MXPA01005580A - Enlarged cell size foams made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers - Google Patents

Abstract

This invention pertains to a composition and a process for preparing a closed cell alkenyl aromatic polymer foam having enlarged cell size, comprising one or more alkenyl aromatic polymers, one or more substantially random interpolymers, one or more blowing agents having zero ozone depletion potential and optionally one or more co-blowing agents, and optionally, one or more nucleating agents and optionally, one or more other additives. This combination allows the manufacture of closed cell, low density alkenyl aromatic polymer foams of enlarged cell size, when blowing agents of relatively high nucleation potential are employed. When such blowing agents are used with alkenyl aromatic polymers in the absence of the substantially random interpolymers, small cell foams result.

Description

ALUMINUM CELLULAR SIZE FOAMS FORMED OF MIXES OF AROMATIC POLYMERS OF ALKENIL AND INTERPOLYMERS OF ALPHA-OLEFINE / VINYLENE OR VINYLIDENE AROMATIC AND / OR VINYL OR VINYLIDENE ALIPHATIC OR CICLOALIATIC, ESTERICALLY HIDDEN This invention describes a method for elongating the cell sizes of alkenyl aromatic foams by mixing the polymers comprising (A) aromatic alkenyl polymers and (B) substantially random interpolymers of vinylidene or vinylidene aliphatic or cycloaliphatic, aromatic and / or aesthetically concealed of vinyl or vinylidene. Suitable alkenyl aromatic polymers include alkenyl aromatic homopolymers and copolymers of alkenyl aromatics and ethylenically unsaturated copolymerizable comonomers. The polymeric alkenyl material comprises more than 50 and preferably more than 70 weight percent of alkenyl aromatic monomer units. More preferably, the aromatic alkenyl polymer material is comprised of aromatic monomeric alkenyl units. Aromatic alkenyl polymers include those derived from alkenyl aromatic compounds such as styrene, alpha-methylstyrene, etc. A preferred alkenyl aromatic polymer is polystyrene. Examples of copomable compounds include acrylic acid, methacrylic acid, acrylonitrile, etc. The substantially random polytermers comprise polymer units derived from ethylene and / or one or more α-olefin monomers with specific amounts of one or more vinyl aromatic vinyl or vinylidene monomers and / or aliphatic or cycloaliphatic, vinylidene, sterically hidden monomers or vinylidene or vinylidene monomers. A preferred substantially random interpolymer is an ethylene / styrene interpolymer. The incorporation of the substantially random interpolymer in the mixture with the aromatic alkenyl polymer gives the formation of foams having elongated cell sizes when the zero or reduced ozone elimination potential blowing agents (which have low solubility and relatively nucleation potential). elevated) are used. Due to the environmental interests present over the use of ozone removal blowing agents, it is desirable to make alkenyl aromatic polymer foams with blowing agents having zero or reduced ozone removal potential. Such blowing agents include suitable inorganic blowing agents include nitrogen, sulfur hexafluoride (SF6) and argon; organic blowing agents such as carbon dioxide and hydrofluorocarbons such as 1, 1, 1, 2-tetrafluoroethane (HFC-1 34a), 1,1, 2,2-tetrafluoroethane (HFC-1 34), difluoromethane (HFC-32) ), 1,1-difluoroethane (HFC-152a), pentafluoroethane (HFC-1 25), fluoroethane (HFC-161), and 1,1,1-trifluoroethane (HFC-143a), and hydrocarbons such as methane, ethane, propane, n-butane, isobutane, p-pentane, isopentane, cyclopentane and neopentane; and chemical blowing agents including azodicarbonamide, azodiisobutyronitrile, benzenesulfonhydrazide, 4,4-oxybenzene, sulfonyl-semicarbazide, p-toluene-sulfonyl semi-carbazide, barium azodicarboxylate, N. N'-dimethyl-N, N'- dinitroso-terephthalamide, trihydrazine triazine and mixtures of citric acid and sodium bicarbonate such as several products sold under the name Hidrocerol ™ (a product and trademark of Boehringer Ingelheim).

All of these blowing agents can be used as single components or any combination mixture thereof, or mixed with other co-blowing agents. One problem with the use of the above-mentioned non-ozone depleting blowing agents is their tendency to form relatively small and transverse cell-sized foams. Such blowing agents typically result in foams having small cell sizes because of their relatively high nucleation potential. Small cell size is especially a problem when particular infrared attenuating agents are employed such as natral gas carbon black, graphite, and titanium dioxide. It would be desirable to be able to employ non-ozone depleting blowing agents to make alkenyl aromatic polymer foams with or without infrared attenuating agents to be able to expand the foam cell size. The lengthening of the cellular size of the foams would allow greater thickness and greater cross-sectional areas to be obtained. Lower foam densities would be desirable for both extruded and expanded alkenyl aromatic polymer foams. Greater thicknesses of foam and cross sections would allow a wider range of products to be manufactured and the reduction in density will allow foams that are manufactured more economically. It is also desirable that the foams exhibit acceptable physical properties.

Previous attempts to make a foam having elongated cell size include the integration of a wax into a foaming gel prior to the extrusion of the gel through a nozzle to form a foam. Such use of a wax is noted in U.S. Patent No. 4,229,396. The use of a wax may, however, present processing problems and cause variations in thermal stability or decrease in physical properties in product foams. Wax can also cause inconsistency in extrusion temperatures. Additional prior art attempts to make a foam having elongated cell size include incorporation of a non-waxy compound into a foaming gel prior to extrusion of the gel through a nozzle to form a foam. Such use of a non-waxy compound is noted in U.S. Patent No. 5,489,407. Alkenyl aromatic polymer foams of long cell size have been prepared using glycerol monoesters of C8-C24 fatty acids as agents that elongate cell size as described in USP 5,776,389. However, the concentration of such agents in a foam that can be used is limited, as high levels reduce the glass transition temperature of the polymer and can result in degradation of physical properties such as slip under load (a 80 ° C). These would be desirable to identify compounds that elongate the cell size that can be used in conjunction with non-ozone depleting blowing agents and have no adverse effect on the mechanical or physical properties of the foam.

The present invention pertains improved closed-cell alkenyl aromatic polymer foams having elongated cell size comprising: (A) from 80 to 99.7 weight percent (based on the combined weight of Components A and B) of one or more aromatic alkenyl polymers and wherein at least one of said alkenyl aromatic polymers has a molecular weight (Mw) of from 100,000 to 500,000; and (B) from 0.3 to 20 weight percent (based on the combined weight of Components A and B) of one or more substantially random interpolymers having a 12, from 0.01 to 1000 g / 1 0 min, and a " Mw / Mn, from 1.5 to 20, comprising (1) from 8 to 65 mole percent of the polymer units derived from: (a) at least one vinyl or vinylidene aromatic monomer, or (b) at less a concealed aliphatic or cycloaliphatic vinylidene or vinylidene monomer, or (c) a combination of at least one aromatic vinyl or vinylidene monomer and at least one aliphatic or cycloaliphatic vinylidene or vinylidene monomer, and (2) of to 92 mole percent of polymer units derived from at least one of ethylene and / or C3-2 o-olefin, and (3) from 0 to 20 mole percent of polymer units derived from one or more polymerizable ethylenically unsaturated monomers different from those derived from (1) and (2), and (C) optionally, one or more age nucleation agents, and (D) optionally, one more different additives; and (E) one or more blowing agents having a zero ozone removal potential, and optionally one or more co-blowing agents, present in a total amount of 0.2 to 5.0 grams-moles per kilogram (based on the combined weight) of Components A and B); wherein the cellular size of said foam is extended 5 percent or more relative to a corresponding foam without the substantially random interpolymer. This combination also allows the manufacture of low density alkenyl aromatic polymer foams of elongated cell size and relatively thick cross-section, when relatively high nucleation potential blowing agents are employed. When those blowing agents are used with aromatic alkenyl polymer in the absence of the substantially random interpolymers, it results in small cell size foams. further, it has unexpectedly been found that cell size can be lengthened by using substantially random interpolymers without substantial degradation of foam mechanical properties (as occurs without high concentrations of cell-size extenders of the prior art such as glycerol monoesters are used). In addition, the foam density can be reduced in some cases, which is desirable both extruded and expanded foams made of alkenyl aromatic polymers. Definitions All references herein to the elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press Inc., 1989. Also any reference in the Group or Groups should be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for the numbering groups. Any numerical value described herein, includes all values from the value below the upper 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 and time, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 1 5 to 85, 22 to 68, 43 to 51, 30 to 32, etc., are expressly listed in this specification. For values that are less than one, a unit that can be 0.0001, 0.001, 0.01, or 0.1 is considered appropriate. These are only examples of what is specifically intended and all possible combinations of the numerical values between the lower value and the upper value listed are considered to be expressly set forth 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 form the interpolymer. This includes copoimers, terpolymers, etc. The term "elongate cell size" is used herein to mean a foam having an increase in cell size of 5 percent, preferably 10 percent, more preferably 15 percent or more relative to an analogous foam made without the interpolymer substantially random. The invention especially covers foams comprising mixtures of one or more alkenyl aromatic homopolymers or copolymers of alkenyl aromatic monomers, and / or copolymers of aromatic alkenyl monomers with one or more copolymerizable ethylenically unsaturated comonomers (other than ethylene or α-olefins). Linear C3-d2) with at least one substantially random interpolymer. The foams of this invention have elongated cell sizes relative to corresponding foams of similar density made without the substantially random interpolymer. The aromatic alkenyl polymer material may also include minor proportions of aromatic polymers without alkenyl. The aromatic alkenyl polymer material may be comprised only of one or more alkenyl aromatic homopolymers, one or more alkenyl aromatic copolymers, a mixture of one or more of each of the alkenyl aromatic homopolymers and copolymers, or mixtures of any of the foregoing with an aromatic polymer without alkenyl. Despite the composition, the alkenyl aromatic polymer material comprises more than 50 and preferably more than 70 weight percent aromatic monomeric alkenyl units. More preferably, the aromatic alkenyl polymer material is comprised entirely of alkenyl aromatic monomer units. Suitable alkenyl aromatic polymers include homopolymers and copolymers derived from alkenyl aromatic compounds such as styrene, alphamethylstyrene, ethylstyrene, vinylbenzene, vinyl toluene, chlorostyrene, and bromostyrene. The aromatic alkenyl polymer material may also include commercial HIPS (high impact polystyrene). A preferred alkenyl aromatic polymer is polystyrene. Minor amounts of monoethylenically unsaturated compounds such as C-e alkyl acids and esters, ionomeric derivatives and C4-6 dienes can be copolymerized with alkenyl aromatics. Examples of co-polymerizable compounds include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, acrylonitrile, maleic anhydride, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, vinyl acetate and butadiene. The term "substantially random" (in the substantially random interpolymer comprising polymeric units derived from ethylene and one or more α-olefin monomers with one or more vinyl or vinylidene aromatic monomers and / or aliphatic or cycloaliphatic vinylidene or vinylidene monomers) as used herein, it means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first and second order Markovian statistical model, as described by JC. Randall in POLYMER SEQUENCE DETERMINATION. Carbon-1 3 NMR Method. Academic Pres New York, 1977, pp 71-78. Preferably, the substantially random interpolymers do not contain more than 1 5 percent of the total amount of vinyl aromatic monomer in aromatic vinyl monomer blocks of more than 3 units. More preferably, the interpolymer is not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the NMR spectrum of the carbon 13 of the substantially random interpolymer the peak areas corresponding to the methylene and methylene chain main moieties representing either bivalent radical meso sequences or racemic bivalent radical sequences can not exceed 75. percent of the total peak area of the main chain methine and methylene carbons The interpolymers used to prepare the foams of the present invention include substantially random interpolymers prepared by polymerizing) ethylene and / or one or more α-olefin monomers and ii) one or more vinyl vinyl aromatic monomers or vinylidene and / or one or more aliphatic or cycloaliphatic vinylidene or vinylidene monomers, and optionally iii) other polymerizable ethylenically unsaturated monomers Suitable a-olefins include, for example, α-olefins which they contain from 3 to 20, preferably from 3 to 12, more preferably from 3 to 8 atoms of carbon Ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 or ethylene are particularly suitable in combination with one or more of propylene, butene-1,4-methyl-1 -pentene, hexene-1 or octene-1. These α-olefins do not contain an aromatic portion. Other optional polymerizable ethylenically unsaturated monomers include norbornene and norbornenes substituted with C6-10 aryl or C?.? 0 alkyl with an illustrative interpolymer being ethylene / styrene / norbornene. Suitable vinyl or vinylidene aromatic monomers that can be used to prepare the interpolymers include, for example, those represented by the following formula: Ax CCH2) r R1 CCR2); wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methylene; Ar is a phenyl group or a phenyl group substituted with 1 to 5 substitutes selected from the group consisting of halo, C 1-4 alkyl, and C 1 - haloalkyl; and n has a value from zero to 4, preferably from zero to 2, more preferably zero. Illustrative vinyl aromatic monomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable monomers include styrene and derivatives substituted with halogen or lower alkyl thereof. Preferred monomers include styrene, α-methylstyrene, substituted phenyl ring or lower alkyl derivatives of styrene (C?-C4), such as, for example, ortho-, meta- and para-methylstyrene, halogenated ring styrenes, para-vinyl toluene or mixtures thereof. A most preferred aromatic vinyl monomer is styrene. By the term "aesthetically concealed aliphatic or cycloaliphatic vinylidene or vinylidene compounds" means the addition of polymerizable vinyl or vinylidene monomers corresponding to the formula: TO" ! - C C (R?). wherein A1 is a sterically bulky aliphatic or cycloaliphatic substitute 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 R 2 independently is 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. Preferred vinylidene, vinylidene, cycloaliphatic or cycloaliphatic compounds in which one of the carbon atoms bearing the ethylenic unsaturation is a tertiary or quaternary substitute. Examples of such substitutes include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl or aryl-substituted or ring-alkyl derivatives thereof, tert-butyl and norbornyl. The most preferred vinylidene, aliphatic or cycloaliphatic or vinylidene compounds are various isomeric vinyl ring substituted derivatives of cyclohexene and substituted cyclohexenes and 5-ethylidene-2-norbornene. 1-, 3- and 4-vinylcyclohexane are especially suitable. Simple linear unbranched α-olefins including, for example, α-olefins containing from 3 to 20 carbon atoms such as propylene, butene-1, 4-methyl-1-pentene, hexene-1 or octene-1 are not examples of sterically hidden vinylidene, aliphatic or cycloaliphatic vinylidene compounds. Substantially random interpolymers include pseudo-random interpolymers as described in EP-A-0,416,815 by James C. Stevens et al. , and U.S. Patent No. 5,703, 187 by Francis J. Timmers, both of which are incorporated herein by reference in their entirety. Substantially random interpolymers are prepared by polymerizing a mixture of polymerizable monomers in the presence of one or more constrained geometric metallocenes or catalysts in combination with several cocatalysts. Preferred operating conditions for such polymerization reactions are pressures from atmospheric to 3000 atmospheres and temperatures from -30 ° C to 200 ° C. Polymerizations and removal of unreacted monomer at temperatures above the autopolymerization temperature of the respective monomers may result in the formation of some amounts of homopolymer polymerization products resulting from the polymerization of free radicals. Examples of suitable catalysts and methods for the preparation of substantially random interpolymers are described in the application of E.U .. Series No. 702,475 filed May 20, 1 991 (EP-A-514,828); as well as U.S. Patent Nos .: 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5, 189, 192; 5,321, 1 06; 5,347,024; 5,350,723; 5,374,696; 5,399,635; 5,470,993; 5,703, 1 87; and 5,721, 185. Substantially randomized aromatic α-olefin / vinyl interpolymers can also be prepared by the methods described in JP 07/278230 which employ the compounds shown in the general formula C - / R l R3 M Cp - R2 wherein Cp1 and Cp2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substitutes thereof, independently of one another; R1 and R2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1 -1 2, alkoxyl groups or aryloxyl groups, independently of one another; M is a group IV metal, preferably Zr or Hf, more preferably Zr; and R3 is an alkylene group or silanodiyl group used to degrade Cp1 and Cp2). The substantially random aromatic α-olefin / vinyl 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). Substantially random interpolymers comprising at least one a-olefin / vinyl aromatic / vinyl aromatic / α-olefin tetrad described in US Application No. 08 / 708,869 filed September 4, 1996 and WO 98 are also suitable. / 09999 both by Francis J. Timmers er al. These etherpolymers contain additional signals in their NMR spectrum of carbon-1 3 with intensities greater than three times the peak-to-peak interference. These signals appear on the chemical change scale 43.70 - 44.25 ppm and 38.0 - 38.5 ppm. Specifically, the main peaks were observed 44.1, 43.9 and 38.2 ppm. A proton test experiment by NMR indicates that the signals in the region of chemical changes of 43.70 - 44.25 ppm are methine carbons and the signals in the region of 38.0 - 38.5 ppm are methylene carbons. It is thought that these new signals are due to sequences involving two inserts of vinyl aromatic monomers from head to tail preceded and followed by at least one α-olefin insert. For example, an ethylene / styrene / styrene / ethylene tetrad wherein the styrene monomer insertions of said tetrads occur exclusively in a 1, 2 (head-to-tail) form. It will be understood by one skilled in the art that for such tetrads involving a vinyl aromatic monomer other than styrene and an a-olefin other than ethylene the aromatic monomer of the ethylene / vinyl tetrad / aromatic vinyl / ethylene monomer will give rise to NMR peaks of carbon-1 3 similar but with slightly different chemical changes. These interpolymers can be prepared by carrying out the polymerization at a temperature of -30 ° C to 250 ° C in the presence of catalysts such as those represented by the formula / tER2} m M S / wherein: each Cp is independently, each time they occur, a substituted cyclopentadienyl group joined-p to M; E is C or Si; M is a group IV metal, preferably Zr or Hf, more preferably Zr; each R is independently, each time H, hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl is present, containing up to about 30 preferably from 1 to 20, more preferably from 1 to 10 carbons or silicon atoms; each R 'each time it occurs is independently H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl containing up to about 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms or silicon or two R groups 'together can be a 1, 3-butanediene substituted with Ci.-io hydrocarbyl, m is 1 or 2; and optionally, but preferably, in the presence of an activating cocatalyst. Particularly, suitable substituted c-clopentadienyl groups include those illustrated by the formula: wherein each R, each time it occurs, is independently H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to about 30, preferably from 1 to 20, more preferably from 1 to 10 carbon atoms or silicon or two R groups together they form a divalent derivative of such a group. Preferably, R independently each time it occurs is (including all isomers where appropriate) hydrogen, methyl, ethyl, propyl, buryl, 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 (dimethylsilanediyl) bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, 1,4-diphenyl-1,3-butadiene (dimethylsilanediyl) -bis- (2-methyl) Racemic 4-phenylindenyl) -circonium, C 1-4 dialkyl of racemic (dimethylsilanediyl) bis (2-methyl-4-phenylimdenyl) -zirconium, C 1-4 alkoxide of (dimethylsilanediyl) -bis- (2- racemic methyl-4-phenylindenyl), or any combination thereof. It is also possible to use the following constrained geometrical catalysts based on titanium, dimethyl of [N- (1,1-dimethylethyl) -1, 1 -dimethyl-1 - [(1, 2, 3,4,5-,?) - 1, 5,6,7-tetrahydro-s-indacen-1-yl-silanaminate (2 -) - N] titanium; dimethyl (1-indenyl) (tert-butylamido) dimethylsilane titanium; dimethyl (3-tert-butyl) (1, 2,3,4, 5-γ) -1-indenyl) (tert-butylamido) dimethylsilane titanium; and dimethyl (3-iso-propyl) (1, 2,3,4, 5-γ) -1-indenyl) (tert-butyl amido) dimethylsilane titanium, or any combination thereof and the like. Additional preparative methods for the interpolymers used in the present invention have been described in the literature. Longo and Grasi (Makromol Chem., Volume 191, pages 2387 to 2396 [1 990] and D'Anniello et al. (Journal of Applied Polymer Science, volume 58, pages 1701 -1706 [1995]) report the use of a system catalyst based on methylaiumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCl3) to prepare an ethylene-styrene copolymer Xu and Lin (Polymer Preprints, Am. Chem. Soc. Div. Polym. Chem.) Volume 35, pages 686, 687 [1994]) have reported copolymerization using a MgCl2 / TiCl4 / NdCI3 / AI (iBu) 3 catalyst to give random copolymers of styrene and propylene. Lu er al. (Journal of Applied Polymer Science, Volume 53, pages 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCl4 / NdCI3 / MgCl2 / AI (Et) 3 catalyst. Sernetz and Mulhaupt, (Macromol. Chem. Phys., V. 197, pp. 1071-1083, 1997) have described the influence of polymerization conditions on the copolymerization of styrene with ethylene using Ziegler-Natta catalysts of Me2Si (Me Cp ) (N-tert-butyl) TiCl2 / methylaluminoxane. The ethylene-styrene copolymers produced by bridged metallocene catalysts have been described by Arai. Toshiaki and Suzuki (Polymer Preprints, Am. Chem. Soc. Div. Polvm. Chem.) Volume 38, pages 349, 350 [1997] and in U.S. Patent No. 5,652,315, issued to Mitsui Toatsu Chemicals, Inc. Manufacturing of the interpolymers of aromatic α-olefin / vinyl monomers such as propylene / styrene and butene / styrene are described in U.S. Patent No. 5,244,996, issued to Mitsui Petrochemical Industries Ltd., or U.S. Patent No. 5,652.31 5 also issued Mitsui Petrochemical Industries Ltd. or as described in DE 197 1 1 339 A1 of Denki Kagaku Kogyo KK. The random ethylene-styrene copolymers as written in Polymer Preprints Vol. 39, No. 1, March 1 998 by Toru Aria et al. , they can also be used as mixing components for the foams of the present invention. While preparing the substantially random interpolymer, an amount of atactic vinyl aromatic homopolymer can be formed due to the homopolymerization of the aromatic vinyl monomer at elevated temperatures. The presence of vinyl aromatic homopolymer in general is not detrimental to the purposes of the present invention and can be tolerated. The vinyl aromatic homopolymer can be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation of the solution with a non-solvent for the interpolymer or the aromatic vinyl homopolymer. For the purposes of the present invention it is preferred that no more than 30 weight percent, preferably less than 20 weight percent, be present based on the total weight of the atactic vinyl aromatic homopolymer interpolymers. Preparation of the Foams of the Present Invention The compositions of the present invention can be used to form extruded thermoplastic polymer foam, expandable thermoplastic foam beads or expanded thermoplastic foams and molded articles formed by expansion and / or coalescence and welding of these particles. The foams can have any known physical configuration, such as sheet, rod, plank, films and extruded profiles. The structure of the foam can also be formed by molding the expandable beads in any of the above configurations or any other configuration. . The foam structures can be made by a conventional extrusion foam forming process. The present foam is generally prepared by melt blending in which the aromatic alkenyl polymeric material and one or more substantially random interpolymers are heated together to form a plasticized or molten polymer material, incorporating therein a blowing agent to form a foamable gel and extruding the gel through a nozzle to form the foam product. Prior to the extrusion of the nozzle, the gel is cooled to an optimum temperature. To form a foam, the optimum temperature is above the glass transition temperature or melting point of the mixtures. For the foams of the present invention the optimum foaming temperature is on a scale sufficient to produce an open cell content in the foam of 20 volume percent or less and optimize the physical characteristics of the foam structure. The blowing agent can be incorporated or mixed into the polymeric melting material by any means known in the art such as with an extruder, mixer, blender, or the like. The blowing agent is mixed with the melting polymer material at a high enough pressure to prevent substantial expansion of the polymeric melting material and to generally disperse the blowing agent homogeneously therein. Optionally, a nucleator can be mixed in the polymer melt or mixed dry with the polymeric material before plasticizing or casting. The substantially random interpolymers may be dry mixed with the polymeric material before being charged to the extruder, or charged to the extruder in the form of a polymer concentrate or an interpolymer / color pigment carrier material. The foamable gel is typically cooled to a lower temperature to optimize the physical characteristics of the foam structure. The gel can be cooled in the extruder or mixed with another device or in separate refrigerators. The gel is then extruded or transported through a nozzle in a desired manner to a zone of reduced pressure or below to form the foam structure. The lower pressure zone is at a lower pressure than that at which the foamable gel is maintained prior to extrusion through the nozzle. The lower pressure can be superatmospheric or subatmospheric (vacuum), but preferably it is at an atmospheric level. The structures of the present foams can be formed into a coalesced strand form by extruding the compositions of the present invention through a multi-orifice nozzle. The holes are arranged so that contact between the adjacent streams of the molten extrudate occurs during the foaming process and the contacting surfaces adhere to each other with sufficient adhesion that results in a unitary foam structure. The streams of the molten extrudate leaving the nozzle take the form of strands or profiles, which conveniently foam, collide and adhere to each other to form a unitary structure. Conveniently, the coalesced individual strands or profiles must remain adhered in a unitary structure to prevent delamination of stressed strands found in the preparation, formation and use of the foam. Apparatus and method for the production of coalesced strand foam structures are found in U.S. Patent Nos. 3,573, 1 52 and 4,824,720. The foam structures present can also be formed by an accumulation extrusion process as seen in U.S. Patent No. 4,323,528. In this process, low density foam structures having large cross-sectional and lateral areas are prepared by: 1) forming under pressure a gel of the compositions of the present invention and a blowing agent at a temperature at which the viscosity of the gel is sufficient to retain the blowing agent when the gel is allowed to expand; 2) Extrusion of the gel in a holding area maintained at a temperature and pressure that does not allow the gel to be foamed, the fastening area having an outlet nozzle defining a hole that opens towards a lower pressure zone in which the gel forms foam, and a folding gate that closes the orifice of the nozzle; 3) periodic opening of the gate; 4) substantially concurrent application of mechanical pressure by a mobile ram on the gel to expel it from the clamping zone through the orifice of the nozzle towards the lower pressure zone, at a speed greater than that at which the formation of substantial foam in the nozzle orifice and lesser to which substantial irregularities occur in the cross-sectional area or in the form, and 5) allow the ejected gei to expand unconstrained in at least one dimension to produce the foam structure. The foam structures present can also be formed into degraded foam beads suitable for molding into articles, by expanding pre-expanded beads containing a blowing agent. Pearls can be molded at the time of expansion to form articles in various ways. The processes for forming the expanded pearls and molded expanded bead foam articles are described in Plástic Foams, Part II, Frisch and Saunders, p. 544-585, Marcel Dekker, Inc. (1973) and Plástic Materoals, Brydson, 5th, Ed., Pp. 426-429, Butterworths (1989). Expandable and expanded beads can be made by a batch process or by extrusion. The discontinuous process of forming expandable beads is essentially the same as for the manufacture of expandable polystyrene (EPS). The granules of a polymer mixture, formed either by melt mixing or mixing in the reactor, are impregnated with a blowing agent in an aqueous suspension or in an anhydrous state in a pressure vessel and at elevated temperature and pressure. The granules are rapidly discharged in a region of reduced pressure to expand the foam beads or cooled or discharged as non-expanded beads. The unexpanded beads are then heated to expand with appropriate means, for example, with steam or hot air. The extrusion method is essentially the same as for the conventional foam extrusion process as described above for the nozzle orifice. The nozzle has multiple holes. In order to form beads without foam, the foamable strands emerging from the nozzle orifice are immediately cooled in a cold water bath to prevent foaming and then formed into granules. Or, the strands become foam beads cutting into the face of the mouthpiece and then allowed to expand. The foam beads can then be molded by any means known in the art, such as loading the foam beads into the mold, compressing the mold to compress the beads and heating the beads such as with steam to effect coalescence and welding of the beads. pearls to form the article. Optionally, the beads can be impregnated with air or other blowing agent at a high pressure and temperature before being loaded into the mold. In addition, the beads can be heated before being charged. The foam beads can then be molded into blocks or articles configured by a suitable molding method known in the art (some of the methods are taught in U.S. Patent Nos. 3,504,068 and 3,953,558). The excellent teachings of the above processes and molding methods are observed in C. P. Park, supra, p. 1 91, pp. 1 97-1 98 and pp. 227-229. To form the foam beads, mixtures of alkenyl aromatic polymers with one or more substantially random interpolymers are formed into discrete resin particles such as grained resin granules and are suspended in a liquid medium, in which they are substantially insoluble such as Water; they are impregnated with a blowing agent by introducing the blowing agent into the liquid medium at a high pressure and temperature in an autoclave or other pressure vessel; and they are rapidly discharged into the atmosphere or a region of reduced pressure to expand to form the foam beads. This process is taught in the US Patents. Nos. 4,379,859 and 4,464,484. A process for forming expandable thermoplastic beads comprises the proportion of an aromatic alkenyl monomer and optionally at least one additional monomer, which is different, and polymerizable with said aromatic alkenyl monomer; and dissolving in at least one of said monomers of the substantially random interpolymers; polymerization of the first and second monomers to form thermoplastic particles; incorporation of a blowing agent into the thermoplastic particles during or after the polymerization; and cooling the thermoplastic particles to form the expandable beads. The alkenyl aromatic monomer is present in an amount of at least about 50, preferably at least about 70, more preferably at least about 90 percent by weight based on the combined weights of the polymerizable monomers. Another process for the formation of expandable thermoplastic beads comprises: heating the beads of the alkenyl aromatic polymers with one or more substantially random interpolymers to form a molten polymer: incorporating a blowing agent into the molten polymeric material at an elevated temperature. foamable gel; cooling the gel to an optimum temperature which is one at which foaming will not occur, extruding through the nozzle containing one or more orifices to form one or more essentially continuous expandable thermoplastic strands; and forming granules of expandable thermoplastic females to form expandable thermoplastic beads. Alternatively, the expanded thermoplastic foam beads can be made, if before extrusion of the nozzle, the gel is cooled to an optimum temperature in which case it is above the glass transition temperature or melting point of the blends. For the expanded thermoplastic foam beads of the present invention, the optimum foaming temperature is on a sufficient scale to produce an open cell content in the foam of 20 volume percent or less. The foam structures present can also be used to form foamed films for boat and other labels. containers using either a blown film or a molten film extrusion process. The films can also be made by a co-extrusion process to obtain foam in the core with one or two surface layers, which may or may not be comprised of the polymer compositions used in the present invention. Due to the environmental interests present over the use of ozone removal blowing agents, it is desirable to make alkenyl aromatic polymer foams with blowing agents having zero or reduced ozone removal potential. Such blowing agents include suitable inorganic blowing agents include nitrogen, sulfur hexafluoride (SF6) and argon; organic blowing agents such as carbon dioxide and hydrofluorocarbons such as 1,1,1,2-tetrafluoroethane (HFC-134a), difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), 1, 2,2-tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), fluoroethane (HFC-161), and 1,1,1-trifluoroethane (HFC-143a), and hydrocarbons such as methane, ethane, propane, n -butane, isobutane, p-pentane, isopentane, cyclopentane and neopentane; and chemical blowing agents including azodicarbonamide, azodiisobutyro-nitrile, benzenesulfonhydrazide, 4,4-oxybenzene, sulfonyl-semicarbazide, p-toluene-sulphonyl semi-carbazide, barium azodicarboxylate, N, N'-dimethyl-N, N'-dinitroso-terephthalamide, trihydrazine triazine and mixtures of citric acid and sodium bicarbonate such as several products sold under the name Hidrocerol ™ (a product and brand of Boehringer Ingelheim). All of these blowing agents can be used as single components or any combination mixture thereof, or mixed with other co-blowing agents. The blowing agents, when mixed with a co-blowing agent, are present in an amount of 50 molar percent or more, preferably 70 molar percent or more (based on the total g-moles of the blowing agent) and the co-blowing agent). Blowing agents useful with the co-blowing agents used in the present invention include inorganic co-blowing agents, organic co-blowing agents and chemical co-blowing agents. Suitable inorganic co-blowing agents include helium, water and air. Organic co-blowing agents include aliphatic alcohols including methane, ethanol, n-propanol and isopropanol. The full and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons and chlorofluorocarbons. Examples of fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, perfluoroethane, 2, 2, -difluoropropane, 1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane. The partially halogenated chlorocarbons and chlorofluorocarbons for use in this invention include methyl chloride, methylene chloride, ethyl chloride, 1,11-trichloro-ethane, 1,1-dichloro-1-fluoroethane (HCFC-141 b), 1-chloro-1, 1-difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and 1-chloro-1, 2,2 , 2-tetrafluoroethane (HCFC-124). Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-1), dichlorodifluoromethane (CFC-12), trichloro-trifiuoroethane (CFC-13), dichlorotetrafluoroethane (CFC-14), cioroheptafluoropropane and dichlorohexafluoropropane. The total amount of the blowing agents and co-blowing agents is incorporated into the polymer melt material to form a polymeric foaming gel of 0.2 to 5.0 grams-moles per kilogram of polymer, preferably 0.5 to 3.0 grams. -moles per kilogram of polymer and more preferably from 1.0 to 2.5 grams-moles per kilogram of polymer. In addition, a nucleating agent can be added in order to control the size of the foam cells. Preferred nucleating agents include inorganic substances such as calcium carbonate, talc, clay, silica, barium stearate, diatomaceous earth, mixtures of citric acid and sodium bicarbonate. The amount of nucleating agent employed can vary from 0 to 5 parts by weight per hundred parts by weight of a polymeric resin. The preferred scale is from 0 to 3 parts by weight. Various additives may be incorporated into the present foam structure such as inorganic fillers, pigments, antioxidants, acid cleaners, ultraviolet light absorbers, flame retardants, processing aids, extrusion aids, other thermoplastic polymers, antistatic agents and the like. Examples of other thermoplastic polymers include aromatic alkenyl homopolymers or copolymers (having a molecular weight of 2,000 to 50,000) and ethylenic polymers. The foam has a density of from 10 to 95 and more preferably from 10 to 70 kilograms per cubic meter in accordance with ASTM D-1622-88. The foam has an average cell size of 0.05 to 5.0, preferably 0.1 to 1.5 millimeters in accordance with ASTM D3576-77. The foam present has an increase in cell size of 5 percent, preferably 10 percent, more preferably 15 percent or more relative to an analogous foam made without the substantially random interpolymer. The foam present is particularly suitable for forming into a sheet or plank, suitably one having a cross-sectional area of 30 square centimeters (cm) or more and a smaller thickness or dimension in cross section of 0.95 cm or more, preferably 2.5 cm or more. The foam present is closed cell. The closed cell content of the foam present is greater than or equal to 80 percent in accordance with ASTM D2856-94. The foam structures present can be used to isolate a surface by applying an insulating panel coated with the present structure to the surface, as used in for example, external cover wall (local thermal insulation), foundation insulation, and residence basements . Such panels are useful in conventional insulation applications such as roofs, constructions, refrigerators. Other applications include springs and floating rafts (flotation applications) as well as various floral and craft applications. Properties of the Interpolymers and Mixture Compositions Used to Prepare the Foams of the Present Invention The polymeric compositions used to prepare the foams of the present invention comprise from 80 to 99.7, preferably from 80 to 99.5, more preferably from 80 to 99 percent by weight. weight, (based on the combined weights of the substantially random interpolymer and homopolymers or aromatic alkenyl copolymers) of one or more alkenyl aromatic homopolymers or copolymers. The molecular weight distribution (Mw / Mn) of the alkenyl aromatic homopolymers or copolymers used to prepare the foams of the present invention are from 2 to 7. The molecular weight (Mw) of the alkenyl aromatic homopolymers or copolymers used to prepare the foams of the present invention is from 100,000 to 500,000, preferably from 120,000 to 350,000, more preferably from 130,000 to 325,000. The aromatic alkenyl polymeric material used to prepare the foams of the present invention comprises more than 50 and preferably more than 70 weight percent of the alkenyl aromatic monomer units. More preferably, the aromatic alkenyl polymer material is comprised entirely of alkenyl aromatic monomer units. The polymeric compositions used to prepare the foams of the present invention comprise from 0.3 to 20, preferably from 0.5 to 20, more preferably from 1 to 20 weight percent (based on the combined weights of the substantially random interpolymer and the homopolymers and copolymers alkenyl aromatics) of one or more substantially random interpolymers. These substantially random interpolymers used to prepare the foams having elongated cell size of the present invention usually contain from 8 to 65, preferably from 10 to 45, more preferably from 13 to 39 molar percent of at least one vinyl aromatic monomer or vinylidene and / or vinyl or vinylidene monomer, aliphatic or cycloaliphatic and from 35 to 92, preferably from 55 to 90, more preferably from 61 to 87 mole percent of ethylene and / or at least one aliphatic α-olefin having from 3 to 20 carbon atoms. The melt index (12) of the substantially random interpolymer used to prepare the foams of the present invention is 0.1 to 50, preferably 0.3 to 30, more preferably 0.5 to 10 g / 10 min. The molecular weight distribution (Mw / Mn,) of the substantially random interpolymer used to prepare the foams having elongated cell size of the present invention is from 1.5 to 20, preferably from 1.8 to 10, more preferably from 2 to 5. In addition, minor amounts of aromatic alkenyl copolymers or homopolymers or copolymers having a molecular weight of 2,000 to 50,000, preferably 4,000 to 25,000 can be aerated in an amount not exceeding about 2 percent by weight (based on to the combined weights of the substantially random interpolymer and various aromatic homopolymers or alkenyl copolymers). The following examples are illustrative of the invention, but can not be considered as limiting the scope of the same in any way. EXAMPLES Test Methods a) Density and Fusion Flow Measurements The molecular weight of the substantially random interpolymers used in the present invention was conveniently indicated using the melt index measurement according to ASTM D-1238, Condition 1 90 ° C / 2.1 6 kg. (formally known as "Condition (E)" and also known as LI2). The melt index inversely is proportional to the molecular weight of the polymer. Therefore, the higher the lower molecular weight, the lower the melting index, although the relationship is not linear. Also, to indicate the molecular weight of the substantially random interpolymers used in the present invention, the Gottfert melt index (G, cm3 / 10 min) which is obtained in a similar way as the melt index (12) is useful. using the procedure of ASTM D1238 for automatic plastometers, with the melting density equipment at 0.7632, the melt density of the polyethylene at 1 90 ° C. The ratio of the melt density to the styrene content for ethylene-styrene interpolymers was measured, as a function of the total styrene content, at 190 ° C for a scale of 29.8 percent to 81.8 percent by weight of styrene . The levels of atactic polystyrene in these samples were typically typically 10 percent or less. The influence of atactic polystyrene was assumed to be minimal due to low levels. Also, the melting density of the atactic polystyrene and the melting densities of the samples with the total upper styrene are very similar. The method used to determine the melt density employed in a Gottfert melt index machine with a melting density parameter set at 0.7632 and the collection of melting strands as a function of time while the weight of l2 is a force . The weight and time for each normal melt was recorded and normalized to give the mass in grams per 10 minutes. The value of the fusion index l2 of the instrument was also recorded. The equation used to calculate the actual fusion density is d = d0. 632 x l2 / l2 Gottfert where d0.7ß32 = 0.7632 and l2 Gottfert = melting index displayed.

A linear least squares fit of the melt density calculated against the total styrene content leads to an equation with a correlation coefficient of 0.91 for the following equation: d = 0.00299 x S + 0.723 where S = weight percentage of styrene in the polymer. The ratio of the total styrene to the melt density can be used to determine a current melt index value, using these equations if the styrene content is known. In this way for a polymer that is 73 percent of the total styrene content with a measured melt flow (the "Gottfert number"), the calculation can be: d = 0.00299 * 73 + 0.723 = 0.9412 where 0.941 2 /0.7632 = l2 / G # (measured) = 1 .23 b) Styrene Analysis The styrene content of the interpolymer and the concentration of atactic polystyrene were determined using proton nuclear magnetic resonance (1 H NM R). All proton NMR samples were prepared in 1,, 2,2-tetrachloroethane-d2 (TCE-d2). The resulting solutions were 1.6 - 3.2 weight percent of the polymer. The melt index (I2) was used as a guide to determine the sample concentration. Therefore, when the l2 is greater than 2 g / 1 0 min. , 40 mg of the ether polymer is used; when one l2 between 1.5 and 2 g / 10 min. , 30 mg of the interpolymer is used; and when the l2 is less than 1.5 g / 1 0 min. , 20 mg of interpolymer are used. The ether polymers were directly weighed in 5 mm sample tubes. An aliquot of 0.75 mL of TCE-d2 was added by syringe and the tube was covered with a tight-fitting polyethylene layer. The samples were heated in a water bath at 85 ° C to soften the interpolymer. To provide mixing, the stoppered samples were occasionally raised to the reflux temperature using a heat gun. The proton NMR spectrum was accumulated in a Varian VXR 300 apparatus with the sample probe at 80 ° C, and reference was made to the residual protons of TCE-d2 at 5.99 ppm. The delay times varied between 1 second and the data was recovered in triplicate in each sample. The following instrumental conditions were used for the analysis of the Varian VRX-300 interpolymer samples, normal 1H Sweep Width, 5000 Hz Acquisition Time, 3,002 sec, Impulse Width, 8 μsec Frequency, 300 MHz, Delay, 1 sec. , Temporary, 1 6 The total analysis time per sample was approximately 10 minutes. Initially, a 1H NMR spectrum for a polystyrene sample was acquired with a one second display time. The protons were "marked": b, branched; a, alpha; or, ortho; m, goal; p, for, as shown in Figure 1.

Figure 1 Integrals were measured around the protons marked in Figure 1; the "A" is designated aPS. The integral A7? , (aromatic, around 7.1 ppm) is thought to be three ortho / para protons; and the integral A6 ß, (aromatic, around 6.6 ppm) the two meta protons. The two aliphatic protons labeled resonate at 1.5 ppm; and the single labeled proton b is at 1.9 ppm. The aliphatic region was integrated from 0.8 to 2.5 ppm and was referred to as Aa? . The theoretical proportion for A7 1; A6 ß ', Aa 1 is 3: 2: 3, or 1 .5: 1: 1 .5, and they correlated very well with the observed proportions for the polystyrene sample during several lag times of 1 second. The proportion calculations used to verify the integration and verify the peak assignments were carried out by dividing the appropriate integral by the integral A6 ß! Proportion Ar is The region A6 ß was assigned the value of 1. The proportion Al is integral Aa? / A6 ß All the collected spectra have the integration ratio 1 .5: 1: 1 .5 of (o + p): m: (a + b). The ratio of aromatic to aliphatic protons is 5 to 3. An aliphatic ratio of 2 to 1 is predicted based on the protons marked a and b, respectively in Figure 1. This ratio was also observed when the two aliphatic peaks were integrated separately. For the ethylene / styrene interpolymers, the 1 H NMR spectrum using a one second delay time, had the integrals C7 1, C6.6, and Ca? defined, so that the integration of the peak at 7.1 ppm includes all the aromatic protons of the copolymer as well as the protons or amps; p from aPS. Similarly, the integration of the aliphatic region Ca1 into the interpolymer aspect includes aliphatic protons of both aPS and the interpolymer with a transparent baseline that resolves the signal of any polymer. The integral of the peak at 6.6 ppm Cß. β is resolved from the other aromatic signals and is thought to be due to only the aPS homopolymer (probably the target protons). (The peak assigned for atactic polystyrene at 6.6 ppm (integral A6.e) was formed based on the comparison of the real polystyrene sample, which is a reasonable assumption since, at very low levels of atactic polystyrene, it is only observed The phenyl protons of the copolymer do not contribute to this signal, and with this assumption, the integral A6.6 becomes the basis for quantitatively determining the content of aPS The following equations were then used to determine the degree of styrene incorporation in the ethylene / styrene interpolymer samples: (Phenyl C) = C7.? + A7.1 - (1.5 x A6.6) (Aliphatic C) = Ca 1 - (1. 5 x Aß.ß) Sc = (Phenyl C) / 5 ec = (Aliphatic C - (3 x sc)) / 4 E = ec / (ec + sc) Sc = sc / (ec + sc) and the following equations were used to calculate the molar percentage of ethylene and styrene in the interpolymers. by weight E = _ E-28 - (! 00.}. (E'28) + (Sc * 104) weight S .__ Sc "104. (100) (? * 28) + (Sc'104) wherein: sc and ec are proton fractions of ethylene and styrene in the interpolymer, respectively, Sc and E are molar fractions of the styrene monomer and ethylene monomer in the interpolymer respectively. The weight percentage of aPS in the interpolymers was then determined by the following equation: The total styrene content was also determined by quantitative Fourier Transform Infrared Spectroscopy (FTIR). Preparation of Ethylene / Styrene Interpolymers ("ESL's") Used in Examples and Comparative Experiments of the Present Invention 1) Preparation of ESI # 's 1-2 ESI #' s 1-2 are substantially ethylene / styrene ether polymers random samples prepared using the following catalysts and polymerization procedures. Preparation of Catalyst A (dimethylfN-d. 1 -dimethylethyl) -1, 1 -dimethyl-1 -f (1 .2.3.4.5-n) -1 .5,6,7-tetrahydro-3-phenyl-s-indacen -1-Insilanamate (2 -) - Nl-titanium) 1) Preparation of 3,5,6,7-Tetrahydro-s-Hindrinacen-1 (2H) -one Indane (94.00 9, 0.7954 mole) and sodium chloride were stirred. 3-Chloropropionyl (100.99 g, 0.7954 moles) in CH2Cl2 (300 mL) at 0 ° C as AICI3 (130.00 g, 0.9750 moles) was slowly added under a nitrogen flow. The mixture was then allowed to stir at room temperature for 2 hours. The volatiles were then removed. The mixture was then cooled to 0 ° C and concentrated H2SO4 (500 mL) was slowly added. The solid in formation had to be broken frequently with a sharp spatula as agitation was lost at the beginning of 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 the spatula was periodically used to stir the mixture. After the reaction period, the crushed ice was placed in the mixture and stirred. 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 H 2 O (2 x 200 mL J. The organic layer was then separated and the volatiles were removed.The desired product was then isolated via recrystallization of hexane at 0 ° C as pale yellow crystals (22.36 g, 16.3 percent). of performance). 1 H NMR (CDCl 3): d2.04-2.19 (m, 2H), 2.64 (t, 3 JHH = 5.7 Hz, 2H), 2.84-3.0 (m, 2H), 3.03 (t, 3JHH = 5.5 Hz, 2H) , 7.26 (s, 1 H), 7.53 (s, 1 H). 13C NMR (CDCI3): d2.71, 26.02, 32.19, 33.24, 36.93, 1 18.90, 122.16, 135.88, 144.06, 152.89, 154.36, 306.50. GC-MS: calculated for C12H12O 172.09, Found 172.05. 2) Preparation of 1, 2,3,5-Tetrahydro-7-phenyl-s-indacen 3,5,6,7-Tetrahydro-s-Hindracen-1 (2H) -one (12.00 g, 0.6967 moles) was stirred in diethyl ether (200 mL) at 0 ° C as PhMgBr (0.105 moles, 35.00 mL of 3.0 M solution in diethyl ether) was slowly added. This mixture was then allowed to stir overnight at room temperature. After the reaction period the mixture was cooled by pouring 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 1000 mL) and then dried over MgSO4. The filtration followed by the removal of the volatiles resulting in the desired product isolation as a dark oil (14.8 g, 90.3 percent 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 C18H16O 232.13. Found 232.05. 3) Preparation of dilithium salt of 1, 2, 3,5-Tetrahydro-7-phenyl-s-indacene. 1, 2,3,5-Tetrahydro-7-phenyl-s-indacene (14.68 g, 0.06291 mol) was stirred in hexane (1 50 mL) as nBuLi (0.080 mol, 40.00 mL of 2.0 M solution in cyclohexane) It was added slowly. This mixture was then allowed to stir overnight. After the reaction period the solid was recovered 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 percent yield). 4) Preparation of Ciorodimethyl (1, 5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silane. 1,2,3,5-Tetrahydro-7-phenyl-s-indacene, dilithium salt (12.2075 g, 0.05102 mol) in THF (50 mL) was added dropwise to a solution of Me2SiCI2 (19.5010 g, 0.1511 mol ) in THF (100 mL) at 0 ° C. This mixture was 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 hexane resulted in the isolation of the desired product as a yellow oil (15.1492 g, 91.1 percent 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, 2 H), 2.9-3.1 (m, 4 H), 3.84 (s, 1 H) , 6.69 (d, 3JHH = 2.8 Hz, IH), 7.3-7.6 (m, 7H), 7.68 (d, 3JHH = 7.4 Hz, 2H). 13 C NMR (CDCl 3): 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. GM-MS: Calculated for C30H21CISi 324.11, found 324.05.

) Preparation of N- (1,1-Dimethylethyl) -1,1-dimethyl-1- (1, 5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silanamine. Chlorodimethyl (1, 5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silane (10.8277 g, 0.03322 mol) was stirred in hexane (150 mL) as Net3 (3.5123 g, 0.03471 mol) and α-butylamine (2.6074 g, 0.0365 mole) was added. This mixture was allowed to stir for 24 hours. After reaction period the mixture was filtered and the volatiles were removed resulting in the solution of the desired product as a thick red-yellow oil (10.6551 g, 88.7 percent yield). H 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, 1 H), 6.69 (s, 1 H), 7.3-7.5 (m, 4H), 7.63 (d, 3JHH = 7.4 Hz, 2H). 3C NMR (CDCI3): d-0.32, -0.09, 26.28, 33.39, 34.1 1, 46.46, 47.54, 49.81, 1 15.80, 1 19.30, 126.92, 127.89, 128.46, 1 32.99, 1 37.30, 140.20, 140.81, 141. 64, 142.08, 144.83. 6) Preparation of N- (1,1-dimethylethyl) -1,1 -dimethyl-1- (1, 5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl) silanamide, dilithium salt . N- (1, 1, -Dimethylethi) -1, 1 -dimethyl-1 - (1, 5, 6, 7-tetrahydro-3-phenylis-s-indacen-1-yl) silanamide (10.6551 g, 0.02947 moles) was stirred in hexane (100 mL) as nBuLi (0.070 mol, 35.00 mL 2.0 M solution in cyclohexane) was added slowly. The mixture was then allowed to stir overnight, during which time the salts were not crushed out of the dark red solution. After the reaction period the volatiles were removed and the residue washed rapidly with hexane (2 x 50 mL). The dark red residue was then dried by pumping without purification or further analysis (9.6517 g, 87.7 percent yield). 7) 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-) N] titanium N- (1,1-Dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-) were added dropwise tetrahydro-3-phenyl-s-indacen-1-yl) silanamide, dilithium salt (4.5355 g, 0.01214 mol) in THF (50 mL) to a paste of TiCl3 (THF) 3 (4.5005 g, 0.01214 mol) in THF (100 mL). This mixture was allowed to stir for 2 hours. Then PbCl2 (1.7136 g, 0.006162 mol) was added and the mixture was allowed to stir for an additional 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 mixed in hexane and cooled to 0 ° C. The desired product was then isolated via filtration as a red-brown crystalline solid (2.5280 g, 43.5 percent yield). 1 H NMR (CDCl 3): d? .71 8 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), 7.35-7.42 (m, 1H), 7.50 (t, 3JHH = 7.8 Hz, 2H), 7.57 (s, 1H), 7.70 (d, 3JHH = 7.1 Hz, 2H), 7.78 (s, 1 H) ). 1H NMR (C6D6): d? .44 (s, 3H), 0.68 (s, 3H9, 1.35 (s, 9H), 1.6-1.9 (m, 2H), 2.5-3.9 (m, 4H), 6.65 (s) , 1H), 7.1-7.2 (m, 1H), 7.24 (t, 3JHH = 7.1 Hz, 2H), 7.61 (s, 1H), 7.69 (s, 1H), 7.77-7.8 (m, 2H) .13C 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, 128.55, 128.79, 129.01, 134.11, 134.53, 136.04, 146.1 5, 148.93, 3C 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, 136.51, 147.24, 148.96. 8) Preparation of dimethyl [N- (1,1-dimethylethyl) -1,1 -dimethyl-1 - [(1, 2,3,4, 5 -?) - 1,5,6,7-tetrahido-3 phenyl-s-indacen-1-yl] silanaminate (2 -) - N] titanium Dichloro- [N- (1,1-dimethylethyl) -1 -1-dimethyl-1 - [(1, 2,3) was stirred , 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 moles, 0.70 mL of 3.0 M solution in diethyl ether) was added slowly. The mixture was then stirred for 1 hour. After the reaction period the volatiles were removed and the residue was extracted and filtered using hexane. Removal of hexane resulted in the isolation of the desired product as a golden yellow solid (0.4546 g, 66.7 percent yield). 1H NMR (C6D6): d0.071 (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 (3JHH = 7.4 Hz, 2H), 7.92 (s) , 1 HOUR). 13C NMR (C6D6): d2.19, 4.51, 27.12, 32.86, 33.00, 34.73, 58.68, 58.82, 118.62, 121.98, 124.26, 127.32, 128.63, 129.98, 131.23, 134.39, 136.38, 143.19, 144.85.

Polymerization for ESI # 1-2 The ESL's 1-2 were prepared in a continuously stirred tank reactor (CSTR) in an autoclave, covered with 22.7 liter oil. A stirrer magnetically coupled with Lightning A-320 propellers provided mixing. The reactor flowed completely 3.275 kPa. The flow of the process was inside the lower part and outside the upper part. A heat transfer oil circulated through the reactor cover to remove some of the heat from the reaction. At the outlet of the reactor, a micromotion flow meter was found that measured the flow and solution density. All the lines at the reactor outlet were drawn with a current of 344.7 kPa and were isolated. The toluene solvent was supplied to the reactor 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. At the discharge of the solvent pump, a side stream was absorbed to give flowing flows for the catalyst injection line (0.45 kg / hr) and the reactor stirrer (0.34 kg / hr). These flows were measured by the differential pressure flow meters and were placed by the manual adjustment of the micro-flow nozzle valves. The uninhibited styrene monomer was measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controls the feeding speed. The styrene stream was mixed with the remaining solvent stream. Ethylene was supplied to the reactor at 4.1 37 kPa. The ethylene stream was measured by a Micro-Motion mass flow meter just before the Valve Control Flow Investigation. A Brooks flow meter / controller was used to supply hydrogen in 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, decreased approximately ~ 5 ° C by an exchanger with -5 ° C of glycol on the cover. This current entered the bottom of the reactor. The three-component catalyst system and its solvent flow also entered the reactor in the bottom but through a different port of the monomer stream. The preparation of the catalyst components took place in a glovebox with an inert atmosphere. The diluted components were placed in cylinders with nitrogen pad and charged to the tanks to run the catalyst in the process area. From these running tanks, the catalyst was pressurized with piston pumps and the flow was measured with Micro-Motion mass flow meters. These currents combine with each other and the catalyst rinses the solvent just before entering through a single injection line in the reactor. Polymerization was stopped with the addition of the destroyed catalyst (water mixture with solvent) in the reactor product line after the flow meter measured the solution density. Other polymer additives can be added with the catalyst scavenger. An in-line static mixer provided the dispersion of the destroyed catalyst and additives in the reactor effluent stream. This current then enters the reaction heaters that provide additional energy for the solvent removal pulse. This impulse was presented as the effluent that left the heater after the reactor and the pressure decreased from 3,275 kPa to less than approximately -250 mm absolute pressure in the reactor pressure control valve. This driven polymer entered a devolatilizer covered with hot oil. Approximately 85 percent 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 the exchanger covered with glycol and introduced the suction of a vacuum pump and discharged to a glycol shell solvent and the styrene / ethylene separation vessel. 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 analyzed for its composition. The ventilated ethylene measurement plus a calculation of the gases dissolved in the solvent / styrene stream was used to calculate the ethylene conversion. The polymer separated in the devolatilizer was pumped out with a gear pump to a devolatilization vacuum extruder ZSK-30. The dried polymer leaves the extruder as a single strand. This strand cooled as it passed through a water bath. The excess water was blown from the strand with air and the strand was cut into granules with a strand cutter.

Polymerization for ESI # 3 ESI 3 is a substantially alloy ethylene / styrene interpolymer prepared using the following catalyst and polymerization procedures.

Preparation of Catalyst B: (1 H-cyclopenta [1-l-phenanthrene-2-yl) dimethyl (t-butylamido) -silanetitanium 1,4-diphenylbutadiene) 1) Preparation of 1 H-cyclopentaf-nfenanthrene-2-yl lithium To a flask 250 ml round bottom containing 1 .42 g (0.00657 moles) of 1 H-cyclopenta [1] phenanthrene and 120 ml of benzene were added dropwise, 4.2 ml of a 1.60 M solution of n-BuLi in hexanes mixed. The solution was allowed to stir overnight. The lithium salt was isolated by filtration, washed twice with 25 ml of benzene and dried under vacuum. The isolated yield was 1.426 g (97.7 percent). The 1 H NMR analysis indicated that the predominant isomer was substituted at position 2. 2. Preparation of (1 H-cyclopenta [1] phenanthrene-2-yl) dimethylchlorosilane To a 500 ml round bottom flask containing 4.16 g (0.0322 mole) of dimethyldichlorosilane (Me2SiCl2) and 250 ml of tetrahydrofuran (THF) was added drop dropwise a solution of 1.45 g (0.0064 mol) 1 H-cyclopenta [1] phenanthrene-2-yl of lithium in THF. The solution was stirred for approximately 16 hours, after which the solvent was removed under reduced pressure, giving an oily solid which was extracted with toluene, filtered through the diatomaceous earth filter medium (Celite ™), washed twice. with toluene and dried under reduced pressure. The isolated yield was 1.98 g (99.5 percent). 3. Preparation of (1 H-cyclopenta [1] phenanthrene-2-yl) dimethyl (t-butylamido) silane To a 500 ml round bottom flask containing 1.98 (0.0064 mole) of (1 H-cyclopenta [ 1] phenanthrene-2-yl) dimethylchlorosilane and 250 ml of hexane were added 2.00 ml (0.01 60 moles) of t-butylamine. The reaction mixture was allowed to stir for several days, then filtered using the diatomaceous earth filter medium (Celite ™), washed twice with hexane. The product was isolated by removing the residual solvent under reduced pressure. The isolated yield was 1.98 g (88.9 percent). 4. Preparation of dilitium (1 H-cyclopenta [1] phenanthrene-2-yl) dimethyl (t-butylamido) silane To a 250 ml round bottom flask containing 1.03 g (0.0030 mole) of (1 H-cyclopenta [1] phenanthrene-2-yl) dimethyl (t-butylamido) silane) and 120 ml of benzene was added dropwise 3.90 ml of a solution of 1.6 M n-BuLi in mixed hexanes. The reaction mixture was stirred for about 16 hours. The product was isolated by filtration, washed twice with benzene and dried under reduced pressure. The isolated yield was 1.08 g (100 percent). 5. Preparation of (1 H-cyclopenta [1] phenanthrene-2-yl) dimethyl (t-butylamido) silanetitanium dichloride To a 250 ml round bottom flask containing 1.17 g (0.0030 moles) of TiCl3 «3THF and about 120 ml of THF were added at a rapid drop rate of 50 ml of a THF solution of 1.08 g of (1 H-cyclopenta [1] phenanthrene-2-yl) dimethyl (t-butylamido) silane of dilithium. The mixture was stirred at about 20 ° C for 1.5 hours at which time 0.55 mg (0.002 mole) of solid PbCI2 was added. After stirring for an additional 1.5 hours the THF was removed under vacuum and the residue was extracted with toluene, filtered and dried under reduced pressure to give an orange solid. The yield was 1.3 g (93.5 percent). 6. Preparation of 1,4-diphenylbutadiene from (1 H-cyclopenta [1] phenanthrene-2-yl) dimethyl (t-butylamido) silanetitanium To a dichloride paste of (1 H-cyclopenta [1] phenanthrene-2-y!) dimethyl (t-butylamido) siianoititanium (3.48 g, 0.0075 mol) 1,551 mg (0.0075 mol) of 1,4-diphenylbutadiene in about 80 ml of toluene at 70 ° C was added 9.9 ml of a 1.6 M solution of n-BuLi (0.01 50 moles). The solution darkened immediately. The temperature was increased to bring the mixture to reflux and the mixture was kept at the temperature for 2 hours. The mixture was cooled to about -20 ° C and the volatiles were removed under reduced pressure. The residue was mixed in 60 ml of mixed hexanes at about 20 ° C for about 16 hours. The mixture was cooled to about -25 ° C for about 1 hour. The solids were recovered in a glass fiber by vacuum filtration and dried under reduced pressure. The dried solid was placed in a glass fiber nozzle and the solid was continuously extracted with hexanes using a Soxhiet extractor. After 6 hours a crystalline solid was observed in the boiling vessel. The mixture was cooled to approximately -20 ° C, it was isolated by filtration of the cold mixture and dried under reduced pressure to give 1.662 g of a dark crystalline solid. The filtrate was discharged. The solids in the extractor were stirred and the extraction was continued with an additional amount of mixed hexanes to give an additional 0.46 mg of the desired product as a dark crystalline solid.

Polymerization for ESI # 3 ESI 3 was prepared in a continuous operation cycle reactor (139 L). An Ingersoli-Dreser double screw pump provided mixing. The reactor ran the complete liquid at 3,275 kPa with a residence time of approximately 25 minutes. The raw materials and the catalyst / cocatalyst streams were fed into the suction of the twin screw pump through the Kenics static mixers and injectors. The twin screw pump was discharged into a 5.08 cm diameter line that supplied two BEM Type 10-68 multi-tube heat exchangers from Chemineer-Kenics in series. The tubes of these exchangers contained twisted ribbons to increase heat transfer. Upon exiting the last exchanger, the cycle flow back through the injectors and the static mixers to the suction of the pump. The heat transfer oil was calculated through the jacket of the exchangers to control the temperature probe of the cycle located just before the first exchanger. The output current of the cycle reactor came out between the two exchangers. The flow and solution density of the output stream was measured by a MicroMotion. The solvent fed to the reactor was supplied by two different sources. A fresh toluene stream from a 8480-S-E Pulsafeeder diaphragm pump with speeds measured by a MicroMotion flow meter was used to provide rinsing flow to the reactor seals (9.1 kg / hr). The recycled solvent was mixed with unenhanced styrene monomer on the suction side of five diaphragm pumps 8480-5-E Pulsafeeder in parallel. These five Pulsafeeder pumps supplied solvent and styrene to the reactor at 4,583 kPa. The fresh styrene flow was measured by a MicroMotion flow meter and the total recycled solvent / styrene flow was measured by a separate MicroMotion flow meter. Ethylene was supplied to the reactor at 4,838 kPa. The ethylene stream was measured by a Micro-Motion mass flow meter. A Brooks fiow / controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve. The ethylene / hydrogen mixture was combined with the solvent / styrene stream at room temperature. The temperature of the complete inlet feed stream as it enters the reactor cycle was decreased to 2 ° C by an exchange with -1 0 ° C of glycol on the cover. The preparation of these three catalyst components took place in three separate tanks: the fresh solvent and the concentrated catalyst / cocatalyst pre-mix was added and mixed in their respective operation tanks and fed into the reactor via the diaphragm pumps of Pulsofeeder 680-S-AEN7 variable speed. As previously explained, the three components of the catalyst systems enter the reactor cycle through an injector and the static mixer on the suction side of the twin screw pump. The feed stream from the raw material was also fed into the reactor cycle through the injector and the static mixer downstream of the catalyst injection point but upstream of the twin screw pump suction. The polymerization was stopped with the addition of the destroyed catalyst (water mixture with solvent) in the product line after the Micro-Motion flow meter measured the density of the solution. A static mixer in the line provided the dispersion of the destroyed catalyst and the additives in the stream leaving the reactor. This current then enters the post-reactor heaters which provided additional energy for the solvent removal pulse. This impulse occurred as the effluent leaves the heater after the reactor and the pressure decreased from 3,275 kPa to less than 60 kPa absolute pressure in the reactor pressure control valve. This driven polymer first entered the two devolatilizers covered with hot oil. Volatiles driven from the first devolatilizer were condensed with a glycol shell exchanger, passed through the suction of a vacuum pump and discharged into the styrene / ethylene and solvent separation vessel. The solvent and styrene were removed from the bottom of this container as the recycled solvent while the ethylene was expelled from the top. The ethylene stream was measured with a MicroMotion mass flow meter. The measurement of ventilated ethylene plus a calculation of dissolved gases in the solvent / styrene stream were used to calculate the ethylene conversion. The remaining polymer and solvent separated in the devolatilizer were pumped with a gear pump to a second devolatilizer. The pressure in the second devolatilizer was operated at 5 mm Hg (0.7 kPa) of absolute pressure to drive the remaining solvent. This solvent was condensed in a glycol heat exchanger, pumped through another vacuum pump and exported to a waste tank for disposal. The dry polymer was pumped (<1000 ppm of total volatiles) with a gear pump to a granule former under water with a 6-hole nozzle, formed into granules, dried by rotation and recovered in 450 kg boxes. The different catalysts, co-catalysts and process conditions used to prepare the individual ethylene-styrene interpolymers (ESI # / s 1 -3) are summarized in Table 1 and their properties are summarized in Table 2.

Table I Preparation Conditions for ESi # 's 1 -3 "N / D = Not available a.Catalyst A is (dimethyl [N- (1, 1 -dimethylethi) -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) b Catalyst B is (1 H-cyclopenta [1] phenanthrene-2-yl) dimethyl (t-butylamido) - silanetitanium 1,4-diphenylbutadiene) c Cocatalyst C is tris (pentafluorophenyl) borane, (CAS # 001 109-15.5). d a methyl methylaluminoxane commercially available from Akzo Nobel as MMAO-3A (CAS # 146905) -79-5) Table 2. Properties of ESI # 's 1 -3 Polystyrene Mixture Components PS 1 is a granular polystyrene having a weight average molecular weight, Mw of 192,000 and a polydispersity of Mw / Mn of about 2. PS 2 is a granular polystyrene having a weight average molecular weight, Mw. of 145,000 and a polydispersity of Mw / Mn of about 6. PS 3 is a granular polystyrene having a weight average molecular weight, Mw of 1 32,000 and a polydispersity of Mw / Mn of about 2.

Examples 1 and 2: Elongated Cell Sizes with PSI / ESI Mixtures Using Isobutane as the Blowing Agent A foaming process comprising a single screw extruder, mixer, coolers and nozzle was used to foam. Isobutane was used as the blowing agent in a load of 7.5 parts percent resin (phr) to foam the polystyrene (PS) and PS / ESI blends. TABLE 3 Elongated Cell Sizes with PS / ESI Mixtures, Using Isobutane as Blowing Agent Example 3: Elongated Cell Sizes with PS / ESI Mixtures, Using CO2 as Blowing Agent A foaming process comprising a single screw extruder, mixer, coolers and nozzle was used to form foam boards. The carbon dioxide (CO2) was used as the blowing agent at a level of 4.7 phr, to foam the polystyrene and a polystyrene mixture with ESI. The other additives were: hexabromocyclododecane = 2.5 phr; barium stearate = 0.2 phr; blue dye = 0.1 5 phr; tetrasodiumpyrophosphate = 0.2 phr; Linear low density polyethylene = 0.4 phr. TABLE 4 Elongated Cell Sizes with PS / ESI Mixtures, Using CO? as Blowing Agent The examples and comparative examples of Tables 3 and 4 demonstrate that foams made of polystyrene blends with substantially random ethylene / styrene interpolymers (using non-ozone depleting blowing agents) have elongated cell size and closed cell structure (more than or equal 80 percent in closed cell volume). In addition, Table 4 shows that the presence of substantially random ethylene / styrene interpolymers in the foams does not have a damaging effect on slip under load at 80 ° C (WD - DIN 1 8164), while the use of the size extender cellular, glycerol monostearate (GMS), had an adverse effect on WD.

Claims (23)

CLAIMS 1. A process for the formation of a closed cell alkenyl aromatic polymer foam having elongated cell size, said process comprising; (I) forming a polymeric melting material comprising; (A) from 80 to 99.7 weight percent (based on the combined weight of Components A and B) of one or more alkenyl aromatic polymers and wherein at least one of said alkenyl aromatic polymers has a molecular weight ( Mw) from 100,000 to 500,000; and (B) from 0.3 to 20 weight percent (based on the combined weight of Components A and B) of one or more substantially random interpolymers having a l2 of 0.01 to 1000 g / 1 0 min, one Mw / Mn , from 1.5 to 20; who understands; (1) from 8 to 65 mole percent of the polymer units derived from: (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one aliphatic or cycloaliphatic vinylidene or hidden cycloaliphatic monomer, or (c) a combination of at least one aromatic vinyl or vinylidene monomer and at least one aliphatic or cycloaliphatic vinylidene monomer or hidden cycloaliphatic, and (2) 35 to 92 mole percent polymer units derived from at least one one of ethylene and / or α-olefin of C3-20; and (3) from 0 to 20 mole percent of polymer units derived from one or more polymerizable ethylenically unsaturated monomers other than those derived from (1) and (2); and (C) optionally, one or more nucleating agents; and (D) optionally, one more different additives; and (II) incorporating into said melt polymeric material at an elevated pressure to form a foamable gel (E) one or more blowing agents present in a total amount of 0.2 to 5.0 grams-moles per kilogram (based on the combined weight of Components A and B); (I I I) cooling said foamable gel to an optimum temperature; Y (IV) Extrude the Stage I gel through a nozzle to a lower pressure region to form a foam, wherein as a result of said process, the cellular size of said foam is increased 5 percent or more relative to a corresponding foam without the substantially random interpolymer. The process according to claim 1, characterized in that said foam has a thickness of 0.95 cm or more and wherein (A) in the Component (A), said at least alkenyl aromatic polymer is more than 50 weight percent of alkenyl aromatic monomer units and has a molecular weight (Mw) of from 120,000 to 350,000 and is present in an amount of from 80 to 99.5 weight percent (based on the combined weight of Components A and B); (B) said substantially random interpolymer, Component (B), has an l2 of 0.3 to 30 g / 10 min. , and an Mw / Mn, from 1 .8 to 10; it is present in an amount of from 0.5 to 20 weight percent (based on the combined weight of components A and B); and comprises (1) from 1 to 45 mole percent of polymer units derived from; (a) said vinylidene or vinyl aromatic monomer represented by the following formula: A) I-C = CH, wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing three carbons or less, and Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substitutes selected from the group consisting of halo, alkyl of C1-4, and haloalkyl of C? .4; or (b) said aliphatic vinylidene or aesthetically hidden cycloaliphatic monomer, is represented by the following formula 10 general: TO' wherein A1 is a sterically bulky aliphatic or cycloaliphatic substitute of 15 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 and methyl, each R2 20 independently is 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 25 together form a ring system; or (c) a combination of a and b; and (2) from 55 to 90 mole percent of polymer units derived from ethylene and / or said olefinine comprising at least one of propylene, 4-methyl-1-pentene, butene-1, hexane-1 or octene- 1; and (3) said polymerizable ethylenically unsaturated monomers other than those derived from (1) and (2) comprise norbornene or a norbornene substituted with C6-? o aryl or a C1-10 alkyl; and (C) said nucleating agent, if present, Component (C), comprises one or more of calcium carbonate, talc, clay, silica, barium stearate, diatomaceous earth, mixtures of citric acid and sodium bicarbonate; Y (D) said additive, if present, Component (D), comprises one or more of the inorganic fillers, pigments, antioxidants, acid cleaners, ultraviolet light absorbers, flame retardants, processing aids, other thermoplastic polymers, agents antistatic and extrusion auxiliaries. (E) said blowing agent, Component (E), is present, in a total amount of from 0.5 to 3.0 g-moles / kg (based on the combined weight of Components A and B), and comprises 50 percent or more than one or more inorganic spraying agents, carbon dioxide, hydrofluorocarbons, hydrocarbons, or chemical blowing agents, wherein the cell size of said foam is stretched 10 percent or more relative to a corresponding foam without the substantially random interpolymer. 3. The process according to claim 1, characterized in that said foam has a thickness of 2.5 cm or more and wherein; (A) in Component (A), said at least alkenyl aromatic polymer has more than 70 weight percent aromatic alkenyl monomer units, has a molecular weight (Mw) of from 30,000 to 325,000, a molecular weight, (Mw / Mn) from 2 to 7, and is present in an amount of from 80 to 99 weight percent (based on the combined weight of components A and B); (B) said substantially random interpolymer, Component (B), has a l2 of 0.5 to 10 g / 10 min. and an Mw / Mn of 2 to 5; it is present in an amount of from 1 to 20 weight percent (based on the combined weight of components A and B); and comprises (1) from 13 to 39 mole percent of polymer units derived from; (a) said vinyl aromatic monomer comprising styrene, α-methyl styrene, ortho-, meta- and para-methylstyrene, and halogenated styrene rings, or (b) said vinyl or vinylidene, aliphatic or cycloaliphatic monomers comprising -ethylidene-2-norbornene or 1-vinylcyclohexene, 3-vinylcyclohexene and 4-vinylcyclohexene; or (c) a combination of a and b; and (2) from 61 to 87 mole percent of polymer units derived from ethylene and / or said α-olefin comprising ethylene, or ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1 , hexane-1 or octene-1; and (3) said polymerizable ethylenically unsaturated monomers other than those derived from (1) and (2) are norbornene; and (C). said nucleating agent, if present, Component (C), comprises one or more of talc and mixtures of citric acid and sodium bicarbonate; (D) said additive, if present, Component (D), comprises one or more of natural gas carbon black, titanium dioxide, graphite, flame retardants and other thermoplastic polymers; and (E) said blowing agent, Component (E), is present in a total amount of from 1.0 to 2.5 g moles per kg (based on the combined weight of Components A and B), and comprises 70 percent or more than one of, nitrogen, sulfur hexafluoride (SF6), argon, carbon dioxide, 1,1,1-tetrafluoroethane (HFC-1 34a), difluoromethane (HFC-32), 1,1-difluoroethane ( HFC-152a), 1,1, 2,2-tetrafluoroethane (HFC-134), 1,1,3,3-pentafluoropropane, pentafluoroethane (HFC-125), fluoroethane (HFC-161), and 1, 1 , 1-trifluoroethane (HFC-143a), methane, ethane, propane, n-butane, isobutane, p-pentane, isopentane, cyclopentane and neopentane, azodicarbonamide, azodiisobutyronitrile, benzenesulfonhydrazide, 4,4-oxybenzene, sulfonyl-semicarbazide, p-toluene-sulfonyl semi-carbazide, barium azodicarboxylate, N, N'-dimethyl-N, N'-dinitroso-terephthalamide, trihydrazine triazine and mixtures of citric acid and sodium bicarbonate; and wherein the cellular size of said foam is extended 15 percent or more relative to a corresponding foam without the substantially random interpolymer. The process according to claim 3, characterized in that said alkenyl aromatic polymer, component (A), is polystyrene, Component B is an ethylene / styrene copolymer and the blowing agent, Component (E), is one or more propane, n-pentane, isobutane, carbon dioxide, 1,1,1,2-tetrafluoroethane (HFC-1 34a) or 1,1,1,2-tetrafluoroethane (HFC-1 34). The process according to claim 3, characterized in that said aromatic alkenyl polymer, Component (A), is polystyrene, in said substantially random interpolymer, Component B1 (a) is styrene; and Component B2 is ethylene and at least one propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1, and the blowing agent, Component (E) is one or more propane , n-pentane, isobutane, carbon dioxide, 1, 1, 1, 2-tetrafluoroethane (HFC-134a) or 1,1, 2,2-tetrafluoroethane (HFC-134). 6. The process according to claim 1, characterized in that the foam has a density of from 1.0 to 50 kilograms per cubic meter (kg / m3) and a cell size of 0.05 to 5.0 millimeters. The process according to claim 1, characterized in that the foam has a density of from 10 to 70 kg / m3 and a cell size of 0.1 to 1.5 millimeters. The process according to claim 1, characterized in that Component A comprises more than 70 weight percent aromatic alkenyl monomer units, said substantially random interopolymer is incorporated to increase cell size 15 percent or more relative to a corresponding foam without the substantially random interpolymer, and the foam has a density of 10 to 150 kg / cm 3 and a cell size of 0.05 to 5.0 millimeters. The process according to claim 1, characterized in that Component A comprises more than 70 weight percent aromatic alkenyl monomer units, said substantially random interopolymer is incorporated to increase cell size 15 percent or more relative to a corresponding foam without the substantially random interpolymer, and the foam has a density of 10 to 70 kg / cm3 and a cell size of 0.1 to 1.5 millimeters. The process according to claim 1, characterized in that in step (IV) said foamable gel is extruded through a multi-orifice nozzle to a lower pressure region so that the contact between the adjacent streams of the molten extrudate occurs during the foaming process and the contact surfaces adhere to each other with sufficient adhesion to result in a unitary foam structure to form a coalesced strand foam. eleven . The process according to claim 1, characterized in that in step (IV) the foamable gel is: (1) extruded in a holding area maintained at a temperature and pressure that does not allow the gel to be foamed, the holding area having an outlet nozzle and an open orifice in a zone of lower pressure at which the gel is foamed and a folding gate that closes the orifice of the nozzle; (2) periodically opens the gate; (3) applies mechanical pressure substantially concurrently by a moving ram on the shaft to expel it from the clamping area through the nozzle orifice in the lower pressure zone, at a speed greater than that at which the forming process of substantial foam in the nozzle orifice occurs and less than that in which the irregularities in cross-sectional shape or area occur; and (4) allows the expelled gel to expand without restriction in at least one dimension to produce the foam structure. The process according to claim 1, characterized in that the foamable gel of step (II) is cooled to an optimum temperature at which no foaming occurs and then extruded through a nozzle to form an expandable thermoplastic strand. It continues to form into granules to form expandable thermoplastic beads. 13. The process according to claim 1, characterized in that in step (IV) said foamable gel is extruded through a nozzle to form essentially continuous expanded thermoplastic strands which are converted into foam beads by cutting on the face of the nozzle and then allowing expansion. 14. A process for making a closed cell alkenyl aromatic foam in the form of thermoplastic foam beads having an elongated cell size, such process comprising: (I) forming a polymeric melting material comprising; (A) from 80 to 99.7 weight percent (based on the combined weight of Components A and B) of one or more alkenium aromatic polymers and wherein at least one of said alkenyl aromatic polymers has a molecular weight ( Mw) from 1,000,000 to 500,000; and (B) from 0.3 to 20 weight percent (based on the combined weight of Components A and B) of one or more substantially random interpolymers having a l2 of 0.01 to 1000 g / 10 min, one Mw / Mn, from 1.5 to 20; who understands; (1) from 8 to 65 molar percent of the 10 polymeric units derived from: (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one aliphatic vinyl or vinylidene monomer or 15 hidden cycloaliphatic, or (c) a combination of at least one vinyl or vinylidene aromatic monomer and at least one vinyl or vinylidene monomer 20 aliphatic or hidden cycloaliphatic, and (2) from 35 to 92 mole percent of polymer units derived from at least one of ethylene and / or C3-20 α-olefin; and 25 (3) from 0 to 20 mole percent of polymer units derived from one or more polymerizable ethylenically unsaturated monomers other than those derived from (1) and (2); and (C) optionally, one or more nucleating agents; and (D) optionally, one more different additives; and (II) cooling and granulating the product of step I to form discrete resin particles; and (III) suspending said resin particles in a liquid medium in which they are substantially insoluble; (IV) incorporating in the suspension formed in Step III at an elevated temperature and pressure in an autoclave or other pressure vessel; (E) one or more blowing agents having zero ozone elimination potential and optionally one or more co-blowing agents, and present in a total amount of from 0.2 to 5.0 g moles per kg (based on the combined weight of Components A and B); (V) rapidly discharging the product formed in Step IV into the atmosphere, or a region of reduced pressure, to form foam beads; wherein the cellular size of said foam is extended 5 percent or more relative to a corresponding foam without the substantially random interpolymer. 15. A polymer foam having an elongated cell size, comprising: (A) from 80 to 99.7 weight percent (based on the combined weight of Components A and B) of one or more alkenyl aromatic polymers and in wherein at least one of said alkenyl aromatic polymers has a molecular weight (Mw) of from 1,000,000 to 500,000; and (B) from 0.3 to 20 weight percent (based on the combined weight of Components A and B) of one or more substantially random interpolymers having an I2 of 0.01 to 1000 g / 10 min, one Mw / Mn , from 1.5 to 20; who understands; (1) from 8 to 65 mole percent of the polymer units derived from: (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one aliphatic or cycloaliphatic vinylidene or hidden cycloaliphatic monomer, or (c) a combination of at least one aromatic vinyl or vinylidene monomer and at least one aliphatic or cycloaliphatic vinylidene or hidden vinylidene monomer, and (2) from 35 to 92 mole percent of polymeric units derived from at least one one of ethylene and / or α-olefin of C3-20; and (3) from 0 to 20 mole percent of polymer units derived from one or more polymerizable ethylenically unsaturated monomers other than those derived from (1) and (2); and (C) optionally, one or more nucleating agents; and (D) optionally, one more different additives; and (E) one or more blowing agents having zero ozone removal potential and optionally one or more co-blowing agents, and present in a total amount of from 0.2 to 5.0 g moles per kg (based on combined weight of Components A and B); wherein the cellular size of said foam is extended 5 percent or more relative to a corresponding foam without the substantially random interpolymer. 16. The foam according to claim 1 5, characterized in that said foam has a thickness of 9.5 cm or more and wherein; (A) in Component (A), said at least alkenyl aromatic polymer has more than 50 weight percent aromatic monomeric alkenyl units and has a molecular weight (Mw) of from 120,000 to 350,000 and is present in a amount from 80 to 99.5 percent by weight (based on the combined weight of Components A and B); (B) said substantially random interpolymer, Component (B), has an l2 of 0.3 to 30 g / 10 min., And an Mw / Mn, of 1.8 to 10; it is present in an amount of from 0.5 to 20 weight percent (based on the combined weight of components A and B); and comprises (1) from 1 to 45 mole percent of polymer units derived from; (a) said vinylidene or vinyl aromatic monomer represented by the following formula: A l l R '- c = cH 2 wherein R1 is selected from the group of radicals consisting of radicals of hydrogen and alkyl containing three carbons or less, and Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substitutes selected from the group consisting of halo, C 1-4 alkyl, and C 1-4 haloalkyl; or (b) said aliphatic vinylidene or aesthetically hidden cycloaliphatic vinylidene monomer is represented by the following general formula A 'R! _ C = C (R2) wherein A1 is a sterically bulky aliphatic or cycloaliphatic substitute 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 and methyl, each R2 independently selects from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system; or (c) a combination of a and b; and (2) from 55 to 90 mole percent of polymer units derived from ethylene and / or said olefin, comprising at least one of propylene, 4-methyl-1-pentene, butene-1, hexane-1 or octene- 1; and (3) said polymerizable ethylenically unsaturated monomers other than those derived from (1) and (2) comprise norbornene or a norbornene substituted with C6-aryl or a C?.? 0 alkyl; and (C) said nucleating agent, if present, Component (C), comprises one or more of calcium carbonate, talc, clay, silica, barium stearate, diatomaceous earth, mixtures of citric acid and sodium bicarbonate; Y (D) said additive, if present, Component (D), comprises one or more of the inorganic fillers, pigments, antioxidants, acid cleaners, ultraviolet light absorbers, flame retardants, processing aids, other thermoplastic polymers, agents antistatic and extrusion auxiliaries. (E) said blowing agent, Component (E), is present, in a total amount of from 0.5 to 3.0 g-moles / kg (based on the combined weight of Components A and B), and comprises 50 percent or more than one or more inorganic blowing agents, carbon dioxide, hydrofluorocarbons, hydrocarbons, or chemical blowing agents. wherein the cell size of said foam is lengthened 10 percent or more relative to a corresponding foam without the substantially random interpolymer. The foam according to claim 1, characterized in that said foam has a thickness of 2.5 cm or more and wherein; (A) in Component (A), said at least alkenyl aromatic polymer has more than 50 weight percent aromatic alkenyl monomer units, has a molecular weight (Mw) of from 30,000 to 325,000, a distribution of molecular weight, (Mw / Mn) from 2 to 7, and is present in an amount of from 80 to 99 weight percent (based on the combined weight of components A and B); (B) said substantially random ether polymer Component (B), has an l2 of 0.5 to 10 g / 10 min. and an Mw / Mp of 2 to 5; it is present in an amount of from 1 to 20 weight percent (based on the combined weight of components A and B); and comprises (1) from 13 to 39 mole percent of polymer units derived from; (a) said vinyl aromatic monomer comprising styrene, α-methyl styrene, ortho-, meta- and para-methylstyrene, and halogenated styrene rings, or (b) said vinyl or vinylidene, aliphatic or cycloaliphatic monomers which they comprise 5-ethylidene-2-norbornene or 1-vinylcyclohexene, 3-vinylcyclohexene and 4-vinylcyclohexene; or (c) a combination of a and b; and (2) from 61 to 87 mole percent of polymer units derived from ethylene and / or from said α-olefin comprising ethylene, or ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1 , hexane-1 or octene-1; and (3) said polymerizable ethylenically unsaturated monomers other than those derived from (1) and (2) are norbornene.; and (C) said nucleating agent, if present, Component (C), comprises one or more of talc and mixtures of citric acid and sodium bicarbonate; (D) said additive, if present, Component (D), comprises one or more of natural gas carbon black, titanium dioxide, graphite, flame retardants and other thermoplastic polymers; and (E) said blowing agent, Component (E), is present in a total amount of from 1.0 to 2.5 g moles per kg (based on the combined weight of Components A and B), and comprises 70 percent or more than one of, nitrogen, sulfur hexafluoride (SF6), argon, carbon dioxide, 1, 1, 1, 2-tetrafluoroethane (HFC-1 34a), 1,1, 2,2-tetrafiuoroethane (HFC-1) 34), 1, 1, 1, 3, 3-pentafluoropropane, difluoromethane (HFC-32), 1,1-difluoroethane (HFC-1 52a), pentafluoroethane (HFC-1 25), fluoroethane (HFC-1 61), and 1, 1, 1-trifluoroethane (HFC-143a), methane, ethane, propane, n-butane, sobutane, p-pentane, isopentane, cyclopentane and neopentane, azodicarbonamide, azodiisobutyronitrile, benzenesulfonhydrazide, 4,4-oxibenzene , sulfonyl-semicarbazide, p-toluene-sulphonyl semi-carbazide, barium azodicarboxylate, N'-dimethyl-N'-dinitroso-terephthalamide, trihydrazine triazine and mixtures of citric acid and sodium bicarbonate; and wherein the cellular size of said foam is extended 15 percent or more relative to a corresponding foam without the substantially random interpolymer. 18. The foam according to claim 1, characterized in that said alkenyl aromatic polymer, component (A), is polystyrene, Component B is an ethylene / styrene copolymer and the blowing agent, Component (E), is one or more propane, n-pentane, isobutane, carbon dioxide, 1, 1, 1, 2-tetrafluoroethane (HFC-1 34a) or 1,1-2,2-tetrafluoroethane (HFC-1 34). The foam according to claim 1 7, characterized in that said alkenyl aromatic polymer, Component (A), is polystyrene, in said substantially random interpolymer, the Component B1 (a) is styrene; and Component B2 is ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1, and the blowing agent, Component (E) is one or more of propane , n-pentane,? -butane, carbon dioxide, 1, 1, 1, 2-tetrafluoroethane (HFC-1 34a) or 1,1,1,2-tetrafluoroethane (HFC-1 34). 20. The foam according to claim 1, having a density of from 10 to 150 kilograms per cubic meter (kg / m3) and a cell size of 0.05 to 5.0 thousand meters. twenty-one . The foam according to claim 1, which has a density of from 10 to 70 kg / m3 and a cell size of 0.1 to 1.5 millimeters. 22. The foam according to claim 1, characterized in that Component A comprises more than 70 weight percent aromatic alkenyl monomer units, said substantially random interopolymer is incorporated to increase cell size 15 percent or more relative to a foam correspondingly without the substantially random interpolymer, and the foam has a density of 10 to 150 kg / cm 3 and a cell size of 0.05 to 5.0 millimeters. 23. The foam according to claim 1, characterized in that Component A comprises more than 70 weight percent aromatic alkenyl monomer units, said substantially random ether polymer is incorporated to increase cell size 15 percent or more relative to a corresponding foam without the substantially random interpolymer, and the foam has a density of 10 to 70 kg / cm3 and a cell size of 0.1 to

1.5 millimeters.