) from 15 to 60 weight percent of at least one naphthenic oil or a mixture of at least one naphthenic oil and at least one paraffinic oil; and wherein (i) component (A) has a melt index from 0.1 to 10 g / 10 min, as measured by ASTM D 1238, 190 ° C / 2160 g; and (ii) said composition has a flexural modulus (by ASTM D-790, 2 percent secant) of 4, 137 kPa at 48,953 kPa, a process index (by gas extrusion rheometry) of 0.1 to 2.0 kpoise, and a thermomechanical analysis (TMA) from 60 ° C to 100 ° C.

9. A composition of claim 8 comprising (A) from 55 to 85 percent by weight of at least one substantially random interpolymer comprising (1) from 6.3 to 1 0.3 percent mole of polymer units derived from styrene, and (2) from 89.7 to 93.7 percent mol of polymer units derived from ethylene, or a combination of ethylene with propylene; (B) from 1 to 45 percent by weight of at least one naphthenic oil and aromatic oils; and where (i) component (A) has a melt index from 0.1 to 2 g / 1 0 min, as measured by ASTM D 1238, 190 ° C / 21 60 g; and (ii) said composition has a flexural modulus (by ASTM D-790, 2 percent secant) of 4.137 kPa at 27.579 kPa, a process index (by gas extrusion rheometry) of 0.1 to 1.0 kpoise, and a thermomechanical analysis (TMA) of 65 ° C to 100 ° C. A composition of claim 8 comprising (A) from 60 to 65 percent by weight of at least one substantially random interpolymer comprising (1) from 7.8 to 10.3 percent mole of polymer units derived from styrene, and (2) from 89.7 to 92.2 percent mole of polymer units derived from ethylene; (B) from 35 to 40 weight percent of at least one naphthenic oil; and wherein (i) component (A) has a melt index of 0.5 to 0.9 g / 1 0 min, as measured by ASTM D1238, 190 ° C / 21 60 g; and (ii) said composition has a flexural modulus (by ASTM D-790, 2 percent secant) of 4.137 kPa at 13,790 kPa, a process index (by gas extrusion rheometry) of 0.1 to 0.3 kpoise, and a Thermomechanical analysis (TMA) from 70 ° C to 100 ° C. eleven . A composition of any one of claims 1-10 containing 1 to 50 percent by weight of one or more additional polymers selected from polystyrene, syndiotactic polystyrene, styrenic copolymers such as styrene / acrylonitrile copolymer, homo and copolymers of polyolefin, polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, urethane polymers and polyphenylene oxide. 12. A composition of any of claims 1 -1 1 in the form of foams, fibers or emulsions. 1 3. A composition of any of claims 1 -1 1 in the form of sealant or adhesive compositions. 14. A composition of any of claims 1 -1 1 in the form of blow molded or extruded parts, by compression, or by injection. 15. A composition of any of claims 1 -1 1 in the form of a film or sheet, or as a multi-layer structure component resulting from calendering, blowing, pouring or (co-) extrusion operations.