MXPA99002104A - BLENDS OF&agr;-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

MIXES OF INTERPO IMEROS OF α-OLEFINA / AROMATIC MONOMER OF VINYLIDENE AND / OR MONOMER OF ALIPHATIC OR CICLOALIFATICO VINYLIDENE IMPEDED The present invention pertains to mixtures of interpolymers of α-olefin / vinylidene aromatic monomer and / or aliphatic or cycloaliphatic hindered vinylidene monomer, having different content of vinylidene aromatic monomer and / or hindered aliphatic or cycloaliphatic vinylidene monomer, or different molecular weight, or both different content of aromatic monomer of vinylidene and / or aliphatic or cycloaliphatic vinylidene ramonomer hindered as different molecular weight. The components of the mixture are selected to provide superior performance and processability in the blends. The generic class of materials covered by substantially random interpolymers of α-olefin / hindered vinylidene monomer, and including materials such as α-olefin interpolymers / aromatic vinyl monomer, are known in the art and offer a range of structures of material and properties that make them useful for different applications, such as compatibilizers for blends of polyethylene and polystyrene, as described in U.S. Patent Number US 5,460,818: A particular aspect described by D'Anniello et al. (Journal of Applied Polymer Science, Volume 58, pages 1701-1706 [1995], is that these interpolymers can show good elastic properties and energy dissipation characteristics.) In another aspect, interpolymers selected may find utility in adhesive systems, as illustrated in U.S. Patent Number 5,244,996, issued to Mitsui Petrochemical Industries Ltd. Although they are to be used in their own right, the industry is constantly seeking to improve the applicability of these interpolymers These improvements can be made by means of additives or the like, but it is desirable to develop technologies to provide improvements in processability and / or operation, without the addition of additives, or other improvements that can be achieved with the addition of additives. the date, the possible advantages of mixing for proportion of Onar materials with superior properties. There is a need to provide mixtures of α-olefin / aromatic vinylidene monomer interpolymers, with superior performance characteristics, which expand the usefulness of this interesting class of materials. The present invention pertains to a mixture of polymeric materials characterized by a plurality of interpolymers, each polymerization interpolymer resulting in: (1) from 1 to 65 mole percent of: (a) at least one aromatic vinylidene monomer, or (b) at least one aliphatic or cycloaliphatic hindered vinylidene monomer, or (c) a combination of at least one aromatic vinylidene monomer and at least one aliphatic or cycloaliphatic vinylidene monomer prevented, and (2) 35 to 99 percent molar of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; Y (3) from 0 to 10 mole percent of at least one polymerizable olefin monomer different from (2); and wherein each of the interpolymer blend components are different because: (i) the amount of vinylidene aromatic monomer residue and / or aliphatic or cycloaliphatic vinylidene monomer residue prevented in any interpolymer, differs from the 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) in any interpolymer and in any other interpolymer.

The mixtures of the present invention may comprise, consist essentially, or consist of any two or more of these interpolymers mentioned herein. In the same way, the interpolymers may comprise, consist essentially, or consist of any two or more of the aforementioned polymerizable monomers. These blends provide an improvement in one or more of the properties of the polymer, such as mechanical operation and / or melt processability. The percentage difference in the comonomer content (vinylidene aromatic monomer residue and / or aliphatic or cycloaliphatic vinylidene monomer residue prevented) between the interpolymers of the mixtures of the present invention is determined by subtracting the comonomer content of the interpolymer with the lowest comonomer content from the interpolymer with the highest comonomer content. In cases where more than two interpolymers are used in the mixture, the difference percentage is determined for combination of two polymers, for example, for a mixture of the interpolymers A, B and C, and the determination is made for the combinations : A and B, A and C, and B and C. The percentage difference in Mn_ between the interpolymers in the mixtures of the present invention, is determined by subtracting the Mn from the interpolymer with the lowest Mn, from the interpolymer with the Mn. higher, and dividing the difference with the Mn of the interpolymer with the lowest Mn, and then multiplying by 100. In cases where more than two interpolymers are used in the mixture, the difference percentage is determined for each combination of two Polymers, for example, for a mixture of the interpolymers A, B and C, the determination is made for the combinations: A and B, A and C, and B and C. The term "hydrocarbyl" means any aliphatic, cycloaliphatic group, aromatic co, aliphatic substituted by aryl, cycloaliphatic substituted by aryl, aromatic substituted by aliphatic, or aromatic substituted by cycloaliphatic. The aliphatic or cycloaliphatic groups are preferably saturated. In the same way, the term "hydrocarbyloxy" means a hydrocarbyl group having an oxygen bond between it and the carbon atom to which it is attached. The term "plurality", as used herein, means two or more. The term "interpolymer" is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc. The term "substantially random" in the substantially random interpolymer resulting from the polymerization of one or more monomers of α-olefin, and one or more vinylidene aromatic monomers or aliphatic or hindered cycloaliphatic vinylidene monomers, and optionally with other monomers Polymerizable ethylenically unsaturated, as used herein, means that the distribution of the monomers of this interpolymer can be described by the Bernoulli statistical model, or by a first-order or second-order statistical model of Sea, as described by JC. Randall in POLYMER SEOUENCE DETERMINATION, Carbon-13 NMR Method, Academic Press, New York, 1977, pages 71-78. Preferably, the substantially random interpolymer resulting from the polymerization of one or more α-olefin monomers, and one or more aromatic vinylidene monomers, and optionally with other polymerizable ethylenically unsaturated monomers, does not contain more than 15 percent of the amount total residue of vinylidene aromatic monomer in aromatic vinylidene monomer blocks of more than 3 units. More preferably, the interpolymer is not characterized by a high degree of isotacticity or syndiotacticity. This means that in the carbon-13 nuclear magnetic resonance spectrum of the substantially random interpolymer, the peak areas corresponding to the methylene and methine carbons of the main chain they represent, whether dyadic meso sequences or racemic dyadic sequences, should not exceed 75 percent of the total peak area of methylene and methine carbons in the main chain. Any numerical values mentioned herein include all values, from the lowest value to the highest value in increments of one unit, with the understanding that there is a separation of at least two units between any lower value and any higher value. As an example, it is reported that the amount of a component or a value of a process variable, such as, for example, temperature, pressure, time, is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as from 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc., are expressly listed in this specification. For values that are less than 1, a unit is considered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These are only examples of what is specifically intended, and it should be considered that all possible combinations of numerical values between the lowest value and the highest value listed, will be specifically mentioned in this application in a similar manner. The interpolymers employed in the present invention include, but are not limited to, substantially random interpolymers prepared by the polymerization of one or more α-olefin monomers, with one or more vinylidene aromatic monomers and / or one or more monomers of vinylidene aromatics or hindered cycloaliphatics, and optionally with other polymerizable ethylenically unsaturated monomers. Suitable α-olefin monomers include, for example, α-olefin monomers containing from 2 to 20, preferably from 2 to 12, and more preferably from 2 to 8 carbon atoms. Preferred monomers include ethylene, propylene, butene-1,4-methyl-1-pentene, hexane-1 and octene-1. More ethylene or a combination of ethylene with α-olefins of 2 to 8 carbon atoms are preferred. These α-olefins do not contain an aromatic fraction. Suitable vinylidene aromatic monomers that can be used to prepare the interpolymers used in the mixtures include, for example, those represented by the following formula: Ar (CH2) n R1 - C = C (R2) 2 wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from j. group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group, or a phenyl group substituted by 1 to 5 substituents selected from the group consisting of halogen, alkyl of 1 to 4 carbon atoms, and haloalkyl of 1 to 4 carbon atoms; and n has a value of zero to 4, preferably zero to 2, more preferably zero. Exemplary monovinylidene aromatic monomers include styrene, vinyltoluene, α-methylstyrene, tertiary butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable monomers include styrene and derivatives substituted by lower alkyl or by halogen thereof. Preferred monomers include styrene, α-methylstyrene, derivatives substituted by lower alkyl- (1 to 4 carbon atoms), or by styrene phenyl ring, such as, for example, ortho-, meta-, and para- methylstyrene, halogenated ring styrenes, para-vinyltoluene, or mixtures thereof. A most preferred aromatic monovinylidene monomer is styrene. The term "aliphatic or hindered cycloaliphatic vinylidene compound" means addition polymerizable vinylidene monomers corresponding to the formula: AJ R1 - C = C (RZ) wherein A1 is a sterically bulky aliphatic or cycloaliphatic substituent of up to 20 carbon atoms, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system. The term "sterically bulky" means that the monomer carrying this substituent is usually unable to have addition polymerization by conventional Ziegler-Natta polymerization catalysts at a rate comparable to ethylene polymerizations. A-olefin monomers containing from 2 to 20 carbon atoms, and having a linear aliphatic structure, such as propylene, butene-1, hexene 1 and octene-1 are not considered as hindered aliphatic monomers. Preferred aliphatic or cycloaliphatic hindered vinylidene compounds are monomers in one of the carbon atoms bearing ethylenic unsaturation is substituted by tertiary or quaternary. Examples of these substituents include cyclic aliphatic groups, such as cyclohexyl, cyclohexenyl, cyclooctenyl, or substituted alkyl or aryl ring thereof, tertiary butyl, norbornyl. The most preferred aliphatic or cycloaliphatic hindered vinylidene compounds are the different isomeric vinyl ring substituted derivatives of cyclohexene, and substituted cyclohexenes and 5-ethylidene-2-norbornene. 1-, 3- and 4-vinylcyclohexene are especially suitable. Other optional polymerizable ethylenically unsaturated monomers include stretched ring de? Ns, such as norbornene and norbornenes substituted by alkyl of 1 to 10 carbon atoms, or by aryl of 10 to 6 carbon atoms, an ethylene / styrene / norbornene interpolymer being exemplary. The number average molecular weight (Mn) of the polymers and interpolymers is usually greater than 5,000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000. Polymerizations and removal of unreacted monomer at temperatures higher than 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. For example, while preparing the substantially random interpolymer, an amount of atactic vinylidene aromatic homopolymer may be formed, due to the homopolymerization of the aromatic vinylidene monomer at elevated temperatures. The presence of aromatic vinylidene homopolymer in general is not detrimental to the purposes of the present invention, and can be tolerated. The vinylidene aromatic homopolymer can be separated from the interpolymer, if desired, by extraction techniques, such as selective precipitation from the solution with a non-solvent for the interpolymer or the aromatic vinylidene homopolymer. For the purpose of the present invention, it is preferred that no more than 20 weight percent, preferably less than 15 weight percent, is present, based on the total weight of the aromatic vinylidene homopolymer interpolymers. The substantially random interpolymers can be modified by typical grafting, hydrogenation, functionalization or other reactions well known to those skilled in the art. The polymers can be easily sulfonated or chlorinated to provide functionalized derivatives according to established techniques. Substantially random interpolymers can be prepared as described in U.S. Patent Application Number 07 / 545,403, filed July 3, 1990 (corresponding to European Patent EP-A-0,416,815) by James C. Stevens and collaborators, and in U.S. Patent Application Number 08 / 469,828, filed June 6, 1995, all of which are hereby incorporated by reference in their entirety. The preferred operating conditions for these polymerization reactions are pressures from atmospheric to 3,000 atmospheres, and temperatures from -30 ° C to 200 ° C. Examples of suitable catalysts and methods for the preparation of substantially random interpolymers are disclosed in U.S. Patent Application Number 07 / 545,403, filed July 3, 1990, which corresponds to the Patent. European Number EP-A-416, 815; in U.S. Patent Application Number 07 / 702,475, filed May 20, 1991, which corresponds to European Patent Number EP-A-514, 828; in U.S. Patent Application Number 07 / 876,268, filed May 1, 1992, which corresponds to European Patent EP-A-520, 732; in U.S. Patent Application Number 08 / 241,523, filed May 12, 1994; as well as the Patents of the United States of North America Nos. 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,189,193; 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 and applications are incorporated herein by reference in their entirety. The substantially random vinylidene aromatic α-olefin / monomeric interpolymers can also be prepared by the methods described by Bradfute et al. (R.R. Grace &Co.) in International Patent Number WO 95/32095; by R.B. Pannell (Exxon Chemical Patents, Inc.) in International Patent WO 94/00500; and in Plastics Technology, page 25 (September 1992), all of which are incorporated herein in their entirety. Also suitable are substantially random interpolymers comprising at least one a-olefin / vinyl aromatic / vinyl aromatic / α-olefin tetrad disclosed in U.S. Patent Application Number 08 / 708,809, filed on September 4, 1996 by Francis J. Timmers et al. These interpolymers contain additional signals with intensities greater than three times the peak-to-peak noise. These signals appear in the range of chemical change 43.75-44.25 ppm and 38.0-38.5 ppm. Specifically, higher peaks are observed at 44.1, 43.9 and 38.2 ppm. A proton test nuclear magnetic resonance experiment indicates that the signals in the region of chemical change 43.75-44.25 ppm are carbons of etin and the signals in the region 38.0-38.5 ppm are methylene carbons. In order to determine the chemical changes of carbon-1 nuclear magnetic resonance of the described interpolymers, the following procedures and conditions are employed. A polymer solution of 5 to 10 weight percent is prepared in a mixture consisting of 50 percent by volume of 1, 1, 2, 3-tetra-chloroethane-d, and 50 percent by volume of tris ( acetylacetonate) of chromium in 1,2,4-trichlorobenzene. Nuclear magnetic resonance spectra are acquired at I30 ° C, using a reverse open decoupling sequence, a 90 ° pulse amplitude, and an impulse delay of five seconds or more. The spectra are referenced to the methylene signal isolated from the assigned polymer at 30,000 ppm. It is believed that these new signals are due to sequences involving two vinyl aromatic monomers from head to tail preceded and followed by at least one α-olefin insert, for example, an ethylene / styrene / styrene / ethylene tetradic, in where the insertions of the styrene monomer of the treradics are presented exclusively in a 1.2 manner (head to tail). It is understood by one skilled in the art that such tetrakics involve a vinyl aromatic monomer other than styrene and an a-olefin other than ethylene, that the ethylene tetrad / vinyl aromatic monomer / vinyl aromatic monomer / ethylene place a similar carbon-13 nuclear magnetic resonance peaks, but with slightly different chemical changes. Interpolymers containing blocked cycloaliphatic ironomer residues are usually prepared by subjecting an interpolymer containing aromatic monomer residues of monovinylidene to hydrogenation thereto, converting some or all of the aromatic rings to cycloaliphatic rings, which may be saturated (e.g. , cyclohexane ring) or unsaturated (cyclohexene ring). The interpolymers of one or more α-olefins, and one or more aromatic monovinylidene numbers and / or one or more vinylidene aliphatic or hindered cycloaliphatic monomers employed in the present invention are substantially random polymers. These interpolymers typically contain from 0.5 to 65, preferably from 1 to 55, and more preferably from 2 to 50 mole percent of at least one aromatic vinylidene monomer and / or a hindered aliphatic or cycloaliphatic vinylidene monomer, and from 99.5, preferably from 45 to 99, more preferably from 50 to 98 mole percent of at least one aliphatic α-olefin having from 2 to 20 carbon atoms. These interpolymers are prepared by conducting the polymerization at temperatures of -30 ° C to 250 ° C, in the presence of catalysts, such as those represented by the formula: _ / \ (ER2) m MR'2 wherein: each Cp is independently, and each presentation, a substituted cyclopentadienyl group linked by 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 in each presentation H, hydrocarbon, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms or silicon; each R 'is independently in each presentation, h, halogen, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms, or two R1 groups may together being 1, 3-butadiene substituted by hydrocarbyl of 1 to 10 carbon atoms; m is 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst. In particular, suitable substituted cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, in each presentation, H, hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, containing up to 30, preferably from 1 to 20, more preferably from 1 to 10 carbon or silicon atoms, or two R groups formed together a bivalent derivative of this group. Preferably, R, independently in each presentation is (including where all isomers are appropriate) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl, or (where appropriate) two of these R groups are linked together, forming a fused ring system, such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl or octahydrofluorenyl. Particularly preferred catalysts include, for example, racemic ((dimethylsilandiyl) bis (2-methyl-4-phenylindenyl)) zirconium dichloride, ((dimethylsilandiyl) bis (2-methyl-4-phenylindenyl)) zirconium-1 , Racemic 4-diphenyl-3,3-butadiene, '((dimethylsilandiyl) bis (2-methy-4-phenylindenyl)) zirconium-dialkyl of 1 to 4 racemic carbon atoms, dialkoxide of 1 to 4 carbon atoms of ((dimethylsilandiyl) bis (2-methyl-4-phenylindenyl)) zirconium racemic, or any combination thereof. Other methods of preparation for the interpolymer components of the present invention have been described in the literature. Longo and Grassi (Makromol, Chem., Volume 191, pages 2387 to 2396 [1990]), and D'Anniello et al. (Journal of Applied Polymer Science, Volume 58, pages 1701-1706 [1995]), reported the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCl3) to prepare an ethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am. Che. Soc., Div. Polyro. Chem.), Volume 35, pages 686, 687 (1994)), have reported copolymerization using an MgCl 2 / TiCl 4 / NdCl 3 / Al catalyst ( iBu) 3 to give random copolymers of styrene and propylene. Lu et al. ('Journal of Applied Polymer Science, Volume 53, pages 1453 and 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCl 4 / NdCl 3 / MgCl 2 / Al (Et) 3 catalyst. Sernetz and Mulhaupt, (Macro ol. Chem. Phys., Volume 197, pages 1071-1083, 1997) have described the influence of polymerization conditions on the copolymerization of styrene with ethylene using Ziegler-Natta catalysts of Me2Si (Me4Cp) (Tertiary N-butyl ) TiCl2 / methylaluminoxane. The manufacture of α-olefin / aromatic vinyl monomer interpolymers, such as propylene / styrene and butene / styrene is described in the U.S. Patent Number ,244,996, issued to Mitsui Petrochemical Industries Ltd. The present invention provides mixtures of interpolymer components of molecular weight and composition distributions selected to obtain an overall molecular weight and a composition distribution that gives better properties or processability. The mixing components of the interpolymer are different because: (i) the amount of vinylidene aromatic monomer residue and / or residue of aliphatic or cycloaliphatic vinylidene monomer residue prevented in any interpolymer component, differs from each other by at least 0.5 mole percent, preferably by at least 1 mole percent, and more preferably by 2 mole percent; I (ii) there is a difference of at least 20 percent, preferably at least 30 percent, and more preferably at least 40 percent between the number average molecular weight (Mn) of the interpolymer components. In one embodiment, the components for the mixture are interpolymers having a relatively narrow molecular weight distribution, with Mw / Mn < 3.5. Using these interpolymers as components, the invention provides interpolymers having a plurality mode with respect to the comonomer residue content, and a narrow molecular weight distribution, such as Mw / Mn < 3.5. In another aspect, the invention provides interpolymers having a plurality modality with respect to molecular weight, such that Mw / Mn < 3.5, and produced from interpolymers of components that have essentially the same comonomer residue content. In yet another aspect, the invention provides interpolymers having a plurality with respect to both the molecular weight distribution, such that Mw / Mn < 3.5, as those produced from polymers of components that have a difference in the content of the comonomer. A further aspect of the present invention pertains to mixtures comprising two or more substantially random interpolymers of styrene and ethylene, or of styrene and a combination of ethylene and one or more different polymerizable monomers, wherein the components of the substantially random interpolymer have a difference in the styrene content from 2 to less than 10 weight percent. These mixtures can be considered miscible, because these mixtures exhibit a single glass transition temperature (Tg) similar in form a, but on the temperature scale between the glass transition temperatures of the individual polymers. These mixing compositions are particularly suitable, for example, to optimize processability. Another aspect of the present invention pertains to mixtures comprising two or more substantially random interpolymers of styrene and ethylene, or of styrene and a combination of ethylene and one or more other polymerizable monomers, wherein the components 1 of the interchanger are optionally random. difference in styrene content greater than 10 percent by weight. These mixing compositions can be considered as immiscible mixtures, because they exhibit a scale of a single extended glass transition temperature, or exhibit two or more glass transition temperatures that reflect the behavior of the individual polymers. These blends are particularly suitable for applications that include those that require energy absorption over specific temperature scales, such as sound and vibration damping. Mixture compositions comprising three or more components are also contemplated, wherein two or more components show a miscible behavior, using the criteria of the glass transition temperature, but the overall blend composition exhibits a scale of a single temperature scale. Transition of expanded glass, or exhibits two or more different glass transition temperatures. The mixtures of the present invention can be prepared by any suitable element known in the art, such as, but not limited to, dry blending in a granulated form in the desired proportions, followed by melt blending in a screw extruder, in a Banbury mixer or similar. The dry-mixed granules can be melt processed directly to the solid article of the final state, by, for example, injection molding. Alternatively, the mixtures can be made by direct polymerization, without isolation of the components of the mixture, using, for example, two or more catalysts in a reactor, or by using a single catalyst and two or more reactors in the reactor. series in parallel. Additives can also be included, such as antioxidants (e.g., hindered phenols, such as, for example, IRGANOX® 1010), phosphites (e.g., IRGAFOS® 168), ultraviolet stabilizers, adhesion additives (e.g., polyisobutylene), anti-blocking additives. , skimming agents, colorants, pigments, fillers, in the interpolymers employed in the blends of the present invention, to the extent that they do not interfere with the improved properties discovered by the Applicants. The additives are used in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant employed is the amount that prevents the polymer or polymer mixture from undergoing oxidation at the temperatures and in the environment employed during the storage and final use of the polymers.

These amounts of antioxidants are usually in the range of 0.01 to 10, preferably 0.05 to 5, more preferably 0.1 to 2 weight percent, based on the weight of the polymer or polymer blend. In a similar manner, the amounts of any of the other additives mentioned, are the functionally equivalent amounts, such as the amount to make the polymer or the polymer mixture is against blocking, to produce the desired amount of filler loading to produce the desired result, in order to provide the desired color from the dye or the pigment. These additives can be suitably employed in the range of 0.05 to 50, preferably 0.1 to 35, and more preferably 0.2 to 20 percent by weight, based on the weight of the polymer or polymer mixture. However, in the case of fillers, these could be used in amounts up to 90 weight percent, based on the weight of the polymer or the polymer mixture. The blends of the present invention can be used to produce, without limitation, a wide range of manufactured articles, such as, for example, calendered sheet, blown or cast films, injection molded, rotationally molded or thermoformed parts. The mixtures can also be used in the manufacture of fibers, foams and latexes. The mixtures of the present invention can also be used in additive formulations. The following examples are illustrative of the invention, but should not be construed to limit its scope in any way.

EXAMPLES Preparation of Interpolymers A, B, C and E A polymer was prepared in a stirred batch semicontinuous reactor of 1.514 liters. The reaction mixture consisted of about 946 liters of a solvent comprising a mixture of cyclohexane (85 weight percent) and isopentane (15 weight percent), and styrene. Before the cidición, the solvent, the styrene and the ethylene were purified to remove the water and the oxygen. The styrene inhibitor was also removed. The inerts were removed by purging the container with ethylene. The pressure in the vessel was then controlled to a point established with ethylene. Hydrogen was cured to control the molecular weight. The temperature in the container was controlled up to a set time, varying the water temperature of the container liner. Before polymerization, the vessel was heated to the desired execution temperature, and the flow of catalyst components was controlled: titanium: (N, l-dimethylethyl) dimethyl (1- (1, 2, 4, 4, eta) = 2, 3,4,5-tetramet-il-2,4-cyclopentadien-1-yl) silanaminate)) (2-) N) -dimethyl, CAS # 135072-62-7, Tris (pentafluorophenyl) boron , CAS # 001109-15-5, Modified methylaluminoxane Type 3A, CAS # 146905-79-5, on a molar ratio basis of 1/3/5, respectively, were combined, and added to the vessel. After starting, the polymerization was allowed to proceed with ethylene supplied to the reactor as required to maintain the container pressure. In some cases, hydrogen was added to the upper reactor space to maintain a molar ratio to the ethylene concentration. At the end of the run, the catalyst flow was stopped, the ethylene was removed from the reactor, then 1000 ppm of the Irganox ™ 1010 antioxidant was added to the solution, and the polymer was isolated from the solution. The efficiency of the catalyst was generally greater than 100,000 # polymer per # Ti. The resulting polymers were isolated from the solution, either by vapor separation in a vessel, or by the use of a devolatilizing extruder. In the case of the material separated by steam, an optional processing was required in an equipment in the form of an extruder to reduce the residual humidity and any unreacted styrene.

Total weight percentage of styrene residue measured by the Fourier Transform Infrared (FTIR) technique.

Preparation of Interpolymer D Interpolymer D was prepared in the following manner. A 130 milliliter continuous cycle reactor was used, consisting of two static mixers, a transmission pump (1,200 milliliters / minute), inlets for liquids and gases, a viscometer and a pair of thermocouples to prepare the polymer. The reactor temperature it was maintained by external heating tapes. The pressure was monitored at the liquid inlet, and controlled by means of a variable valve at the outlet. The reactor was fed with a mixture of 75 weight percent styrene and 25 weight percent toluene at 12.00 milliliters / minute, ethylene at 0.700 grams / minute, hydrogen at 0.411 milligrams / minute, and a catalyst system composed of toluene solutions 0.001 M tertiary butyl-amidodimethyl (tetramethylcyclopentadiene) silanetitanium dimethyl and tris- (pentafluorophenyl) borane, both at 0.25 milliliters / minute. The reactor temperature was maintained at 100 ° C, and the viscosity was allowed to stabilize at about 15 cP (0.015 Pas «s). The resulting polymer solution was mixed with 0.05 milliliters / minute of a catalyst deactivator / polymer stabilizer solution (1 liter of toluene, 20 grams of Irganox 1010 and 15 milliliters of 2-propanol), cooled to room temperature, and it was collected for 20 hours and 50 minutes. The solution was dried in a vacuum oven overnight, resulting in 750 grams of a styrene-ethylene / styrene residue copolymer at 16.6 mole percent, with 6.5 percent by weight of atactic polystyrene having a higher melt index of 200. Test parts and characterization data were generated for the interpolymers and their mixtures according to the following procedures: Compression Molding; They melted show to 190 ° C for 3 minutes, and compression molded at 190 ° C under a pressure of 20,000 lbs (9,072 kg) for another 2 minutes. Subsequently, the molten materials were quenched in a press balanced at room temperature.

Density; The density of the samples is measured according to ASTM-D792.

Differential Scanning Calorimetry (DSC); It uses a Dupont DSC-2920 to measure thermal transition temperatures and transition heat for interpolymers. In order to eliminate the previous thermal history, the samples were first heated to 200 ° C. Heating and cooling curves were recorded at 10 ° C / minute. The melting (from the second heat) and crystallization temperatures were recorded from the peak temperatures of the endotherm and the exotherm, respectively.

Reclamation of Cutting Effort of the Fusion; Oscillatory shear rheology measurements were made with a Rheometrics RMS-800 rheometer. The rheological properties were monitored at an established isothermal temperature of 190 ° C in a frequency sweep mode.

Dynamic Mechanical Solid State Test; The dynamic mechanical properties of the compression molded samples were monitored using a Rheometrics 800E mechanical spectrometer. The samples were executed in rectangular torsion geometry, and purged under nitrogen to prevent thermal degradation. Typically, the samples were run at a fixed forced frequency of 10 rad / second, using an established torsion tension of 0.05 percent, and collecting the data isothermally at 4 ° C intervals.

Mechanical Test; All properties were generated at 23 ° C. Shore A hardness is measured according to ASTM-D240. The flexural module is evaluated in accordance with ASTM-D790. The tensile properties of the compression molded samples were measured using an Instron 1145 tensile machine equipped with a strain gauge. Samples of ASTM-D638 were tested at a tension rate of 5 min-1. The average of four traction measurements is given. The breaking stress and the breaking traction at the point of inflection were recorded in the tension / traction curve. The energy at break is the area below the voltage / traceion curve.

Tension Relaxation by Traction; The relaxation of uniaxial tensile stress is evaluated using an Instron 1145 tensile machine. The compression molded film (approximately 0.508 millimeters thick), with a caliber length of 1 inch (25.4 millimeters) is deformed to a level of 50 percent traction at a tensile index of 20 in-1. The force required to maintain a 50 percent elongation is monitored for 10 minutes. The magnitude of the stress relaxation is defined as (f1-ff / fi), where f is the initial force, and ff is the final force. The characteristics of each of the interpolymers were given in Table 1. The unmixed interpolymers provide the comparative examples employed herein.

Table 1 a Could not be measured by DSC! b Could not be measured c Measured by nuclear magnetic resonance techniques EXAMPLES 1-3 Preparation of the mixture; Three mixing compositions, Examples 1, 2 and 3, were prepared from the interpolymers (A) and (B) above, in the weight proportions of (A) / (B) of 75/25, 50/50, and 25/75, with a Hakke mixer equipped with a Rheomix 3000 bowl. The components of the mixture were first mixed dry, and then fed to the balanced mixer at 190 ° C. Feeding and temperature balance took 3 to 5 minutes. The molten material is mixed at 190 ° C and at 40 rpm for 10 minutes. The characterization data for the mixtures and interpolymer components are presented in Table 2. The components of the interpolymer mixture (A) and (B) have molecular weights that were significantly different, and a styrene content that differs by 28 percent molar.

Table 2 * It is not an example of the present invention, a Not Applicable Table 2 shows that the mixture composition of Examples 1, 2 and 3, have all high tensile breaking forces, which yield in a significant way the performance of the non-mixed interpolymers, comparative examples (A) and (B). In addition, the mixtures retain an unexpected level of tension relaxation, compared to what can be anticipated from the component polymers. The examples of mixture 1, 2 and 3 also have values as S at low rates of shear stress in the melt, which were significantly lower than those of any of the component polymers (A) and (B). This results in a higher melt elasticity, and in better part forming characteristics under certain melt processing operations.

EXAMPLE 4 A mixture composition, Example 4, was prepared from the interpolymers (A) and (C) in a weight ratio of 50/50 of the components, according to the same procedure used in Examples 1-3. . The characterization data for the mixtures and components of the interpolymer were presented in Table 3.

The mixing components of interpolymer (A) and (C) have molecular weights (Mn) exceeding 100,000, and styrene residue contents differing by 28 mole percent.

Table 3 * Not an example of the present invention a Not applicable Table 3 shows that the Example of the mixture composition 4 has a high breaking tensile energy, which significantly exceeds the performance of the non-mixed interpolymers, examples comparatives (A) and (C). In addition, the mixture retains a level of forced stress relaxation towards the operation of the component (A). Mixture Example 4 also has a value d at low shear rates in the melt, which was lower than that of any of the component polymers (A) and (C). The shear thinning [n (100 / 0.1] of the mixture, related to the melt processing characteristics, was identical to that of component (A).

EXAMPLES 5-8 The mixing component of the interpolymer (D) has a significantly lower number average molecular weight (Mn)., and a wider molecular weight distribution (higher Mw / Mn) compared with the other four interpolymers, (A), (B), (C) and (E). The mixing component of the interpolymer (D) has a styrene content different from the interpolymers (A) and (C), and a styrene residue content essentially similar to that of the interpolymer (E), differing only by 3 percent molar. Mixtures were prepared from the interpo-polymer (D) and interpolymers (A), (C) and (E), in a weight ratio of 10/90 of the components to give Examples 5, 6 and 7 , respectively, and from the interpolymers (D) and (C) in a proportion by weight of 30/70 of the components, to give Example 8, according to the same procedure used in Examples 1 to 3. The data of characterization for the examples of mixtures and components of the interpolymer were presented in Table 4. Table 4 shows that the interpolymer 'of mixture components, and Comparative Example, (D), was a low viscosity polymer with a low tensile energy at break.

Table 4 1 is not an example of the present invention to "(100 / 3.9S) 1) Can not be measured c Not Applicable Examples of blends 5, 6, and 8 all show that even the low additions of (D) cause reductions very large in viscosity [nxl0-5 (0.1 rad / sec) for the nterpolymers (A), (C) and (E) .This was achieved while retaining or improving the mechanical properties of the ..nterpolymers (A ), (C) and (E), as clearly shown by the tensile energy data at break, and the stress relaxation behavior.

Preparation of Interpolymers F, G, H, I and J Reactor Description The only reactor used was a 6 gallon (22.7 liters) oil-jacketed continuously stirred tank reactor (CSTR). A magnetically cyclic agitator with Lightning A-320 propellers provides the mixture. The reactor worked full of liquid at 475 psig (3,275 kPa). The flow of the process was in the background and outward from the top. A heat transfer oil was circulated through the reactor jacket to remove some heat from the reaction. After the exit from the reactor, there was a micromotion flow meter, which measured the flow and density of the solution. All lines at the rector's outlet were steam traced at 50 psi (344.7 kPa), and were isolated.

Procedure Solvent, ethylbenzene was supplied unless otherwise reported to the mini-plant at 30 psig (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 Lateral current was taken to provide evaporation flows for the catalyst injection line (1 lb / hr (0.45 kg / hr)), and the reactor agitator (0.75 lb / hr ( 0.34 kg / hr)). These flows were measured by differential pressure flow meters, and controlled by manual adjustment of microflow needle valves. An uninhibited styrene monomer was supplied to the miniplant at 30 psig (207 kPa). The feed to the reactor was measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controlled the feeding speed. The styrene stream was mixed with the remaining solvent stream. Ethylene was supplied to the mini-plant at 600 psig (4,137 kPa). The ethylene stream was measured by a Micro-Motion mass flow meter just before the Research valve controlled the flow. A Brooks flow meter / controller was used to deliver hydrogen to the ethylene stream at the outlet of the e_tileno control valve. The ethylene / hydrogen mixture is combined with the solvent / styrene stream at room temperature. The temperature of the solvent / monomer when it enters the reactor dropped to -5 ° C by means of an exchanger with glycol at -5 ° C in the jacket. This current entered the bottom of the reactor. The three component catalyst system and its solvent evaporation also enter the reactor at the bottom, but through a gate different from the monomer stream. The preparation of the catalyst components (catalyst, mixed alkylaluminoxane (M-MAO), methyldialkyl ammonium salt of tetrakis-pentafluroaryl-borate) was carried out in an inert atmosphere gloves handling box. The diluted components were placed in nitrogen-filled cylinders and loaded into the catalyst execution tanks in the process area. From these execution tanks, the catalyst was pressurized with piston pumps, and the flow was measured with Micro-Motion mass flow meters. These streams combine with each other and with the catalyst evaporation solvent, just before entering through a single injection line into the reactor. The polymerization was stopped with addition of catalyst annihilator (water mixed with solvent) in the product line of the reactor, after the Micro-Motion flow meter measured the density of the solution. Other polymeric additives can be added with the catalyst annihilator. A static mixer in the line provided the distortion of the catalyst annihilator and the additives in the reactor effluent stream. This current soon entered heaters after the reactor, which provide additional energy for evaporation to remove the solvent. This evaporation occurred when the effluent left the heater after the reactor, and the pressure dropped from 475 psig (3,275 kPa) to approximately 250 millimeters of absolute pressure in the reactor pressure control valve. This evaporated polymer entered a devolatilizer jacketed in hot oil. About 85 percent of the volatiles in the polymer were removed in the devolatilizer. The volatiles exit through the top of the devolatilizer. The stream was condensed, and with a glycol-jacketed exchanger, it entered the suction of a vacuum pump, and was discharged to a solvent separation tank of glycol jacket and styrene / ethylene. 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 its composition was analyzed. The measurement of the ventilated ethylene 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 transmission pump, into a devolatilizing vacuum extruder ZSK-30. The dried polymer leaves the extruder as a single strand. This strand cooled as it was pulled through a water bath. Excessive water was blown from the strand with air, and the strand was crushed into granules with a strand crusher.

Table 5 (1) Catalyst: CgH3-3-Ph-5, 6-C3H6-SiMe2-N (tBu) -TiMe2 (2) Catalyst: [(h5-C5Me4) Me2SiN (tBu)] Ti (CH2 = CH-CH-CHMe ) * This test was done with toluene solvent instead of ethylbenzene.

Examples 9-24 A summary of the blend components and the blend compositions is given in Table 6.

Examples of the present invention are not Tg Measured from dynamic mechanical spectroscopy (DMS); maximum at the loss peak so d for the Tg. Xyl% crystallinity; normalized with respect to the composition of the mixture ..? Shoulder or broad peak for Tg in the loss spectrum of DMS n / a Not applicable * t? 48 The ethylene / styrene interpolymer containing e percent by weight) of this interpolymer, the 9.1 by atactic 5, and has an index rate of melt index The interpolymer G ethylene / styrene containing e percent by weight) of is interpolymer, 3.5 per atactic c, and has an index rate of melt index H ethylene / styrene interpolymer containing 15 percent by weight of styrene as a whole, 1.8 percent by weight has an I2 melt index melting index I10 / I2 of 7.4. Interpolymer I is an interpolymer of * * * 49 ethylene / styrene containing 6.6 mole percent (20.9 percent by weight) of copolymerized styrene in the interpolymer, 7.7 percent by weight of atactic polystyrene, and has an I2 melt index of 1.0, and a 5 percent by weight ratio. melt index IIQ / I2 of 8- ° The blending examples of Table 6 further illustrate the utility and balances of unique properties that can be achieved by blending the interpolymers. Mixtures 9, 10 show two processes of transition of glass other than the dynamic mechanical test, combined with a high breaking tensile energy, and a forced stress relaxation level towards the operation of the component (E). The mixture 11 shows two glass transition processes other than the dynamic mechanical test, which reflect the miscibility of the G and H components, giving a single peak of glass transition temperature, the F component being present as a separate phase. This mixture retains good mechanical properties and high tension relaxation. 20 The class - 7 shows whether it is a ran * Y 50 component polymers. Mixtures 18-23 further illustrate that good thermal performance can be achieved, as evidenced by the penetration of TMA probe, while retaining good mechanical properties and high stress relieving behavior.

Claims (5)

1. A mixture of polymeric materials characterized by a plurality of substantially random interpolymers, each interpolymer resulting from the polymerization of: (1) from 1 to 65 mole percent of: (a) at least one aromatic vinylidene monomer or (b) ) at least one aliphatic or cycloaliphatic hindered vinylidene monomer, or 10 (c) a combination of at least one aromatic vinylidene monomer and at least one aliphatic or cycloaliphatic hindered 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 15 (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 or aliphatic or cycloaliphatic vinylidene monomer residue TO ? 52 number average molecular weight (Mn) of each interpolymer component; or (iii) (i) and (ii) are met.

2. A mixture of claim 1, wherein each of the 5 interpolymer components results from the polymerization: (1) from 1 to 65 mole percent of (a) at least one aromatic vinylidene monomer or (b) at least one aliphatic or cycloaliphatic hindered vinylidene monomer, or 10 (c) a combination of at least one aromatic vinylidene monomer and at least one aliphatic or cycloaliphatic vinylidene monomer, and (2) from 35 to 99 percent molar of at least one aliphatic alpha olefin having from 2 to 12 carbon atoms; and 15 (3) of a molar percent of at least one polymerizable alpha olefin monomer different from (2); and wherein: (i) the amount of vinylidene aromatic monomer residue or the residue of aliphatic or cycloaliphatic vinylidene monomer * or v 53 number average molecular weight (Mn) of each interpolymer component; or (iii) (i) and (ii) are met.

3. A mixture of claim 1, wherein each of the 5 interpolymer components results from the polymerization: (1) from 1 to 65 molar percent styrene and (2) from 35 to 99 molar percent 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 the styrene residue in any interpolymer component differs from that or another interpolymer component by at least 2 molar percent; or (ii) there is a difference of at least 40 percent between the number average molecular weight (Mn) of each interpolymer component; or (iii) (i) and (ii) are met.

4. A mixture of claim 1, wherein each of the interpolymer components results from the polymerization: * it V 54 of interpolymer differs from that amount in another irterpolymer component by at least 0.5 mole percent; or (ii) there is a difference of at least 20 percent between the number average molecular weight (Mn) of each interpolymer component; or (iii) (i) and (ii) are met. A mixture of claim 1, wherein each of the interpolymer components results from the polymerization of a composition comprising: 10 (1) from 1 to 65 mole percent styrene and (2) from 35 to 99 percent mole of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene where: (i) the amount of the styrene residue in any interpolymer component differs from that amount in another interpolymer component by at least 1 molar percent; or (ii) there is a difference of at least 30 percent between the number average molecular weight (Mn) of each component of of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1, octene-1 or norbornene wherein: the amount of the styrene residue in any ipterpolymer component differs from that amount in another component of ipterpolymer from 2 to at least 10 molar percent, such mixtures exhibiting a single glass transition temperature (Tg) similar in form a, but on a temperature scale between the Tg's of the individual interpolymer components as measured by dynamic mechanical spectroscopy. A mixture of claim 1, wherein each of the interpolymer components results from the polymerization (1) of 1 to 65 mole percent styrene and (2) from 35 to 99 mole percent 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 the styrene residue in any interpolymer component differs from that amount in another component of interpolymer in more than 10 mole percent, such blending compositions exhibiting an expanded glass transition temperature, or exhibiting two or more glass transition temperatures as measured by dynamic mechanical spectroscopy. A mixture of claim 1, comprising three or more ipterpolymer components resulting from the polymerization (1) of 1 to 65 molar percent styrene and (2) 35 to 99 molar percent 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 overall blend composition exhibits an expanded single glass transition temperature scale, or exhibits two or more different glass transition temperatures as measured by dynamic mechanical spectroscopy. 9. A mixture of any of claims 1-8, wherein the interpolymer components are produced by the copolymerization of two or more appropriate monomers in the presence of a metallocene catalyst and a cocatalyst. 10. An adhesive or sealant system comprising an interpolymer mixture of any one of claims 1-9. 11. A sheet or film that results from calendering, blowing or pouring an interpolymer mixture of any one of claims 1-9. 12. Injection, compression, exempted, blow molded, rotationally molded or thermoformed molded parts prepared from an interpolymer mixture of any one of claims 1-9. 13. Fibers, foams or latexes prepared from an interpolymer mixture of any of claims 1-9. 14. Fabricated articles or foamed structures prepared from a polymer mixture of any one of claims 1-9, and which find use in sound and vibration damping applications.