CA2264731A1 - Blends of .alpha.-olefin/vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers - Google Patents

Abstract

Blends of polymeric materials comprising a plurality of interpolymers each having (1) from 0.5 to 65 mole percent of either (a) at least one vinylidene aromatic monomer or (b) at least one hindered aliphatic or cycloaliphatic vinylidene monomer, or (c) a combination of at least one vinylidene aromatic monomer and at least one hindered aliphatic vinylidene monomer, and (2) from 35 to 99 mole percent of at least one aliphatic alpha olefin having from 2 to 20 carbon atoms; and wherein interpolymer components differ in that (i) the amount of vinylidene aromatic monomer residue and/or hindered aliphatic or cycloaliphatic vinylidene monomer residue in any interpolymer component differs from another by at least 0.5 mole percent; and/or (ii) there is a difference of at least 20 percent between the number average molecular weight (Mn) of interpolymer components. These blends of interpolymer components give enhanced properties or processability when compared to the individual polymers comprising the blend.

Description

102025303540W0 98/10018CA 02264731 1999-03-03PCT/US97/15546BLENDS OF a—OLEFIN/VINYLIDENE AROMATIC MONOMER AND/OR HINDEREDALIPHATIC OR CYCLOALIPHATIC VINYLIDENE MONOMER INTERPOLYMERSThe present invention pertains to blends of a-olefin/vinylidenearomatic monomer and/or hindered aliphatic or cycloaliphaticvinylidene monomer interpolymers having different vinylidene aromaticmonomer and/or hindered aliphatic or cycloaliphatic vinylidene monomercontent or different molecular weight or both different vinylidenearomatic monomer and/or hindered aliphatic or cycloaliphaticvinylidene monomer content and different molecular weight. The blendcomponents are selected to provide superior performance orprocessability in the blends.The generic class of materials covered by a—olefin/hinderedvinylidene monomer substantially random interpolymers and includingmaterials such as d—olefin/vinyl aromatic monomer interpolymers areknown in the art and offer a range of material structures andproperties which makes them useful for varied applications, such ascompatibilizers for blends of polyethylene and polystyrene asdescribed in US 5,460,818.One particular aspect described by D’Anniello et al. (Journal ofApplied Polymer Science, Volume 58, pages 1701-1706 [1995]) is thatsuch interpolymers can show good elastic properties and energydissipation characteristics.In another aspect, selected interpolymerscan find utility in adhesive systems, as illustrated in United Statespatent number 5,244,996,Ltd.issued to Mitsui Petrochemical IndustriesAlthough of utility in their own right, Industry is constantlyseeking to improve the applicability of these interpolymers. Suchenhancements may be accomplished via additives or the like, but it isdesirable to develop technologies to provide improvements inprocessability and/or performance without the addition of additives orfurther improvements than can be achieved with the addition ofadditives. To date, the possible advantages of blending to providematerials with superior properties have not been identified.There is a need to provide blends of d—o1efin/vinylidenearomatic monomer interpolymers with superior performancecharacteristics which will expand the utility of this interestingclass of materials.The present invention pertains to a blend of polymeric materialscharacterized by a plurality of interpolymers, each interpolymerresulting from polymerizing:10152025303540W0 98/10018CA 02264731 1999-03-03PCT/US97l15546(1) from 1 to 65 mole percent of(a) at least one vinylidene aromatic monomer, or(b) at least one hindered aliphatic or cycloaliphatic vinylidenemonomer, or(c) a combination of at least one vinylidene aromatic monomerand at least one hindered aliphatic or cycloaliphaticvinylidene monomer, and(2) from 35 to 99 mole percent of at least one aliphatic a—olefinhaving from 2 to 20 carbon atoms; and(3) from O to 10 mole percent of at least one polymerizable olefin(2); andwherein each of the interpolymer blend components are distinct inthat:monomer different from(i) the amount of vinylidene aromatic monomer residue and/orhindered aliphatic or cycloaliphatic vinylidene monomer residuein any interpolymer differs from that amount in any otherinterpolymer by at least 0.5 mole percent; and/or(ii)there is a difference of at least 20 percent between the numberaverage molecular weight (Mn) in any interpolymer and any otherinterpolymer.The blends of the present invention can comprise, consistessentially of or consist of any two or more of such interpolymersenumerated herein. Likewise, the interpolymers can comprise, consistessentially of or consist of any two or more of the enumeratedpolymerizable monomers.These blends provide an improvement in one or more of thepolymer properties such as mechanical performance and/or meltprocessability.The percent difference in comonomer content (vinylidene aromaticmonomer residue and/or hindered aliphatic or cycloaliphatic vinylidenemonomer residue) between the interpolymers in the blends of thepresent invention is determined by subtracting the comonomer contentof the interpolymer with the lowest comonomer content from theinterpolymer with the highest comonomer content. In those instanceswhere more than 2 interpolymers are employed in the blend, the percentdifference is determined for each combination of two polymers forexample for a blend of interpolymers A, B and C, the determination ismade for the combinations: A & B, A & C and B & C.The percent difference in Mn between the interpolymers in theblends of the present invention is determined by subtracting the Mn ofthe interpolymer with the lowest Mn from the interpolymer with thehighest Mn and dividing the difference with the Mn of the interpolymer-2-10152025303540WO 98/10018CA 02264731 1999-03-03PCT/US97/ 15546with the lowest Mn, then multiplying by 100. In those instances wheremore than 2 interpolymers are employed in the blend, the percentdifference is determined for each combination of two polymers forexample for a blend of interpolymers A, B and C, the determination ismade for the combinations: A & B, A & C and B & C.The term "hydrocarbyl" means any aliphatic, cycloaliphtic,aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic,aliphatic substituted aromatic, or cycloaliphatic substituted aromaticgroups. The aliphatic or cycloaliphatic groups are preferablysaturated. Likewise, the term "hydrocarbyloxy" means a hydrocarbylgroup having an oxygen linkage between it and the carbon atom to whichit is attached.The term "plurality" as used herein means two or more.The term "interpolymer" is used herein to indicate a polymerwherein at least two different monomers are polymerized to make theinterpolymer. This includes copolymers, terpolymers, etcThe term "substantially random” in the substantially randominterpolymer resulting from polymerizing one or more a-olefin monomersand one or more vinylidene aromatic monomers or hindered aliphatic orcycloaliphatic vinylidene monomers, and optionally, with otherpolymerizable ethylenically unsaturated monomer(s) as used hereinmeans that the distribution of the monomers of said interpolymer canbe described by the Bernoulli statistical model or by a first orsecond order Markovian statistical model, as described by J. C.Randall in POLYMER SEQUENCE DETERMINATION, Carbon-13 NMR Method,l977, pp. 71-78. Preferably, thesubstantially random interpolymer resulting from polymerizing one orAcademic Press New York,more a—olefin monomers and one or more vinylidene aromatic monomers,and optionally, with other polymerizable ethylenically unsaturatedmonomer(s) does not contain more than 15 percent of the total amountof vinylidene aromatic monomer residue in blocks of vinylidenearomatic monomer of more than 3 units. More preferably, theinterpolymer is not characterized by a high degree of eitherisotacticity or syndiotacticity. This means that in the carbon*3 NMRspectrum of the substantially random interpolymer the peak areascorresponding to the main chain methylene and methine carbonsrepresenting either meso diad sequences or racemic diad sequencesshould not exceed 75 percent of the total peak area of the main chainmethylene and methine carbons.Any numerical values recited herein include all values from thelower value to the upper value in increments of one unit provided thatthere is a separation of at least 2 units between any lower value and-3-101520253035WO 98/10018CA 02264731 1999-03-03PCT/U S97/ 15546any higher value. As an example, if it is stated that the amount of acomponent or a value of a process variable such as, for example,temperature, pressure, time is, for example, from 1 to 90, preferablyit is intended that30 to 32 etc. arefrom 20 to 80, more preferably from 30 to 70,22 to 68, 43 to 51,expressly enumerated in this specification.values such as 15 to 85,For values which are less0.001, 0.01 or 0.1 asThese are only examples of what is specifically intendedthan one, one unit is considered to be 0.0001,appropriate.and all possible combinations of numerical values between the lowestvalue and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner.The interpolymers employed in the present invention include, butare not limited to, substantially random interpolymers prepared bypolymerizing one or more a—olefin monomers with one or more vinylidenearomatic monomers and/or one or more hindered aliphatic orcycloaliphatic vinylidene monomers, and optionally with otherpolymerizable ethylenically unsaturated monomer(s).Suitable d—olefin monomers include for example, a—olefinmonomers containing from 2 to 20, preferably from 2 to 12, morepreferably from 2 to 8 carbon atoms. Preferred such monomers includeethylene, propylene, butene—1, 4—methyl—1-pentene, hexene—1 andoctene—l. Most preferred are ethylene or a combination of ethylenewith C24 a—olefins. These a—olefins do not contain an aromaticmoiety.Suitable vinylidene aromatic monomers which can be employed toprepare the interpolymers employed in the blends include, for example,those represented by the following formula:ArI(C|:H2)nR‘ — C = C(R2)2wherein R1 is selected from the group of radicals consisting ofhydrogen and alkyl radicals containing from 1 to 4 carbon atoms,preferably hydrogen or methyl; each R7 is independently selected fromthe group of radicals consisting of hydrogen and alkyl radicalscontaining from 1 to 4 carbon atoms, preferably hydrogen or methyl; Aris a phenyl group or a phenyl group substituted with from 1 to 5substituents selected from the group consisting of halo, CL4-alkyl,and Cp4—haloalkyl; and n has a value from zero to 4, preferably fromExemplary monovinylidene aromatict—butylzero to 2, most preferably zero.monomers include styrene, vinyl toluene, a—methylstyrene,101520253035W0 98/10018CA 02264731 1999-03-03PCT/US97l15546styrene, chlorostyrene, including all isomers of these compounds.Particularly suitable such monomers include styrene and lower alkyl—Preferred monomers(C1 ~ C4) oror halogen—substituted derivatives thereof.include styrene, d—methyl styrene, the lower alkyl—phenyl—ring substituted derivatives of styrene, such as for example,ortho-, meta—, and para—methylstyrene, the ring halogenated styrenes,para—vinyl toluene or mixtures thereof. A more preferred aromaticmonovinylidene monomer is styrene.By the term “hindered aliphatic or cycloaliphatic vinylidenecompounds”, it is meant addition polymerizable vinylidene monomerscorresponding to the formula:AlIR‘ — C = c<R2>2wherein Al is a sterically bulky, aliphatic or cycloaliphaticsubstituent of up to 20 carbons, R1 is selected from the group ofradicals consisting of hydrogen and alkyl radicals containing from 1to 4 carbon atoms, preferably hydrogen or methyl; each R2 isindependently selected from the group of radicals consisting ofhydrogen and alkyl radicals containing from 1 to 4 carbon atoms,preferably hydrogen or methyl; or alternatively R1 and A1 together forma ring system. By the term “sterically bulky” is meant that themonomer bearing this substituent is normally incapable of additionpolymerization by standard Ziegler~Natta polymerization catalysts at arate comparable with ethylene polymerizations. a-Olefin monomerscontaining from 2 to 20 carbon atoms and having a linear aliphatichexene—1 and octene—l are notstructure such as propylene, butene-1,considered as hindered aliphatic monomers. Preferred hinderedaliphatic or cycloaliphatic vinylidene compounds are monomers in whichone of the carbon atoms bearing ethylenic unsaturation is tertiary orquaternary substituted. Examples of such substituents include cyclicaliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, orring alkyl or aryl substituted derivatives thereof, tert—butyl,norbornyl. Most preferred hindered aliphatic or cycloaliphaticvinylidene compounds are the various isomeric vinyl- ring substitutedand 5-and 4-derivatives of cyclohexene and substituted cyclohexenes,ethylidene—2—norbornene. Especially suitable are 1-, 3—,vinylcyclohexene.Other optional polymerizable ethylenically unsaturatedmonomer(s) include strained ring olefins such as norbornene and C14010152025303540W0 98/ 10018CA 02264731 1999-03-03PCT/US97/15546alkyl or C640 aryl substituted norbornenes, with an exemplaryinterpolymer being ethylene/styrene/norbornene.(Mn)interpolymers is usually greater than 5,000, preferably from 20,000 to1,000,000, more preferably from 50,000 to 500,000.The number average molecular weight of the polymers andPolymerizations and unreacted monomer removal at temperaturesabove the autopolymerization temperature of the respective monomersmay result in formation of some amounts of homopolymer polymerizationproducts resulting from free radical polymerization. For example,while preparing the substantially random interpolymer, an amount ofatactic vinylidene aromatic homopolymer may be formed due tohomopolymerization of the vinylidene aromatic monomer at elevatedtemperatures. The presence of vinylidene aromatic homopolymer is ingeneral not detrimental for the purposes of the present invention andcan be tolerated. The vinylidene aromatic homopolymer may beseparated from the interpolymer, if desired, by extraction techniquessuch as selective precipitation from solution with a non solvent foreither the interpolymer or the vinylidene aromatic homopolymer. Forthe purpose of the present invention it is preferred that no more than20 weight percent, preferably less than 15 weight percent based on thetotal weight of the interpolymers of vinylidene aromatic homopolymeris present.The substantially random interpolymers may be modified bytypical grafting, or other reactionshydrogenation, functionalizing,well known to those skilled in the art. The polymers may be readilysulfonated or chlorinated to provide functionalized derivativesaccording to established techniques.The substantially random interpolymers can be prepared asdescribed in US Application Number 07/545,403 filed July 3, 1990(corresponding to EP—A—0,416,815) Stevens et al.allowed US Application Number 08/469,828 filed June 6, 1995 all ofwhich are incorporated herein by reference in their entirety.by James C. and inPreferred operating conditions for such polymerization reactions arepressures from atmospheric up to 3,000 atmospheres and temperaturesfrom —30°C to 200°C.Examples of suitable catalysts and methods for preparing thesubstantially random interpolymers are disclosed in U.S. Application No.07/545,403,Application No.filed July 3, 1990 corresponding to EP-A—416,815;07/702,475, filed May 20,514,828; U.S. Application No. 07/876,268, filed May 1, 1992corresponding to EP-A—520,732; U.S. Application No. 08/241,523,May 12, 1994; 5,055,438; 5,057,475;U.S.1991 corresponding to EP-A-filedas well as U.S. Patents: 5,096,867;-5-10152025303540W0 98/10018CA 02264731 1999-03-03PCT/US97/155465,064,802; 5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723;5,374,696; 5,399,635; 5,460,993 and 5,556,928 all of which patents andapplications are incorporated herein by reference in their entirety.The substantially random a—olefin/vinylidene aromaticinterpolymers 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. Pannellin WO 94/00500; and in PlasticsTechnology, p. 25 (September 1992), all of which are incorporated(Exxon Chemical Patents, Inc.)herein by reference in their entirety.Also suitable are the substantially random interpolymers whichcomprise at least one a—olefin/vinyl aromatic/vinyl aromatic/a—olefin08/708,809 filed SeptemberThese interpolymers containtetrad disclosed in U. S. Application No.4, 1996 by Francis J. Timmers et al.additional signals with intensities greater than three times the peakto peak noise. These signals appear in the chemical shift range43.75-44.25 ppm and 38.0-38.5 ppm.43.9 and 38.2 ppm.indicates that the signals in the chemical shift region 43.75-44.25Specifically, major peaks areobserved at 44.1, A proton test NMR experimentppm are methine carbons and the signals in the region 38.0-38.5 ppmare methylene carbons.In order to determine the carbon'” NMR chemical shifts of theinterpolymers described, the following procedures and conditions areemployed. A five to ten weight percent polymer solution is preparedin a mixture consisting of 50 volume percent l,l,2,2—tetrachloroethane—d2 and 50 volume percent 0.10 molar chromiumtris(acetylacetonate) in l,2,4-trichlorobenzene. NMR spectra areacquired at 130°C using an inverse gated decoupling sequence, a 90°pulse width and a pulse delay of five seconds or more. The spectraare referenced to the isolated methylene signal of the polymerassigned at 30.000 ppm.It is believed that these new signals are due to sequencesinvolving two head—to—tail vinyl aromatic monomer preceded andfollowed by at least one a—olefin insertion, for example anethylene/styrene/styrene/ethylene tetrad wherein the styrene monomerinsertions of said tetrads occur exclusively in a 1,2 (head to tail)manner. It is understood by one skilled in the art that for suchtetrads involving a vinyl aromatic monomer other than styrene and ana—olefin other than ethylene that the ethylene/vinyl aromaticmonomer/vinyl aromatic monomer/ethylene tetrad will give rise tosimilar carbon”3 NMR peaks but with slightly different chemicalshifts.-11015202530W0 98/10018CA 02264731 1999-03-03PCT/US97/ 15546The interpolymers which contain hindered cycloaliphatic monomerresidues are usually prepared by subjecting an interpolymer containingmonovinylidene aromatic monomer residues to hydrogenation thereforconverting some or all of the aromatic rings to cycloaliphatic ringswhich can be saturated (for example, cyclohexane ring) or unsaturated(cyclohexene ring).The interpolymers of one or more a—olefins and one or moremonovinylidene aromatic monomers and/or one or more hindered aliphaticor cycloaliphatic vinylidene monomers employed in the presentinvention are substantially random polymers.These interpolymers usually contain from 0.5 to 65, preferablyfrom 1 to 55, more preferably from 2 to 50 mole percent of at leastone vinylidene aromatic monomer and/or hindered aliphatic orcycloaliphatic vinylidene monomer and from 35 to 99.5, preferably from45 to 99, more preferably from 50 to 98 mole percent of at least onealiphatic a-olefin having from 2 to 20 carbon atoms.These interpolymers are prepared by conducting thepolymerization at temperatures of from —30°C to 250°C in the presenceof such catalysts as those represented by the formulaCp/ \(ER2)m MR'2Cpwherein: each Cp is independently, each occurrence, a substitutedcyclopentadienyl group n—bound to M; E is C or Si; M is a group IVmetal, preferably Zr or Hf, most preferably Zr; each R isindependently, each occurrence, H, hydrocarbyl, silahydrocarbyl, orhydrocarbylsilyl, containing up to 30 preferably from 1 to 20 morepreferably from 1 to 10 carbon or silicon atoms; each R’ isindependently, each occurrence, H, halo, hydrocarbyl, hyrocarbyloxy,silahydrocarbyl, hydrocarbylsilyl containing up to 30 preferably from1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R‘groups together can be a Clno hydrocarbyl substituted l,3—butadiene; mis 1 or 2; and optionally, but preferably in the presence of anactivating cocatalyst. Particularly, suitable substitutedcyclopentadienyl groups include those illustrated by the formula:1=‘cT/Us 97/15546101520253035CA 02264731 1999-03-03EPO- DG‘.(R)3 Q5 10 1996Gwherein each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl,or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferablyfrom 1 to 10 carbon or silicon atoms or two R groups together form a divalentderivative of such group. Preferably, R independently each occurrence is (includingwhere appropriate all isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl,benzyl, phenyl or silyl or (where appropriate) two such R groups are linked togetherforming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, or octahydrofluorenyl.Particularly preferred catalysts include, for example, racemic-((dimethylsilanediyl)bis(2-methyl-4-phenylindenyl))zirconium dichloride, racemic-((dimethylsilanediyl)bis(2-methyl-4-phenylindenyl))zirconium 1,4-diphenyl-1,3-butadiene, racemic-((dimethylsilanediyl)bis(2-methyl—4-phenylindenyl))zirconiumdi-C14 alkyl, racemic-((dirnethylsilanediyl)bis(2-methyl-4-phenylindenyl))zirconiumdi-C14 alkoxide, or any combination thereof.Further preparative methods for the interpolymer components of the presentinvention have been described in the literature. Longo and Grassi (Makromol.Chem., Volume 191, pages 2387 to 2396 [1990]) and D’Annie1lo et al. (Journal ofApplied Polymer Science, Volume 58, pages 1701-1706 [1995]) reported the use of acatalytic system based on methylalumoxane (MAO) and cyclopentadienyltitaniumtrichloride (CpTiCl3) to prepare an ethylene-styrene copolymer. Xu and Lin(Polymer Preprints, Am.Chem.Soc.,Div.Polym.Chem.J Volume 35, pages 686,687[1994]) have reported copolymerization using a MgCl2/TiC14/ NdCl3/ A1(iBu)3catalyst to give random copolymers of styrene and propylene. Lu et al (loumal ofApplied Polymer Science, Volume 53, pages 1453 to 1460 [1994]) have described thecopolymerization of ethylene and styrene using a TiCl4/ NdCl3/ MgCl2 / Al(Et)3catalyst. Sernetz and Mulhaupt, (Macromol. (_Ihem. Phvs., v. 197, pp 1071-1083,1997) have described the influence of polymerization conditions on thecopolymerization of styrene with ethylene using Me2Si(Me4Cp)(N-tert-butyl)TiC12/ methylaluminoxane Ziegler-Natta catalysts. The manufacture of oz-olefin/ vinyl aromatic monomer interpolymers such as propylene/ styrene andbutene/ styrene are described in United States patent number 5,244,996, issued toMitsui Petrochemical Industries Ltd.-9.AMENDED SHEETREPLACEMENT PAGE "DEA/Ep10152025303540W0 98/ 10018CA 02264731 1999-03-03PC1VUS97fl5546The present invention provides blends of interpolymer componentsof molecular weight and composition distributions selected to obtainan overall molecular weight and composition distribution which givesenhanced properties or processability.The interpolymer blend components are distinct in that:(i) the amount of vinylidene aromatic monomer residue and or hinderedaliphatic or cycloaliphatic vinylidene monomer residue in anyinterpolymer component differs from another by at least 0.5 molepercent, preferably by at least 1 mole percent and most preferably by2 mole percent; and/or(ii) there is a difference of at least 20 percent, preferably atleast 30 percent and most preferably at least 40 percent between thenumber average molecular weight(Mn) of interpolymer components.In one embodiment, the components for the blend areinterpolymers having a relatively narrow molecular weightdistribution, with Mw/Mn < 3.5. Utilizing these interpolymers ascomponents, the invention provides interpolymers having pluralmodality with respect to comonomer residue content and a narrowmolecular weight distribution, such that Mw/Mn < 3.5.In another aspect, the invention provides interpolymers havingplural modality with respect to molecular weight, such that Mw/Mn >3.5 and produced from component interpolymers having essentially thesame comonomer residue contents.In still another aspect, the invention provides interpolymershaving plurality with respect to both molecular weight distribution,such that Mw/Mn > 3.5, and produced from component polymers having adifference in comonomer content.A further aspect of the present invention pertains to blendscomprising two or more substantially random interpolymers of styreneand ethylene or styrene and a combination of ethylene and one or moreother polymerizable monomers, wherein the substantially randominterpolymer components have a difference in styrene content of from 2to less than 10 wt. percent. These blends can be considered asmiscible, in that such blends exhibit a single glass transition(T9)between the Tg's of the individual polymers.temperature similar in form to, but in the temperature rangeThese blend compositionsare particularly suitable, for example, to optimize processability.Another aspect of the present invention pertains to blendscomprising two or more substantially random interpolymers of styreneand ethylene or styrene and a combination of ethylene and one or moreother polymerizable monomers, wherein the substantially randominterpolymer components have a difference in styrene content of-10-102025303540WO 98/10018CA 02264731 1999-03-03PCT/US97/15546greater than 10 wt.%. These blend compositions can be considered asimmiscible blends, in that they exhibit a broadened single glasstransition temperature range, or exhibit two or more glass transitiontemperatures which reflects the behavior of the individual polymers.These blends are particularly suitable for applications includingthose which require energy absorption over specific temperatureranges, such as sound and vibration damping.Also contemplated are blend compositions comprising three ormore components wherein two or more components show miscible behaviorusing Tg criteria, but the overall blend composition exhibits abroadened single glass transition temperature range, or exhibits twoor more distinct glass transition temperatures.The blends of the present invention may be prepared by anysuitable means known in the art such as, but not limited to, dryblending in a pelletized form in the desired proportions followed bymelt blending in a screw extruder, Banbury mixer or the like. The dryblended pellets may be directly melt processed into a final solidstate article by for example injection molding. Alternatively, theblends may be made by direct polymerization, without isolation of theblend components, using for example two or more catalysts in onereactor, or by using a single catalyst and two or more reactors inseries or parallel.Additives such as antioxidantsIRGANOX® 1010),(for example, hindered phenolssuch as,IRGAFOS® 168)):for example,U. V.phosphites (for example,stabilizers, cling additives (for example,polyisobutylene), antiblock additives, slip agents, colorants,pigments, fillers can also be included in the interpolymers employedin the blends of the present invention, to the extent that they do notinterfere with the enhanced properties discovered by Applicants.The additives are employed in functionally equivalent amountsknown to those skilled in the art. For example, the amount ofantioxidant employed is that amount which prevents the polymer orpolymer blend from undergoing oxidation at the temperatures andenvironment employed during storage and ultimate use of the polymers.Such amounts of antioxidants is usually in the range of from 0.01 to10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percentby weight based upon the weight of the polymer or polymer blend.Similarly, the amounts of any of the other enumerated additivesare the functionally equivalent amounts such as the amount to renderthe polymer or polymer blend antiblocking, to produce the desiredamount of filler loading to produce the desired result, to provide thedesired color from the colorant or pigment. Such additives can-11-10152025303540WO 98/10018CA 02264731 1999-03-03PCTIU S97! 15546suitably be employed in the range of from 0.05 to 50, preferably from0.1 to 35 more preferably from 0.2 to 20 percent by weight based uponthe weight of the polymer or polymer blend.of fillers,weight based on the weight of the polymer or polymer blend.However, in the instancethey could be employed in amounts up to 90 percent byThe blends of the present invention can be utilized to produce,but not limited to, a wide range of fabricated articles such as, forexample, calendered sheet, blown or cast films, injection molded,rotomolded or thermoformed parts. The blends can also be used in themanufacture of fibers, foams and latices.The blends of the presentinvention can also be utilized in adhesive formulations.The following examples are illustrative of the invention, butare not to be construed as to limiting the scope thereof in anymanner.EXAMLESPreparation of Interpolymers A, B, C, and EPolymer was prepared in a 400 gallon agitated semi—continuousbatch reactor. The reaction mixture consisted of approximately 250gallons of a solvent comprising a mixture of cyclohexane (85 weightpercent) and isopentane (15 weight percent), and styrene. Prior toaddition, solvent, styrene and ethylene were purified to remove waterand oxygen. The inhibitor in the styrene was also removed. Inertswere removed by purging the vessel with ethylene. The vessel was thenpressure controlled to a set point with ethylene. Hydrogen was addedto control molecular weight. Temperature in the vessel was controlledto set-point by varying the jacket water temperature on the vessel.the vessel was heated to the desired run(N—l,1—dimethylethyl)dimethyl(l—(l,2,3,4,5-eta)-2,3,4,5-tetramethyl— 2,4-CAS# 135072—62—7,CAS# O0l109—15—5, Modified methylalumin-oxane Type 3A, CAS# l46905—79—5, were flow controlled,combined and added to the vessel.Prior to polymerization,temperature and the catalyst components: Titanium:cyclopentadien—l—yl)silanaminato))(2—)N)-dimethyl,Tris(pentafluorophenyl)boron,on a mole ratiobasis of l/3/5 respectively, Afterstarting, the polymerization was allowed to proceed with ethylenesupplied to the reactor as required to maintain vessel pressure. Insome cases, hydrogen was added to the headspace of the reactor tomaintain a mole ratio with respect to the ethylene concentration. Atthe end of the run,the catalyst flow was stopped, ethylene wasremoved from the reactor, lOOO ppm of Irganoxm 1010 anti—oxidant wasthen added to the solution and the polymer was isolated from thesolution. Catalyst efficiency was generally greater than 100,000 #polymer per # Ti. The resulting polymers were isolated from solution-12-W0 98/1001810152025CA 02264731 1999-03-03PCT/U S97/ 15546by either stripping with steam in a vessel or by use of adevolatilizing extruder. In the case of the steam stripped material,additional processing was required in extruder—like equipment toreduce residual moisture and any unreacted styrene.Inter— Solvent Styrene Pressure Temp. Total Run Polymerpolymer loaded loaded H3 Time inAdded Solutionlbs kg lbs kg Psi kPa ° C Grams Hours Wt. %9(A) 252 114 132 59 42 290 60 O 2.8 11.50 9(B) 839 381 661 30 105 724 60 53.1 4.8 11.60(C) 1196 542 225 10 70 483 60 7.5 6.1 7.22(E) 842 382 662 30 105 724 60 8.8 3.7 8.60Interpo Melt Total Talc Isolatiolymer Index Wt% Level n12 Styrene Wt % MethodResidueinPolymer*(A) 0.18 81.7 <2.5 SteamStrip(B) 2.6 45.5 0 Extruder(C) 0.03 29.8 0 Extruder(E) 0.01 48.3 <1.0 SteamStrip* Total wt.percent styrene residue measured via FourierTransform Infrared (FTIR) technique.Preparation of Interpolymer DInterpolymer D was prepared in the following manner.A 130 mL continuous loop reactor,(1200 mL/min),consisting of two staticmixers, a gear pump inlets for liquids and gasses, aviscometer and a pair of thermocouples, was used to prepare thepolymer. The reactor temperature was maintained by external heatingtapes. Pressure was monitored at the liquid inlet and controlled viaa variable valve on the outlet. The reactor was fed with a mixture of75 weight percent styrene and 25 weight percent toluene at 12.00mL/min, ethylene at 0.700 g/min, hydrogen at 0.411 mg/min and acatalyst system composed of 0.001 M toluene solutions of tert-butylamidodimethyl(tetramethylcyclopenta—dienyl)silanetitanium—dimethyl and tris-(pentafluoro—phenyl)borane both at 0.25 mL/min. Thereactor temperature was held at 100°C and the viscosity allowed to(0.015 Pans).blended with 0.05 mL/min of a catalyst deactivator/polymer stabilizer20 g of Irganox 1010 and 15 mL of 2-stabilize at ~15 cP The resulting polymer solution wassolution (1 L of toluene,-13- 10152025303540WO 98/10018CA 02264731 1999-03-03PCT/US97/15546propanol), cooled to ambient temperature and collected for 20 hoursand 50 minutes. The solution was dried in a vacuum oven overnight,resulting in 750g of a 16.6 mole percent styrene residueethylene/styrene copolymer with 6.5 weight percent atactic polystyrenehaving a melt index greater than 200.Test parts and characterization data for the interpolymers andtheir blends were generated according to the following procedures:Compression Molding:and compression molded at 190°C under 20,000 lbSamples were melted at 190°C for 3 minutes(9,072 kg) of pressurefor another 2 minutes. Subsequently, the molten materials werequenched in a press equilibrated at room temperature.Density: The density of the samples is measured according toASTM—D792.Differential Scanning Calorimetry (DSC): A Dupont DSC—292O isused to measure the thermal transition temperatures and heat oftransition for the interpolymers. In order to eliminate previousthermal history, samples were first heated to 200 °C. Heating andcooling curves were recorded at 10°C/min. Melting (from second heat)and crystallization temperatures were recorded from the peaktemperatures of the endotherm and exotherm,Melt Shear Rheology:were performed with a Rheometrics RMS—80O rheometer.respectively.Oscillatory shear rheology measurementsRheologicalproperties were monitored at an isothermal set temperature of 190°C ina frequency sweep mode.Solid state dynamic mechanical testing: Dynamic mechanicalproperties of compression molded samples were monitored using aRheometrics 800E mechanical spectrometer. Samples were run in torsionrectangular geometry and purged under nitrogen to prevent thermaldegradation.Typically, samples were run at a fixed forced frequencyof 10 rad/sec using a torsional set strain of 0.05%, and collectingdata isothermally at 4°C intervals.Mechanical Testing:Shore A hardness is measured following ASTM—D240.evaluated according to ASTM—D790.All properties were generated at 23°C.Flexural modulus isTensile properties of thecompression molded samples were measured using an Instron 1145 tensilemachine equipped with an extensiometer. ASTM—D638 samples were testedat a strain rate of 5 min'1. The average of four tensile measurementsis given. The yield stress and yield strain were recorded at theinflection point in the stress/strain curve. The Energy at break isthe area under the stress/strain curve.Tensile Stress Relaxation: Uniaxial tensile stress relaxationis evaluated using an Instron 1145 tensile machine. Compression-14-CA 02264731 1999-03-03W0 98/10018 PCT/US97/15546molded film (~ 20 mil thick) with a 1 in. (25.4 mm) gauge length isdeformed to a strain level of 50 percent at a strain rate of 20 min"1.The force required to maintain 50 percent elongation is monitored for10 min. The magnitude of the stress relaxation is defined as (fi-ff/fi) where fi is the initial force and ff is the final force.The characteristics of each of the interpolymers were given intable 1. The unblended interpolymers provide the comparative examplesemployed herein.-15-CA 02264731 1999-03-03W0 98/10018 PCT/US97/15546Table 1INTERPOLYMERInterpolymer (A) (B) (C) (D) (E)Compositionwt % atactic 8.6 10.3 1 6.5 3.7Polystyrene °wt % Styrene 69.4 43.4 29.3 42.4 47.3Residue°wt % Ethylene 30.6 56.6 70.7 57.6 52.7Residue“mol % Styrene 37.9 17.1 10 16.5 19.5Residue“mol % Ethylene 62.1 82.9 90 83.5 80.5Residue“ 'Molecular WeightMFR, 12 0.18 2.62 0.03 > 200 0.01Mnx103 161.1 66.8 118.1 13.6 144.9MW/Mnflivolydxsperslty) 2 Physical PropertiesDensity. g/cc 1.0352 0.9626 0.943 0.9756 0.9604Tm, °C a 49.6 71.3 62.1 45.7% Crystallinity a 4.8 14.7 4.6 4.7Tc, “C a 22.1 58.1 46.6 17Tg(DSC) 24.2 ~ -12 -17.2 a —12.7Mechanical PropertiesShore A 96 75 88 78 76Tensile Modulus, 594.3 6.5 20 19.3 6.8MpaFlexural Modulus, 617.1 68.8 62.1 84.8 140.7MpaYield Stress, MPa 5.6 1.3 2.4 2.3 1.5% Strain @ Break 257.8 475.3 377.5 412.8 337.8Stress @ Break, 21.5 22.6 34.3 2.5 17.4MpaEnergy @ Break, 118.5 102.2 145.5 33.9 73.2N°m% Stress 92.9 38 30.2 43.2 26.2RelaxationMelt Rheologynx10b(0.1 6.53 1.05 16.6 b 31rad/sec), Poisen (100/0.1) 0.048 0.15 0.16 b 0.038Tan 5 (0.1 4.42 4.2 2.37 b 1.26rad/sec)a Could not be measured by DSC.b Could not be measured.c Measured by N.M.R. techniquesEXAMPLES 1-3Blend Preparation: Three blend compositions, examples 1, 2 and3, were prepared from interpolymers (A) and (B) above in weight ratiosof (A)/(B) of 75/25, 50/50 and 25/75 with a Hakke mixer equipped witha Rheomix 3000 bowl. The blend components were first dry blended andthen fed into the mixer equilibrated at 190°C. Feeding and-16-10152025W0 98/10018CA 02264731 1999-03-03PCT/US97/15546temperature equilibration took 3 to 5 minutes. The molten material ismixed at 190°C and 40 rpm for 10 minutes.The characterization data for the blends and the interpolymercomponents was presented in table 2. Interpolymer blend components(A) and (B) have molecular weights which were significantly different,and styrene content which differ by 28 mol. percent.Table 2[ Example or Comparative Experiment No. |(A)* (B)* 1 2 3Blend Composition, 100% (A) 100% (B) (A)/(B) (A)/(B) (A)/(B)wt ratio 75/25 50/50 25/75styrene residue N/A‘ N/A‘ 20.8 20.8 20.8mole % difference% Mn difference N/A‘ N/A‘ 141 141 141Mechanical PropertiesShore A 96 75 96 91 80Tensile Modulus, 594.3 6.5 1143.2 326.8 28.2MPaFlexural Modulus, 617.1 68.8 531.1 169.9 24.4MPaYield Stress, MPa 5.6 1.3 10.8 4.6 2.3% Strain @ Break 257.8 475.3 287.7 370.2 415.6Stress @ Break, MPa 21.5 22.6 23.7 25 25.5Energy @ Break, N'm 118.5 102.2 146.3 152.4 126.8% Stress Relaxation 92.9 38 86.9 82.2 67.2Melt Rheologynx10”(0.1 rad/sec), 6.53 1.05 3.75 2.34 1.57Poisen(100/0.1) 0.048 0.15 0.058 0.078 0.16Tan 8 (0.1 rad/sec) 4.42 4.2 2.16 2.46 2.14* Not an example of the present inventiona Not applicable2 and 3 allhave high tensile energies at break, which significantly exceed theTable 2 shows that the blend composition examples 1,performance of the unblended interpolymers, comparative examples (A)and (B). Further, the blends retain an unexpected level of stressrelaxation compared to what may be anticipated from the componentpolymers.Blend examples 1, 2 and 3 also have tan 8 values at low shearrates in the melt which were significantly lower than either of thecomponent polymers (A) and (B). This translates to higher meltelasticity and improved part forming characteristics under certainmelt processing operations.EXAMPLE 4A blend composition, example 4, was prepared from interpolymers(A) and (C)in a 50/50 weight ratio of components, according to thesame procedure employed in examples 1-3.-17-152025W0 98/10018CA 02264731 1999-03-03PCT/US97/15546The characterisation data for the blends and the interpolymercomponents was presented in table 3. Interpolymer blend components (A)and (C) (Mn) which both exceed 100,000 andstyrene residue contents which differ by 28 mol. percent.have molecular weightsTable 3Example or ComparativeExperiment No.(A)* (C)* 4Blend Composition, 100% 100% (A)/(C)wt ratio (A) (C) 50/50styrene residue mole% difference N/A‘ N/A‘ 27.9% Mn difference N/A’ N/A’ 36.4Mechanical PropertiesShore A 96 88 96Tensile Modulus, MPa 594.3 20 424.7Flexural Modulus, 617.1 62.1 202MPaYield Stress, MPa 5.6 2.4 5.9% Strain @ Break 257.8 377.5 313Stress @ Break, MPa 21.5 34.3 37Energy @ Break, N-m 118.5 145.5 188% Stress Relaxation 92.9 30.2 75.1Melt Rheologynxl0”(0.1 rad/sec), 6.53 16.6 10.3Poisen (100/0.1) 0.048 0.16 0.048Tan 8(O.1 rad/sec) 4.42 2.37 2.14* Not an example of the present inventiona Not applicableTable 3 shows the blend composition example 4 has a high tensileenergy at break, which significantly exceeds the performance of theunblended interpolymers, comparative examples (A) and (C). Further,the blend retains a level of stress relaxation biased towards theperformance of component (A).Blend example 4 also has a tan 5 value at low shear rates in the(A) andrelated to meltmelt which was lower than either of the component polymers(C). The shear thinning (n(100/0.1] of the blend,processing characteristics,EXAMPLES 5-8was identical to that of component (A).Interpolymer blend component (D) has a significantly lowernumber average molecular weight(Mn) and broader molecular weightdistribution (higher Mw/Mn) compared to the other four interpolymers,(A), (B), (C) and (E). Interpolymer blend component (D) has adifferent styrene content to interpolymers (A) and (C), and anessentially similar styrene residue content to interpolymer (E),differing by only 3 mol. percent.-13-101520WO 98110018CA 02264731 1999-03-03PCT/US97/15546Blends were prepared from interpolymer (D) and interpolymers(A), (C) and (E) in a 10/90 weight ratio of components to giveexamples 5, 6 and 7 respectively, and from interpolymers (D) and (C)in a 30/70 weight ratio of components to give example 8, according tothe same procedure employed in examples 1-3.The characterization data for the blend examples and theinterpolymer components was presented in table 4.Table 4 shows that blend component interpolymer, and comparativeexample, (D) was a low viscosity polymer with low tensile energy tobreak.Table 4Example or Comparative Experiment No.(A) * (C) * (D)* (E) * 5 6 7 8Blend 100% 100% 100% 100% (D)/( (D)/( (D)/( (D)/(Composition, wt (A) (C) (D) (E) A) E) C) C)ratio 10/90 10/90 10/90 30/70styrene residuemole% difference N/AC N/A° N/A° N/A° 21.4 3 6.5 6.5% Mn difference N/A“ N/A“ N/A” N/A° 1,126 965 768 768Mechanical PropertiesShore A 96 88 78 76 95 73 84 82Tensile Modulus, 594.3 20 19.3 6.8 550.9 8.3 24.8 20.7MPaFlexural 617.1 62.1 84.8 140.7 96.5 28.3 64.1 51Modulus, MPaYield Stress,MPa 5.6 2.4 2.3 1.5 4.8 1.3 2.4 2.2% Strain @ Break 257.8 377.5 412.8 337.8 260.6 475.8 372.3 452.4Stress @ Break, 21.5 34.3 2.5 17.4 24.9 22.7 25 28.4MPaTensile Energy @ 118.5 145.5 33.9 73.2 125.2 118 126 150.4Break, N°m% Stress 92.9 30.2 43.2 26.2 90.9 33.4 30.1 32.8RelaxationMelt Rheologynx10”(0.1 6.53 16.6 b 31 4.25 12 4.15 5.3rad/sec)n (100/0.1) 0.048 0.16 b 0.038’ 0.052 0.066 0.043 0.046Tan 5 (0.1 4.42 2.37 b 1.26 4.44 2.33 2.61 3.74rad/sec)* Not an example of the present inventiona n(100/3.98)b Could not be measuredc Not applicableBlend examples 5, 6, 7 and 8 all show that even low additions of(D) brings very large reductions in viscosity [nx10-5(0.l rad/sec) for(A), (C) and (E).enhancing the mechanical properties of interpolymers (A), (C)interpolymers This was achieved whilst retaining orand (E),as was clearly shown by the tensile energy to break data, and stressrelaxation behavior.-19-10152025303540W0 98/10018CA 02264731 1999-03-03PC17US97fl5546Preparation of Interpolymers F, G, H, I,& JReactor DescriptionThe single reactor used was a 6 gallon (22.7 L),(CSTR).coupled agitator with Lightning A—32O impellers provides the mixing.(3,275 kPa).A heat transfer oil was circulatedoil jacketed,Autoclave continuously stirred tank reactor A magneticallyThe reactor ran liquid full at 475 psig Process flow wasin the bottom and out the top.through the jacket of the reactor to remove some of the heat ofreaction. After the exit from the reactor was a micromotion flowmeter that measured flow and solution density. All lines on the exitof the reactor were traced with 50 psi (344.7 kPa) steam andinsulated.ProcedureSolvent, ethylbenzene unless stated, was supplied to the mini-(207 kPa).Micro-Motion mass flow meter.plant at 30 psig The feed to the reactor was measured by aA variable speed diaphragm pumpcontrolled the feed rate. At the discharge of the solvent pump a sidestream was taken to provide flush flows for the catalyst injection(1 lb/hr (0.45 kg/hr)) (0.75 lb/hr (0.34 kg/ hr)). These flows were measured by differential pressureflow meters and controlled by manual adjustment of micro-flow needleline and the reactor agitatorvalves. Uninhibited styrene monomer was supplied to the mini—plant at(207 kpa).Motion mass flow meter.30 psig The feed to the reactor was measured by a Micro-A variable speed diaphragm pump controlledthe feed rate. The styrene stream was mixed with the remainingsolvent stream.(4,137 kPa).flow meter just prior to the Research valve controlling flow. AEthylene was supplied to the mini—plant at 600 psigThe ethylene stream was measured by a Micro-Motion massBrooks flow meter/controllers was used to deliver hydrogen into theethylene stream at the outlet of the ethylene control valve. Theethylene/hydrogen mixture combines with the solvent/styrene stream atambient temperature. The temperature of the solvent/monomer as itenters the reactor was dropped to ~5 °C by an exchanger with —5°Cglycol on the jacket. This stream entered the bottom of the reactor.The three component catalyst system and its solvent flush also enterthe reactor at the bottom but through a different port than themonomer stream. Preparation of the catalyst components (catalyst;mixed alkyl aluminoxane(M—MAO); methyl dialkyl ammonium salt oftetrakis pentafluoroaryl borate) took place in an inert atmosphereglove box. The diluted components were put in nitrogen paddedcylinders and charged to the catalyst run tanks in the process area.From these run tanks the catalyst was pressured up with piston pumps-20-10152025WO 98110018CA 02264731 1999-03-03PCTIUS97/15546and the flow was measured with Micro—Motion mass flow meters. Thesestreams combine with each other and the catalyst flush solvent justprior to entry through a single injection line into the reactor.Polymerization was stopped with the addition of catalyst kill(water mixed with solvent) into the reactor product line after themicromotion flow meter measuring the solution density. Other polymeradditives can be added with the catalyst kill. A static mixer in theline provided dispersion of the catalyst kill and additives in thereactor effluent stream. This stream next entered post reactorheaters that provide additional energy for the solvent removal flash.This flash occured as the effluent exited the post reactor heater andthe pressure was dropped from 475 psig (3,275 kPa) down to ~250mm ofThis flashedApproximately 85pressure absolute at the reactor pressure control valve.polymer entered a hot oil jacketed devolatilizer.percent of the volatiles were removed from the polymer in thedevolatilizer. The volatiles exit the top of the devolatilizer. Thestream was condensed and with a glycol jacketed exchanger, entered thesuction of a vacuum pump and was discharged to a glycol jacket solventand styrene/ethylene separation vessel. Solvent and styrene wereremoved from the bottom of the vessel and ethylene from the top. Theethylene stream was measured with a Micro-Motion mass flow meter andanalyzed for composition. The measurement of vented ethylene plus acalculation of the dissolved gasses in the solvent/styrene stream wereused to calculate the ethylene conversion. The polymer seperated inthe devolatilizer was pumped out with a gear pump to a ZSK-30devolatilizing vacuum extruder. The dry polymer exits the extruder asa single strand. This strand was cooled as it was pulled through awater bath. The excess water was blown from the strand with air andthe strand was chopped into pellets with a strand chopper.-21-CA 02264731 1999-03-03PCTIUS97/15546W0 98l10018.m wanme CH cm>Hm mum: mcofluflmoaeoo Ucmfln Ucm mgzwcoasou Ucman mcu mo >umEE:m <$z_$u5-$u£8 2 Sam: z$82tmzmu-m£_.w:wNcwnH>Lum mo Ummumca ucw>a0m ®C®5HO# nuwz mvma mm:vmum mmaafimxm"um>Hmumu .SSH maze 42$22.-3m£z-828L.mmo-m :.T£»m-£8 LQSSS Em.mw mo.v o.m o.m. mm.H o.m »o.NH m.mm m.moH oowaumaaamm nibm.»m mv.v m.m o.> mm.o H.m ¢m.~H m.mN >.mm oomouwmflaom RBHm.Hm »>.v m.o~ o.»fi mH.H m.m mm.NH m.mm m.mm oovouvmmomm .:mm.mm mv.m o.mH o.Na >».o >.H vv.w w.ma N.om oovaummmoom _:op.mm mo.m o.om o.m nv.o o.H Nn.m m.mH v.Ho oomaummwonm ¢:.mmmEfiomW 5:3 E): zoom fit? 2}: Eli 23: U0 mainzoam.>coo zoam ammo 30am 30am .mEmHucm> mcmuxum nun»: m:wa>zum .>aom uouomwmm magmam -22-CA 02264731 1999-03-03PCT/U S97/ 15546W0 98/10018mdm W3; o.mm mmm mam mm E ~.Z\m.om m N; mm?» w\n nowwho mam «.3 mmm mam vm om m.m~\v.om m N6 onion mi, "3«.3 m;.m >4. mum W3 mp mm o.R\m.om m m4 flkmm w\m um:who H43 Tom 2% mm mm on w.m$.mw 3...? Ham 335 mi "S7? W3 5S 9? mam 3 mp «$3.8 Wm- mqm om\om mi "3m.mm N42: m.S mvm m.mm mm mm. m.m\~.$ m.oT 53 2.3.5. EH :393 T2; m.m~ mmm m.om om mu m.3§.$ m m; 33» oh "3m.mm m.mm m.vH pmm m.om up we m.oH\m.mm m m om\on o\H "ma7% Hév m.m mm» 73 mm mm o.3\m.nm m m.N mimm wfi “NHmam mam H.» 3% m.mN om mm mxc wa om vmkumxmm :82 "Smam W2 W3 com m.vm 3 mm 3; m;.. mam om\om Em "3Hém 92. W3 Sm W2 8 8 3: ma w.om omxom mi um.m\~\H.mucwcomfiouSui ofimu vcmdmcowuwmomaou ".02 oamfimxmm.om 7:3 Tom Sm m.om 3 mm m.mm\m.om nmoun mam Bmdm mama mam mom Tam mm m» m.mH\m.$ m.m- m.mm .HTom 53” N 33 v 8 mm 3: ma- mm .mme man mA 33 m E 3 En Tm mém .wTmm >42. 3 mam mama 3 mm 3: mam \..m> Lw £33 $2 w $2 dflx o nucunomaoummmflm 52 5m 53. 3: .303 6oz xwfl m Scam uo £29 foo :5. doe u 43 $8 mfg 9Ø3m magma-23-CA 02264731 1999-03-03PCTIUS97l15546WO 98/10018.wanmoflHaQm uoc umxc.EsuuomQm mmoa mzo cfl me now xmwa Umoun no uwvanonm um.cowuwwomEoo Ucman ou uommmou SUHZ Umuwameuoc u>uHcfiaHmum>uu w "a>ux.me now xmwa mmoa w emu cw Eafiflxme uAmzQV>QoomouuomQm Hmuwcmnoma uflemcxv Eouu Uwgsmmwe "ma.:oHucm>:H ucwmmnm mnu mo mwaafimxw uoz «m.om v.Nm m.~H Nav m.oN om H» H.NN\«.mw m.m- m.mN vmxmmxmm m\m\n nvmm.mm v.mam >.>N mam ~.mm mm mm o.mm\m.om m ».~m mmxmp mxb "mmm.»» mma H.mH mcv m.Nv ma mm o.Nm\>.om m p.mN omxom m\n “mmm.>w ~.moH m.oH mmm v.mN mm mm H.H~\m.mm m m.Hm mhxmm mxn "Hmu.ucou m magma10152025303540WO 98/10018CA 02264731 1999-03-03PCT/US97/15546Interpolymer F is an ethylene/styrene interpolymer whichcontains 41.8 mole (72.7 wt.) percent copolymerized styrene in theinterpolymer, 9.1 wt. percent of atactic polystyrene and has an I2melt index of 2.5, and a melt index ratio Im/I2 of 10.1Interpolymer G is an ethylene/styrene interpolymer whichcontains 26.7 mole (57.5 wt.) percent copolymerized styrene in theinterpolymer, 3.5 wt. percent of atactic polystyrene and has an I2melt index of 1.0, and a melt index ratio Im/I2 of 7.6Interpolymer H is an ethylene/styrene interpolymer whichcontains 22.6 mole (52 wt.) percent copolymerized styrene in theinterpolymer, 1.8 wt. percent of atactic polystyrene and has an I2melt index of 1.0, and a melt index ratio Im/I3 of 7.4Interpolymer I is an ethylene/styrene interpolymer whichcontains 12.8 mole (35.3 wt.) percent copolymerized styrene in theinterpolymer, 8.6 wt. percent of atactic polystyrene and has an I2melt index of 1.1, and a melt index ratio Im/I2 of 7.6Interpolymer J is an ethylene/styrene interpolymer whichcontains 6.6 mole (20.9 wt.) percent copolymerized styrene in theinterpolymer, 7.7 wt. percent of atactic polystyrene and has an I2melt index of 1.0, and a melt index ratio IN/I2 of 8.0The blend examples of Table 6 further illustrate the utility andunique property balances which can be achieved by blending ofInterpolymers.Blends 9, 10 show two distinct glass transition processes fromdynamic mechanical testing, combined with high tensile energy at breakand a level of stress relaxation biased towards the performance of(E).Blend 11 shows two distinct glass transition processes fromcomponentdynamic mechanical testing, reflecting the miscibility of components Gand H giving a single Tg peak, with component F being present as aseparate phase. This blend retains good mechanical properties and highstress relaxation.Blends 12-17 show either a broad temperature range for Tg, ortwo distinct Tg processes, combined with high tensile energies atbreak and unexpected levels of stress relaxation compared to what maybe anticipated from the component polymers.Blends 18-23 further illustrate that good thermal performance,as evidenced by TMA probe penetration, can be achieved whilstretaining good mechanical properties and high stress relaxationbehavior.-25-

Claims (14)

CLAIMS:

1. A blend of polymeric materials characterized by a plurality of interpolymers, each interpolymer resulting from polymerizing:
(1) from 1 to 65 mole percent of either (a) at least one vinylidene aromatic monomer or (b) at least one hindered aliphatic or cycloaliphatic vinylidene monomer, or (c) a combination of at least one vinylidene aromatic monomer and at least one hindered aliphatic or cycloaliphatic vinylidene monomer, and (2) from 35 to 99 mole percent of at least one aliphatic alpha olefin having from 2 to 20 carbon atoms; and (3) from 0 to 10 mole percent of at least one polymerizable olefin monomer different from (2); and wherein:
(i) the amount of vinylidene aromatic monomer residue and/or hindered aliphatic or cycloaliphatic vinylidene monomer residue in any interpolymer differs from that amount in any other interpolymer) by at least 0.5 mole percent; and/or (ii) there is a difference of at least 20 percent between the number average molecular weight (Mn) of each interpolymer component.

2. A blend of claim 1, wherein each of the interpolymer components result from polymerizing:
(1) from 1 to 65 mole percent of either (a) at least one vinylidene aromatic monomer or (b) at least one hindered aliphatic or cycloaliphatic vinylidene monomer, or (c) a combination of at least one vinylidene aromatic monomer and at least one hindered aliphatic or cycloaliphatic vinylidene monomer, and (2) from 35 to 99 mole percent of at least one aliphatic alpha olefin having from 2 to 12 carbon atoms; and (3) from 0 to 10 mole percent of at least one polymerizable olefin monomer different from (2); and wherein:
(i) the amount of vinylidene aromatic monomer residue and/or hindered aliphatic or cycloaliphatic vinylidene monomer residue in any interpolymer component differs from that amount in another interpolymer component by at least 1 mole percent;
and/or (ii) there is a difference of at least 30 percent between the number average molecular weight (Mn) of each interpolymer component.

3. A blend of claim 1, wherein each of the interpolymer components result from polymerizing a composition comprising:
(1) from 1 to 65 mole percent of styrene and (2) from 35 to 99 mole percent of ethylene or a combination of ethylene and at least one higher aliphatic alpha olefin having from 3 to 12 carbon atoms; and wherein:
(i) the amount of styrene residue in any interpolymer component differs from that of another interpolymer component by at least 2 mole percent; and/or (ii) there is a difference of at least 40 percent between the number average molecular weight(Mn) of each interpolymer component.

4. A blend of claim 1, wherein each of the interpolymer components results from polymerizing:
(1) from 1 to 65 mole percent of styrene and (2) from 35 to 99 mole percent of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene wherein:
(i) the amount of styrene residue in any interpolymer component differs from that amount in another interpolymer component by at least 0.5 mole percent; and/or (ii) there is a difference of at least 20 percent between the number average molecular weight(Mn) of each interpolymer component.

5. A blend of claim 1, wherein each of the interpolymer components results from polymerizing:
(1) from 1 to 65 mole percent of styrene and (2) from 35 to 99 mole percent of ethylene; or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene wherein:
(i) the amount of styrene residue in any interpolymer component differs from that in another interpolymer component by at least 1 mole percent; and/or (ii) there is a difference of at least 30 percent between the number average molecular weight(Mn) of interpolymer components.

6. A blend of claim 1, wherein each of the interpolymer components results from polymerizing:
(1) from 1 to 65 mole percent of styrene and (2) from 35 to 99 mole percent of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene; and wherein:
the amount of styrene residue in any interpolymer component differs from that amount in another interpolymer component by from 2 to less than 10 wt. percent, such blends exhibiting a single glass transition temperature (Tg) similar in form to, but in the temperature range between the Tg's of the individual interpolymer components as measured by dynamic mechanical spectroscopy.

7. A blend of claim 1, wherein each of the interpolymer components results from polymerizing:
(1) from 1 to 65 mole percent of styrene and (2) from 35 to 99 mole percent of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene wherein:
the amount of styrene residue in any interpolymer component differs from that amount in another interpolymer component by greater than 10 wt.%, such blend compositions exhibiting a broadened single glass transition temperature range, or exhibiting two or more glass transition temperatures as measured by dynamic mechanical spectroscopy.

8. A blend of claim 1, comprising three or more interpolymer components resulting from polymerizing:
(1) from 1 to 65 mole percent of styrene and (2) from 35 to 99 mole percent of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene wherein:
wherein the overall blend composition exhibits a broadened single glass transition temperature range, or exhibits two or more distinct glass transition temperatures as measured by dynamic mechanical spectroscopy.

9. A blend of any of claims 1-8 wherein the interpolymer components are produced by copolymerization of two or more appropriate monomers in the presence of a metallocene catalyst and a co-catalyst.

10. An adhesive or sealant system comprising an interpolymer blend of any one of claims 1-9.

11. Sheet or film resulting from calendering, blowing or casting an interpolymer blend of any one of claims 1-9.

12. Injection, compression, extruded, blow molded, rotomolded or thermoformed parts prepared from an interpolymer blend of any one of claims 1-9.

13. Fibers, foams or latices prepared from an interpolymer blend of any one of claims 1-9.

14. Fabricated articles, or foamed structures prepared from an interpolymer blend of any one of claims 1-9 and finding utility in sound and vibration damping applications.