DE2907840A1 - VINYL HALOGENIDE POLYMER MATERIALS WITH IMPROVED IMPACT RESISTANCE - Google Patents

Description

The invention relates to a vinyl halide polymer composition which can be shaped into impact-resistant objects,
according to the preamble of the main claim.

Polyvinyl halides (the vinyl halide homopolymers as well as copolymers of vinyl halide and up to about 5o% include an olefinic comonomer copolymerizable with the vinyl halide) represent widely used, malleable thermoplastic materials that

have a number of favorable technological properties. However, polyvinyl halides, for example vinyl chloride homopolymers, break very easily at room temperature and especially at lower temperatures and temperatures below room temperature when impacted about 20 ° C, only about 2.18
to less than about 5.44 kg-cm / cm (0.4 to 1 ft- lb./in.). At temperatures below room temperature, that is

down to temperatures of -28.9 ° C (-2o ° F) or less, the notched Izod impact strength of these polymers is extremely low or negligible. In general, the
Impact strength of conventional vinyl halide polymers
improved at room temperature by the fact that the vinyl halide polymer with a small proportion, i.e. less than 50%, of an impact-improving polymeric additive, which is generally referred to as a polyvinyl halide impact modifier,
mechanically mixed. The impact modifiers mentioned lead to a moderate improvement in the impact strength of the vinyl halide polymers at room temperature, that is, they increase the notched Izod impact strength of the polymer at room temperature in general to about lo.9 to 54.4 kg-cm / cm (2 to Io ft-lbs / in.).

35 '

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The polymeric additives used as modifiers include polymer compositions consisting essentially of methyl methacrylate, 1,3-butadiene and styrene monomer units are made up (and those commonly referred to as "14BS polymers" are) as well as polymer compositions, which essentially consist of acrylonitrile, 1,3-butadiene and styrene monomer units consist (and which are commonly referred to as "ABS polymers") one of these polymeric additives when made for use as an impact modifier for polyvinyl halide, however relatively expensive. This is particularly true when the mixture of the polyvinyl halide and the impact strength modifier should be transparent or translucent. In such cases the MBS or ABS impact modifier must be used be prepared or synthesized under special conditions, so that he about the has the same refractive index as the vinyl halide resin (which is generally about 1.52 to 1.55), µm to achieve that the vinyl halide resin remains transparent or translucent.

It would therefore be technologically desirable to combine part of the MBS or ABS polymer with an MBS or ABS polymer to replace modified polyvinyl halide composition with a polymer that meets the requirements of impact modification fulfilled and which is preferably also readily available with a refractive index that is approximately corresponds to that of the polyvinyl halide.

3o It is known that an easily accessible class of

Polymers, namely the thermoplastic block elastomers of alkadiene hydrocarbons with 4 to 10 carbon atoms and monoalkenyl-substituted aromatic compounds of the benzene or naphthalene series with up to 2o

35 carbon atoms (typical representatives are the

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Block polymers made from 1,3-butadiene or isoprene and styrene) have a refractive index about that of polyvinyl halides corresponds to (see "Modern Plastics Encyclopedia 1974-1975", Vol. 51, No. loÄ (October 1974) 563, Item 35 in the 4th and 7th vertical columns). However, as the examples below show, these are Block polymers are generally incompatible with polyvinyl halide. This incompatibility of the polymer components a vinyl halide polymer blend can affect the blend's impact resistance, as well as the transparency or translucence of the mixture and often leads to the deformation of the mixture a solid material (exudate) on the surface of the molded Mixing occurs which makes the bulk undesirable

15 makes it rough or gives it an uncomfortable lumpy grip.

Although the MBS or ABS polymers mentioned as impact strength modifiers provide a moderate improvement in the

Impact strength of vinyl halide homopolymers and copolymers effect, these modifiers are relatively ineffective in making the polymer a satisfactory one Impact toughness at temperatures below room temperature is imparted by the notched Izod impact strength of the polymer contained in the impact modifier at -28.9 ° C (-2o ° F) well below 5.44 kg-cm / cm and generally about 2.18 to 2.72 kg-cm / cm (0.4 to 0.5 ft-lb / in).

It has been found that the polymerization of vinyl halide (or a mixture of vinyl halide and ethylenically unsaturated comonomers that can be copolymerized with it) in the presence of an elastomeric hydrocarbon polyolefin to a polymeric product (that is, a

35 vinyl halide / polyolefin graft polymers) that leads to

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Vinyl halide polymer chains randomly linked, that is, grafted, along the chain of the olefin core polymer and contains ungrafted vinyl halide polymer- The graft polymer product, in particular which has graft polymers prepared by a polymerization reaction in the bulk and in the liquid phase significantly improved impact strength both at room temperature and at temperatures below that. doors compared to the conventional

Io chen, that is, ungrafted, vinyl halide poly

meren, even if the latter with a conventional polymeric additive to improve the impact strength of the Polyvinyl halide are mixed. The graft polymer product prepared by bulk polymerization is different differs from the corresponding graft polymer that has not been formed in the mass, but, for example, by a suspension polymerization, by a increased impact strength both at low temperatures and at room temperature and due to a breaking behavior that corresponds to the desired ductile fracture rather than the undesired brittle fracture.

Although the said graft polymer at below room temperature has a significantly better impact strength than conventional impact modifiers containing Vinyl halide polymer compositions, it has been found that the Low-temperature impact strength of the graft polymer decreases with aging. Thus, for example, one tends to be out of the Graft polymer existing molded article on aging

3o at room temperature for about a month or more

(or during a correspondingly shorter time at elevated temperature) to a significant loss of its original low-temperature impact strength, which can be up to 35%. This loss of low-temperature impact strength on aging is particularly disadvantageous when the graft

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polymers used outdoors in climatic conditions where temperatures of -17.8 to -28.9 ° C (-17.8 to -28.9 ° C) or below are commonly encountered during the winter months be (after the graft polymer in the summer months relatively high temperatures of for example 26.7 to 37.8 ° C (Sun to loo ° F) or above, causing an accelerated Aging loss of the low-temperature impact strength).

The invention now relates, according to one embodiment, to a improved thermoplastic mass which can be formed into an impact resistant article and a mixture or a blend of a vinyl halide polymer which contains vinyl halide monomer residues as a major proportion of the monomer units and a polymeric impact modifier for the polyvinyl halide, which is selected from the group is selected, the

1) Polymers in which the majority of the monomer units are methyl methacrylate, 1,3-butadiene and styrene residues are and

2) ABS polymers which have approximately the same refractive index as the vinyl halide polymer. 25th

According to the invention, the mixture additionally contains a thermoplastic Block elastomer which, as a major part of the monomeric units, contains residues of a monoalkenyl-substituted Arene of the benzene or naphthalene series with 8 to 20 carbon atoms and a conjugated alkadiene hydrocarbon with 4 to 10 carbon atoms. The block polymer is usually with the vinyl halide polymer incompatible. The vinyl halide polymer is included as the main ingredient in the mixture while the polymer impact modifier and the blocking

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polymer, added together, are contained in a small amount in the mixture. Preferably the weight ratio of block polymer to MBS polymer is about 1: 5 to about 5: 1.
5

If the vinyl halide polymer compositions according to the invention, containing the block polymer impact modifier, under normal temperature and pressure conditions deformed, molded articles are obtained whose

Impact strength is generally greater than that of the corresponding polyvinyl halide compositions, which only have " the MBS or ABS polymer have been modified and corresponding masses (i.e., in general an incompatible mixture) of the polyvinyl halide, which is modified exclusively with the block polymer has been. In other words, the inventive combined presence of the MBS or ABS polymer and the block polymer component in addition to the polyvinyl halide generally a synergistic increase in the impact strength of the polyvinyl halide. the Constituents of the polymer mixture or polymer blend according to the invention are compatible with one another even during shaping and do not separate a single solid phase. As a result, there is no formation of solid exudates (which lead to a disadvantageous and undesirable rough grip) on the surface of the masses during the Deforming, generally with the inventive Combination of an MBS or an ABS polymer and the block polymer as an impact strength modifier

3o for polyvinyl halide all requirements in general to an impact modifier for Polyvinyl halides are met or exceeded.

According to a further embodiment, the invention relates

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a vinyl halide / hydrocarbon polyolefin graft polymer composition, which can be deformed into impact-resistant objects and which are thermoplastic as defined above Contains block elastomers, the block elastomer in an amount of about 1 to 2o%, based on the total weight the graft polymer and the block elastomer.

■ The addition of the block estomer according to the invention to the Graft polymer leads to a mass whose low-temperature impact strength, that is, its impact strength Temperatures below room temperature, which can reach values as low as -28.9 ° C (-2o ° F) or below, with aging the mass increases (for example, during one or more months at room temperature or accelerated for 48 hours at 65 ° C).

Although the non-aged molded composition according to the invention composed of the graft polymer and the block elastomer a low-temperature impact strength or an impact strength at temperatures below room temperature possesses, which is much less than that of the corresponding mass, which only the graft polymer contains, the graft polymer results upon aging and the mixture containing block elastomers, an increase in the low-temperature impact strength to a value which is greater than that obtained by using the graft polymer in the absence of the block polymer additive ages. With preferred graft polymer according to the invention / Block polymer masses, as they are described below, the low-temperature impact strength on a Increased value that corresponds essentially to the impact strength of the corresponding unaged mass that the ■ contains unmodified graft polymers, that is, the Impact strength at low temperatures, for example

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at -28.9 ° C (-2o F) of these preferred according to the invention Mass after aging is no more than about 3 to 12% less than that of the unaged, unmodified Graft polymer mass. In other words, the addition of the block elastomer to the graft polymer results in fact, according to the preferred embodiment of the invention, stabilization of the low-temperature impact strength of the graft polymer.

It should be noted that the improvement in low-temperature impact strength on aging, which is achieved by adding the block polymer to the graft polymer, does not can be achieved with thermoplastic block elastomer additives, the hydrogenated derivatives of the invention

15 represent the thermoplastic elastomers used,

that is, derivatives of the block elastomers according to the invention, whose diene-derived monomer residues of the elastomer have been hydrogenated to remove the ethylenic unsaturation to satiate the leftovers. If you have such hy-

2o drilled thermoplastic block elastomers (those under

the general name Kraton G manufactured and sold are) into the vinyl halide graft polymers according to the invention incorporated, there is a loss of low-temperature resistance with aging (as it is due to

25 Example 35 below is illustrated).

The incorporation of the block polymers used according to the invention into the vinyl halide graft polymer to improve aging the low-temperature impact strength according to the teaching of the present invention does not lead to any adverse effect to a significant extent on other desirable properties of the graft polymer, such as dimensional stability in the heat and heat resistance of the molten polymer (which can be found in a Brabender PIastograph certainly). If desired, the invented

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block polymer / vinyl halide graft polymer compositions according to the invention, the impact strength-improving additives, such as contain the above-mentioned ABS or MBS polymers.

In the masses according to the invention, which the block polymer, an MBS or an ABS impact modifier and contain a polyvinyl halide, the amounts of the block polymer and the ABS or MBS additive and the Ratio of the block polymer to the ABS or MBS additive required to achieve optimum impact strength are required, depending on the particular ABS or MBS additive used and the one used Block polymers vary in some ways. The combination of the ABS or MBS component and the block polymer component is generally included as a smaller component in the mixture according to the invention, the that is, in an amount that is from about 1 to less than about 50 weight percent, which amount is preferably in the range from about 5 to about 20% by weight and in particular in the range from about 8 to about 15% by weight. Corresponding the vinyl halide is included as the main component, that is, makes up more than about 50% by weight to about 99% by weight the mixture of and is preferably in a concentration of from about 80 to about 95% by weight and more preferably contained in a concentration of about 85 to about 92% by weight.

In order to achieve the synergistic increase in the To achieve impact strength should be the weight ratio of block polymer to MBS polymer used as an additive about 1: 5 to about 5: 1, and more preferably about 1: 4 to about 4: 1.

The weight ratio of the block polymer to the ABS polishing, that is, the additive, can be within a wide range

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Range, but is preferably within a range of about 1: 5 to about 5: 1, and more preferably within a range of about 1: 4 to about 4: 1.
5

In the compositions according to the invention, which comprise a vinyl halide graft polymer composition modified with the thermoplastic block elastomer, the proportion of the thermoplastic block elastomer which is used according to the invention to increase the low-temperature impact strength during aging is generally about 1 to about 20 % . The block polymer component is preferably used in an amount of about 1 to about 15% and in particular in an amount of about 2 to about 10%, based on the total

15 me the weights of the vinyl halide graft polymer and the block polymer component.

That used as an ingredient in the composition of the invention Vinyl halide polymers can be prepared using any of the conventional polymerization processes used for these polymers are known to be produced, for example by polymerization in the vapor phase Emulsion polymerization, suspension polymerization or liquid phase polymerization in solution or in

25 of the crowd. Usually vinyl halide polymers are used, which by liquid phase polymerization in the Mass have been produced.

A particularly suitable polyvinyl halide according to the invention, that has been produced by liquid phase polymerization in the mass is obtained by a two-stage Free radical reaction, in which the polymerization in a first stage with rapid stirring with strong Shear forces are applied until about 3 to 15% conversion of the monomer (s) to the polymer

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is reached, whereupon in a second stage the polymerization with slow stirring and using less Shear forces is terminated. This procedure is described in US-PS 3,522,227 and GB-PS 1 o 47 489, which literature references are hereby expressly referred to is taken.

The polyvinyl halide resin used in the present invention is a hard resin, that is, a resin that contains less than about 10% of a plasticizer or no plasticizer at all. Typically the resin is an easily available, commercially available resin that is processed at temperatures in the range of about 177 ° C (35o ° F) or above. Although vinyl chloride is the preferred vinyl halide monomer for the preparation of the vinyl halide polymers according to the invention, other suitable vinyl halide monomers can also be used, such as OL halogen-substituted ethylenically unsaturated compounds which, like vinyl chloride, can undergo an addition polymerization reaction, such as vinyl fluoride, vinyl bromide, vinyl iodide, Vinylidene fluoride, vinylidene chloride, vinylidene bromide, vinylidene iodide and the like. It is also possible to use vinyl halide polymers which have been prepared by the polymerization of two, three or more different vinyl halide monomers. It goes without saying that the polyvinyl halide resin used according to the invention can be a modified resin, that is to say a copolymer of vinyl halide which contains a smaller amount, that is to say less than 50% by weight, of a comonomer, for example vinyl acetate, in the total monomer mixture contains, or preferably a copolymer that can be obtained by copolymerizing monomeric! Vinyl halide is obtained with about 1 to about 30% by weight of a comonomer which is copolymerizable with the vinyl halide. Thus, if the poly used according to the invention

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vinyl halide component preferably composed solely of a vinyl chloride homopolymer or another Vinyl halide homopolymers, includes the invention also include the copolymers described above. Suitable ethylenically unsaturated comonomers that are used to form of the vinyl halide copolymer used as the base material (i.e. vinyl halide bipolymers, terpolymers, -Tetrapolymers and higher polymers, interpolymers and the like) used in reaction with the vinyl halide

Io can include the following monoolefinic

Compounds: ethylene, propylene, butene-l, 4,4-dimethylbutene-1, Decene-1, styrene and its on the nucleus ei-alkyl or -aryl-substituted derivatives, for example o-, m- or p-methyl-, -ethyl- or -butyl-styrene; halogenated styrofoam, like o (-chlorostyrene; monoolefinically unsaturated esters, such as vinyl esters, for example vinyl acetate, vinyl stearate, Vinyl benzoate, vinyl p-chlorobenzoates; Alky! Methacrylate, for example methyl, ethyl, propyl and stearyl methacrylate, Alkyl crotonates, for example octyl crotonate;

2o alkyl acrylates, for example methyl, 2-ethylhexyl and

Stearyl acrylate; Hydroxyether and tert-butylamino acrylates, for example 2-ethoxyethyl acrylate; Isopropenyl ester, for example isopropenyl acetate; Isopropenyl halides, for example isopropenyl chloride; Vinyl esters of halogenated acids, for example vinyl-tf-chloroacetate and Vinyl o (bromopropionate; allyl and methallyl esters, for example Allyl chloride, allyl cyanide, allyl chlorocarbonate, allyl nitrate, allyl formate and allyl acetate and the corresponding MethaiyI compounds; Esters of alkenyl alcohols,

3o for example ß-ethylallyl alcohol; Haloalkyl acrylates, for example methyl and ethyl-Of-chloroacrylate; Alkyl- (X-cyanoacrylate, for example methyl K-cyanoacrylate; Itaconates, for example monomethyl itaconate, diethyl itaconate and itaconic acid based on alcohols with

35 3 to 8 carbon atoms; Maleates, for example mono-

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methyl maleate, diethyl maleate and maleates based on alcohols having 3 to 8 carbon atoms; Fumarates,
for example monomethyl fumarate, diethyl fumarate and fumarates based on alcohols having 3 to 8 carbon atoms; Diethyl glutaconate, monoolefinically unsaturated organic nitriles such as fumaronitrile,
Acrylonitrile, methacrylonitrile, '1,1-dicyanopropene-1 and
Oleonitrile; monoolefinically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, cinnamic acid,

Io maleic acid, itaconic acid, maleic anhydride and the like.

You can also vinyl alkyl ethers and vinyl ethers, for example vinyl methyl ether, vinyl ethyl ether, vinyl 2-chloroethyl ether, vinyl cetyl ether and the like and vinyl sulfides,
for example vinyl-ß-chloroethyl sulfide, vinyl-ß-ethoxy-

15 use ethyl sulfide and the like as well as diolefinic unsaturated hydrocarbons which have two olefinic groups in conjugate position, and Halogen derivatives thereof, for example 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dichlorobutadiene-1,3 and 2-bromo

2o-1,3-butadiene and the like.

When the vinyl halide polymer component of the composition of the invention is a copolymer, it can be copolymers also a "graft copolymer of a vinyl halide

(or from a vinyl halide and a comonomer copolymerizable therewith) and a polyolefin rubber, that is, an elastomer which is soluble in the monomeric vinyl halide at room temperature and at ambient pressure,
is partially soluble or dispersible. These

3o known vinyl halide graft copolymers are obtained

by polymerizing a mixture of monomeric vinyl halide and one or more ethylenically unsaturated Comonomers of the type described above (or preferably only the monomeric vinyl halide alone) in Presence of the olefin used as a reactant

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Hull polymers. The polyolefin elastomer or the polyolefin rubber is a homopolymer, a bipolymer, a terpolymer, a tetrapolymer or a higher Copolymer (especially a homo- or bipolymer of an aliphatic olefinic monomer). The olefin polymers can also be the remainder of an aliphatic polyene hydrocarbon, for example a non-conjugated, straight chain or cyclic diene having 14 to 18 carbon atoms as a monomer unit.

The olefin homopolymers mentioned can be obtained by polymerization a suitable monomer such as Athens, propene, that is, propylene, butene-1, isobutene, octene or 5-methylhexene-1, obtain.

Comonomers suitable for the preparation of the polyolefins are those which are used for the preparation of the oleefin homopolymers mentioned above used, such as propene or butene-1, which are used with Athens and the like. Suitable termono

2o mers are those that are used to prepare the homopolymers and copolymers described above, such as propene, Athens and the like, as well as polyenes. Particularly suitable terpolymers derived from polyene and higher Copolymers can be made from mixtures of olefins and monomers.

provide up to 15% by weight, preferably up to about 6% by weight of the (preferably non-conjugated) polyene, for example 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, Cyclooctadiene and other dienes with straight or cyclic chains contain. The polyolefin used can also be a halogenated polyolefin, for example a chlorinated, brominated or fluorinated polyolefin be polymeric, albeit a hydrocarbon polyolefin trunk, that is, a polyolefin whose carbon atoms having only hydrogen atoms, is preferred.

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The polyolefins used are characterized in that they are monomeric at room temperature and ambient pressure Vinyl chloride is soluble, partially soluble or dispersible and typically has monomer units Have 2 to 6 carbon atoms. That. weight average molecular weight of the olefin polymers, copolymers, Terpolymers and tetrapolymers can vary from about 50,000 to about 1,000,000 or more, but is preferred in a range from about 5o, ooo to about Xo, 3oo, ooo. For the production of those used according to the invention Polyolefin rubbers suitable for vinyl halide graft polymers are ethene / propene polyolefin elastomers and ethene / propene / diene polyolefin elastomers.

The vinyl halide graft polymers based on the polyolefin elastomers are obtained by polymerizing the vinyl halide in the presence of about 0.05 to about 20 %, preferably about 1 to about 20 %, based on the weight of the monomeric vinyl halide, of the polyolefin rubber described above. The preparation of such vinyl halide / polyolefin graft copolymers by the emulsion polymerization method or the suspension polymerization method is described by G. Natta et al. in US Pat. No. 3,812,2o4, which is hereby incorporated by reference. The preparation of such vinyl halide / polyolefin graft copolymers is by polymerization in the vapor phase or in solution. by J. Dumoulin et al. in U.S. Patent 3,789,083 and by PM Rugg et al. in US Pat. No. 2,947,719, which is hereby incorporated by reference

3o has been described. It is convenient to do that

Production of the in the compositions according to the invention as a polyvinyl halide component suitable vinyl halide / polyolefin graft copolymers with the aid of a liquid phase polymerization technique in the mass, as described by A »Takahashi in U.S. Patent 4,071,582 and U.S. Patent Application

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■ - 24 -

No. 746 o46 from 3o. November 1976 and by L. E. Walker are described in U.S. Patents 4,007,235 and 4,067,928, which literature references are hereby expressly referred to.

It is understood that the vinyl halide described / Polyolefin graft copolymers have an impact strength, which is significantly greater than the impact strength of conventional (i.e. not grafted) vinyl halide

genid homopolymers and copolymers. Still, the Impact strength properties of such graft copolymers are generally further improved by the fact that they are according to the invention mixed with an MBS or ABS polymer, that is, the additive and the block polymer.

If desired, vinyl halide graft polymer compositions of the invention to create that are resistant to loss of low-temperature impact strength with aging a vinyl halide / polyolefin graft polymer composition is used as the substrate, which contains a hydrocarbon polyolefin as a polyolefin.

Those used as constituents of the compositions according to the invention Ethyl methacrylate / 1,3-butadiene / styrene polymers represent a readily available class of polymers (generally branded polymers) made in the manner have been that they have a refractive index approximately corresponding to that of polyvinyl halide, and the widely used as an impact modifier for Polyvinyl halide resins can be used. As a means MBS polymers used to modify the impact strength of polyvinyl halide are generally graft polymers, which are obtained by polymerizing methyl methacrylate (and possibly small amounts, based on the monomeric methyl methacrylate, ethylenically unsaturated co-

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polymeric, which can be copolymerized with it, such as acrylonitrile or styrene) in the presence of a polybutadiene or a polybutadiene / styrene core polymer rubber as obtained by L. I. Nass Ed. "Encyclopedia of PVC", 5 M. Dekker Inc., Vol 2- (1977) 613, section. 2 (a) is which publication is hereby expressly referred to. It goes without saying that one in the manufacture of the MBS polymers used as impact strength modifiers the grafting conditions and the choice of monomers

Io can vary within wide ranges. Typical graft polymerization sequences and / or comonomers, which together with the monomer methacrylate in the preparation of the Modifiers used MBS polymers can be used are described in the following patents:

K. Saito et al U.S. Patent 3,670,052; K. Saito et al U.S. Patent 3,651,177; K. Saito et al U.S. Patent 3,287,442; S. S. Feuer, U.S. Patent 2,943,074;

L. E. DaIy, U.S. Pat. 2 ol8,268; L. A. Beer, U.S. Patent 3,444,269; A. C. Condo, U.S. Patent 3,445,416; T. Tanaka et al U.S. Patent 3,652,483; S. Yonezu et al U.S. Patent 3,652,727;

T. Tanaka et al U.S. Patent 3,657,390; S. Koyanagi et al U.S. Patent 2,717,688; Y. Araagi et al., U.S. Patent 3,775,514; T. J. G. Lonning, U.S. Patent 3,780,134; T. Tanaka et al U.S. Patent 3,842,144;

H. Kumabe et al., U.S. Patent 3,9o7,928; F. E. Love, U.S. Patent 3,922,320; N. Murayama et al., U.S. Patent 4,021,5o9; F. Ide et al. US-PS 4 041 Io6 and S. Koyanagi et al., DE-OS 2o 64 297 of July 1, 1971,

35 which publications are hereby expressly referred to

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be men.

Brand names for MBS polymers used as impact modifiers used for vinyl halide polymers include Acryloid KM229, KM 607-N and KM611 from the company Rohm and Haas Co. (described by R. P. Petrich, Polymer Eng. And Sci., (July 1973), Vol. 13, No. 4, 248-258 and by J. T. Lutz, Jr. in Adv. in Chem. Ser., No. 134 (1974) 61-72, to which publications are hereby expressly referred to) and Kane Ace B-12 and B-22 manufactured by Kanegafuchi Chemical Industry Co. The latter MBS polymer, that is, Kane Ace B-22, which performs particularly well when used as an MBS polymer component in accordance with the invention is obtained by the procedure described in U.S. Patents 3,387,443, 3,651,177, and 3,670,052 by K. Saito et al. are described.

The used as a component of the compositions according to the invention Acrylonitrile / 1,3-butadiene / styrene polymers an easily accessible class of polymers (generally branded polymers), widely known as Impact modifier for polyvinyl halide resins be used. If so desired, they are with something like that the same refractive index as the vinyl halide resins. As known to those skilled in the art, the ABS polymers include either

1. a mixture of a styrene / acrylonitrile copolymer (which typically has a styrene / acrylonitrile monomer ratio of 6o to 8o: 4o to 2o) and a minor amount (e.g. 10 to 40% by weight) of an acrylonitrile / butadiene copolymer (with typically a monomer ratio from 5 to 4o: 95 to 5) or

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2. a mixture of a styrene / acrylonitrile copolymer (with typically a monomer ratio from 60 to 80: 40 to 20) and a smaller amount (typically 10 to 40%) of a graft product of the last-mentioned styrene / acrylonitrile copolymer on polybutadiene.

The ABS polymers are particularly from R. E. Gallagher in U.S. Patent 3,988,393 and by W. C. Calvert in AU-PS 22o 155 describes which patents are hereby expressly incorporated by reference.

The block elastomer used as a component of the compositions according to the invention is a thermoplastic block polymer, its monomer units predominantly from 1) a monoalkenyl substituted arene (i.e., an aromatic one Compound) of the benzene or naphthalene series with 8 to 20 carbon atoms and 2) a conjugated alkadiene hydrocarbon with 4 to Io carbon atoms are derived. In the block polymer can like it will be explained below, smaller amounts of other monomers may also be included.

As a monomer in the preparation of the in the invention Mass block polymers used monoalkylarene of the benzene or naphthalene series can for example styrene; o-, m- or p-methylstyrene; O-, m- or p-n-butyl styrene; m-isopropyl styrene; p-tert-butylstyrene; p-octyl styrene; 2,3-dimethyl styrene; 3-ethylstyrene; OC-methylstyrene; p-n-dodecylstyrene; p-methoxystyrene; m-n-octyl styrene; 1-vinyl-2-m-octy! naphthalene; 1-vinyl 1-2 isopropylnaphthalene; 1-vinyl-2-methoxynaphthalene or a mixture of these monomers. The carbon-carbon double bond in the side chain of the alkenyl arene is in relation to the aromatic nucleus in

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Ci., Ss-position. It is preferably the monoalkenyl-substituted one Arene is a hydrocarbon that has the vinyl group (CH "= CH-) as an alkenyl group. The monoalkenyl-substituted arene is preferably a compound of the benzene series and in particular an alkenyl-substituted one A compound of the benzene series, which has up to 12 carbon atoms. Block polymers are particularly preferred, which have been made using styrene as the monoalkenyl substituted aromatic monomer Io are.

The conjugate used to produce the block polymer used as constituents of the composition according to the invention Alkadiene hydrocarbon monomers can, for example, 1,3-butadiene, isoprene, 2,3-dimethy! Butadiene, 2-n-butyl-1,3-butadiene, 1,3-cyclohexadiene, 2-n-hexyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-decadiene, 2-isopropyl-1,3-butadiene, 2-tert-butyl-1,3-butadiene, 1,3-cyclodecadiene, 2,4-octadiene or a mixture of the mentioned cyclic or open-chain alkadiene hydrocarbons be en. Preferably, for making the block polymer component, this is that of the present invention Bulk used alkadiene monomers an open chain alkadiene and in particular 1,3-butadiene or isoprene.

Although it is preferred that all of the monomer units of the block polymer component of the invention be made up of residues the alkadxy hydrocarbons described above and the monoalkenyl-substituted arenes described above exist, it is understood, however, that small amounts of residues of others can be used as comonomer units, if desired Ethylenically unsaturated compounds with the monomeric alkadiene and the alkenyl-substituted aromatic Monomers are copolymerizable, be present

35 can, for example, residues of vinyl pyridine, acrylonitrile,

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Lower alkyl esters of acrylic acid (where the expression Lower alkyl for straight-chain or branched alkyl groups having 1 to 6 carbon atoms, for example the Methyl group)., Methacrylonitrile and vinyl carboxylates, for example vinyl acetate.

The weight ratio of the residues of the monoalkenyl substituted aromatic compound to the residues of the alkadiene compound can vary within a wide range. Own because of their easy accessibility however, the block polymers preferably used according to the invention have a weight ratio of residues of the monoalkenyl-substituted Arene compound to residues of the alkadiene compound in the range from about 1: 1 to about 1: Io, preferably from about 1: 1.5 to about 1: 6, and more preferably from about 1: 1.5 to 1: 2.3.

The block polymers used according to the invention are obtained one generally by a sequential polymerization of the monomers used using an anionic Addition polymerization method. The reaction is generally carried out in the presence of a catalyst for the anionic polymerization, such as typically an organolithium catalyst such as n-butyllithium, carried out. (When these reaction conditions are used, essentially only a block copolymer is formed and the formation of a common copolymer, that is, a random, crosslinked or a Prevents graft copolymers from the monomers mentioned.) The polymerization reaction is carried out in an inert atmosphere under essentially anhydrous conditions. The polymerization can be carried out in the absence or in the presence of an inert diluent or solvent for the reaction mixture, for example, in the presence of one of active hydrogen atoms

909883/0574

containing functional groups of free ether, such as Tetrahydrofuran, or an aromatic hydrocarbon, such as benzene, toluene, xylene and the like. The use of an ether solvent is particularly important partaking.

The production of the block polymers described above has been described in more detail by:

L. M. Potter, U.S. Patent 3,140,182;

R. N. Cooper, U.S. Patent 3,030,346;

R. P. Selinski, U.S. Patent 3,287,333;

KJ Silberberg, U.S. Patent 3,380,863, column 3, lines 5-28 and column 5, lines 10-4o;
RA Hinton, U.S. Patent 3,452,119;

J.K. Craver and R.W. Tess Ed. "Applied Polymer Science"

Organic Coating and Plastics Chemistry Div. of American Chem.

Soc, 1975, 394-429;

M. Morton Ed. "Rubber Technology", Van Nostrand-Rheinhold Co., 2nd edition, 1973, 188, 515-533 and

Allport, D.C., et al., Ed. "Block Copolymers", Wiley (Halstead Press), 1973, 81-87,

G. Holden et al., U.S. Patent 3,265,765;

R. L. Huxtable et al., U.S. Patent 3,198,774; R. E. Dollinger, U.S. Patent 3,297,793;

Dollinger, R. E. et al. U.S. Patent 3,356,763; Encyclopedia of Polymer Science and Technology, Vol. 15 J, Wiley and Sons, 1971 (Supplement) "Styrne-Diene Block

Polymers ",, 508-53o; and
3o Encyclopedia of Polymer Science and Technology "(Supplement)

Vol. 2, J. Wiley and Sons, 1977, 129-132, which publications are hereby expressly referred to is taken.

The block polymers described above can be linear or

909883/0 5 74

straight chain block polymers made up of two homopolymeric segments or blocks (and referred to as two-block polymers) or three (then referred to as
polymers comprising three blocks) or several homopolymeric segments. In the case of the polymers having three blocks, the radicals of the monoalkenyl-substituted arene generally form the end block, while the radicals of the alkadiene form the inner or middle block. The invention

Io block polymers can have graded or transition areas

having (tapered) block polymers, in which, for example, a polymer segment or block of the polymer
begins with a certain monomer unit and gradually
and after another monomer unit is incorporated until the block at the other end consists entirely of the second monomer units. In general, these form
graded or transition regions having block polymers (as in the case of the above-mentioned polymers having three blocks) the radicals of the monoalkenyl-substituted

Arens the end blocks, while the alkadiene residues form the inner block or blocks.

Block polymers from a monoalkenyl-substituted monomeric aromatic hydrocarbon (for example sty-

rol) and an alkadiene hydrocarbon (for example 1,3-butadiene or isoprene), which contain blocks having transition regions, are described in more detail in US Pat
above-mentioned publication by JK Craver and RW Tess on page 395, on pages 83 and 84 of the above

3o spoken publication by D. C. Allport et al. and in said U.S. Patent 3,265,765.

The thermoplastic block elastomers according to the invention can also have a star-like or radial polymer structure have in which two, three, four or more hanopolymers

909883/0574

Blocks (preferably alkadiene blocks) radiating from another, central homopolymeric block, preferably a block from the monoalkenyl-substituted arene). These radial block polymers can be used in this way prepare by adding a small amount of a coupling agent (for example a polyfunctional alkenyl arene compound, such as 1,4-divinylbenz'ol, or a polyfunctional one inorganic .Compound, such as silicon tetrachloride) to the partially converted reaction mass of the above-mentioned anionic polymerization (which is already sufficient to form a two-block Polymers has been implemented) adds.

The production of block polymers with a star-shaped or radial configuration is described in the literature mentioned above Craver and Tess at pages 395 (Table II), 421 and 422 (Table VI) in the referenced article in The Encyclopedia of Polymer Science and Technology, Supplement, Vol. 2, 131-132; by N. Platzer, Chemtech, (October 1977) 634-641, especially page 637, column 1, lines 33-35 and Fig. 2; in an anonymously published Article "New Rubber is Backed by Stars" in Chemical Week (June 11, 1975) 35; and in particular by R. P. Zelinski et al. in U.S. Patents 3,078,254 and 3,281,383, which references are hereby referred to is also expressly referred to.

It should be noted that Fig. 2 of the reference Platzer graphically shows the essential difference between the block copolymers used according to the invention and corresponding conventional copolymers (the random, crosslinked and graft copolymers include). The different physical, mechanical and especially processing properties, which the thermally used according to the invention

909883/067 *

block thermoplastic elastomers from conventional elastomers differ, which are made from the same monomers that are used for the block polymers can be found in more detail in the above-mentioned Morton reference.

Block copolymers of styrene and 1,3-butadiene or of Styrene and isoprene are readily available as branded polymers under the name "Kraton" from Shell Chemical Company and available under the designation "Solprene" from Phillips Petroleum Company. As indicated in the 4th and 6th horizontal lines of Table VI on page 422 of the literature, Craver and Tess are the Kraton copolymers as (non-hydrogenated) linear block polymers of styrene and 1,3-butadiene or isoprene while the solpren copolymers are stated to be radial block polymers or Block polymers are those containing blocks having transition regions whose monomer units are derived from styrene

2o and 1,3-butadiene are derived.

The compositions according to the invention can also be different contain functional additives or auxiliaries, those for "the production of vinyl halide molding compounds commonly used. Typical additives of this type are heat and / or light stabilizers, external and internal lubricants and processing aids for the polyvinyl halide or vinyl halide graft polymer.

Purely for the production of the vinyl halide polymer compositions according to the invention suitable stabilizers include all materials known to be polyvinyl halide to stabilize against the degradation effect of heat and / or light. They include all classes from

909883/0574

knew stabilizers of an organic and inorganic nature, such as metal salts of mineral acids, salts of organic Carboxylic acids, for example from carboxylic acids with 6 to 18 carbon atoms, organotin compounds, Epoxy compounds, Arain compounds and organic phosphites. An organotin compound, such as a methyltin mercaptide, is advantageously used as the stabilizer.

A more detailed description of suitable stabilizers, Io lubricants and processing aids to be included in the Compositions according to the invention can be incorporated can be found in BE-PS 855 764, which is hereby expressly referred to Be referred to.

More classes of additives used for polyvinyl halide resins can be used and optionally in addition to the stabilizers, lubricants and processing aids mentioned Can be incorporated into the compositions of the invention include pigments, dyes and fillers as described by L. R. Brecker in "Plastics Engineering" (March 1976) "Additives 76", pp. 3 to 4, are described, to which literature reference also is expressly referred to.

In general, the amount in which the additional additives mentioned are in each case in accordance with the invention Are used mass, about o, ol to about 5 wt .-% and preferably about 0.1 to about 3 wt .-%, based on the entire resin mass.

The compositions according to the invention are essentially hard vinyl halide resin compositions, which is no more than about 10% by weight of a plasticizer for the vinyl halide graft polymer and are preferably free of such plasticizing additives. Typical plasticizing additives (those in

909883/0574

general organic compounds are) that usually are used in polyvinyl halide compositions, include, for example, the esters of aliphatic alcohols with medium chain length, for example 7 comprises up to 11 carbon atoms, with phenyldicarboxylic acids, for example di-n-octyl phthalate and di-isononyl phthalate, and organic phosphate esters such as cresyl diphenyl phosphate and octyl diphenyl phosphate. The chemical structure and the technology of the plasticizers commonly used in polyvinyl halide compositions is more precisely that above referenced reference L. R. ' Brecker, page 5, describes which document is hereby expressly referred to Be referred to.

The compositions according to the invention can be prepared using conventional Manufacture grinding and mixing methods that are customary for the production of modified ones with regard to impact strength Vinyl halide polymer blends or polyblends, that is, conventional ones modified with MBS or ABS polymers Polyvinyl halides can be used. In general, the polymers (and, if desired, the additional additives and auxiliaries applied above) as a mixture of solid particles in a roller mill or a Banbury mixer and at an elevated temperature suitable for processing hard vinyl halide polymer compositions, marry. The one obtained by grinding and mixing Polymer blending is done either by injection molding or by compression molding at elevated temperature and at increased pressures required for deforming rigid polyvinyl halide compositions are suitable, deformed into objects of the desired shape. If you use it as a mix substrate an MBS or ABS modified vinyl halide polymer is used, one uses for the production of the mentioned objects, which can be shaped differently, both

909883 / ÖS74

for example rods, plates, rings, rods, sheets and foils, customary compression molding methods.

The following examples serve for further explanation the invention.

Unless otherwise stated, in the description and in the patent claims the temperatures are in ⁰ C and all parts, ratios and percentages are based on the weight of Io.

example 1

The rollers of a mixing device (Amil Mill), which is operated under the following conditions:

Front roller temperature 18o to 182 ° C

(355 to 36o ° F)

Back roller temperature 166-169 ° C

(33o to 335 ° F)

Roller speed 14.6 m / min (48 ft / min)

with a particulate solid mixture of 100 parts by weight of a vinyl chloride homopolymer, which is

sigphasenpolymerisation has been produced in bulk and a notched Izod impact strength (ASTM test D-256) in the range of about 2.18 to less than 5.44 kg-cm / cm (0.4 to 1 ft- lbs./in); 6.5 parts by weight of a commercially available methyl methacrylate / 1,3-butadiene / -

3ο styrene polymer, commonly used to improve impact resistance of vinyl halide polymers (manufactured by Kanegafuchi Chem. Ltd. under the designation Kane B-22); 6.5 parts by weight of a commercially available radial styrene / 1,3-butadiene block poly

mers that contain about 40% by weight of styrene and about 6o% by weight of 1.3-

909883/0574

Butadiene obtained (manufactured by Phillips Petroleum Co. under the name Solprene 414-P); 2.85 Parts by weight of an acrylic polymer processing aid commonly used in processing vinyl halide resins is used (manufactured by Rohm and Haas Corp. under the name Acryloid K-12o-ND); 1.14 parts by weight of a commercially available short-chain paraffin wax that is commonly used as an internal lubricant used in vinyl halide polymer molding compounds (manufactured by Cincinnati-Milacron Co.

under the name Advawax 14o); o, 23 parts by weight of one commercially available wax, which is a derivative of a long chain (28 to 32 carbon atoms) Montan wax acid, which is a diester of a two-valued

15 term alcohol and usually as an external

Lubricant (with little internal lubricating effect) used in molding vinyl halide polymers is (manufactured by American Hoechst Corp. under the name Wax E) and 1.8 parts by weight of an im Commercially available methyltin mercaptids, commonly used as a thermal stabilizer in vinyl halide polymers (manufactured by Cincinnati MiIacron Co. under the designation TM-181).

The melting time of the mixture in the mixing device is about 10 to 15 seconds. The mixture remains on the mixing rollers for about 5 minutes, after which the appearance of the streaks of the mixture on the rollers is satisfactory is. The mixture is withdrawn from the mixing device in the form of a sheet and expanded to about Room temperature (about 2o C) cooled.

The resulting polymer blend is compressed into rods 15.2 cm (6 inches) long by 15.2 cm (6 inches) and a thickness of o.32 cm (1/8 inch)

909883/0574

pressed, for which a large press (Carver Press) is used, which is operated under the following temperature and pressure conditions: 3 minutes at 177 C {35o F) and
68.9 bar (looo psi); 2 minutes at 177 ° C (35o ° F) and
2o68 to 22o6 bar (3o, ooo to 32, ooo psi); and 2 minutes at room temperature and 2o68 to 22o6 bar (3o, ooo to
32,000 psi). ·

The resulting molded rod samples are cut into notched rod samples 1.27 cm (1/2 inch) wide and at room temperature and at -28.9 ° C (-2o F) in substantial accordance with ASTM test specification D-256 examined their notched Izod impact strength. The results This examination and the appearance of the shaped rods are summarized in Table I below.

Examples 2 to 9

In Examples 2 to 9, the procedure of
Example 1 was essentially repeated in the manner described there, with the difference that the amounts in
to which the methacrylate polymer component, that is, the MBS additive, and the block polymer component are added
can be varied, with either the MBS polymer or the block polymer being dispensed with in certain cases. The results of these examples are also summarized in Table I below.

909883/057 *

TABLE I. example

Amount of MBS polymer (%, based on the weight of the total resin mass)

Amount of block polymer (%, based on weight d. total Resin mass)

Izod impact strength values (kg'cm / cm (ft-lbs / inch))

Room temperature -28.9 ° C (-2o ° F)

Appearance of the
Molded article

0 »

it »

• Si

O
in

5.5

4, ο

2.5

Ι, ο

(Comparative example)

5 Ιο, 9 (comparative example)

6 I 5.8

(Comparative example)

(Comparative example)

8 I ο

(Comparative example)

(Comparative example)

5.5

7, o

8.5

lo, o

5.8 8.6

lo, 9

Io 2.3 (18.8) 4.74 (o.87)

Io4, o (19.1) 3.21 (o.59)

72.4 (13.3) 3.59 (o.66)

24.5 (4.5) 3.65 (o.67)

51.2 (9.4) 2.94 (o.54)

12.5 (2.3) 2.5o (o.46)

8.16 (1.5) 3.48 (o.64)

13.1 (2.4) 3.76 (o.69)

8.71 (1.6) 4.19 (o.77)

Transparent, essentially colorless with a slight, good-looking bluish tinge; no exuded material on the surface

Essentially transparent (very little haze), essentially colorless with weak, attractive blue cast; no exuded material on the surface

Essentially transparent (very little haze), essentially colorless with weak, attractive blue cast; no exuded material on the surface

Transparency impaired by haze; essentially colorless with a bluish tinge; Exuded material on the surface

Transparent; essentially colorless

Transparent; essentially colorless

Low turbidity; essentially colorless with a bluish tinge

Transparency impaired by cloudiness, significant bluish tinge; sweaty Material on the surface

Transparency impaired by haze C (more than in example 5); \ .vsentIy bluish tinge; Exuded material on the surface

TABLE I (continued)

Footnote: The sweat indicated for the molded products of Comparative Examples 4, 8 and 9 Material on the surface occurs when the masses are formed and appears in the form of small solid ones Lump "on the surface of the product, giving the product surface a rough feel will.

If one compares the values of the impact strength at room temperature of Examples 1 to 3 (which the invention The masses and the block polymer and the MBS polymer in a ratio of about 1: 1 to 4: 1 and in which the styrene / butadiene ratio in the block polymer is about 2: 3) with the corresponding Impact strength values of Comparative Examples 5 to 6 (which do not contain the block polymer) on the one hand and Comparative Examples 7 to 9 (which do not use MBS polymer) on the other hand, it can be recognize that the impact resistance of the invention Mass by the inventive combined presence of both the block polymer and the MBS polymer in the vinyl halide resin mixture is increased synergistically.

Comparative Examples 8 to 9 also show that "the block polymer used as an additive is as such with the vinyl halide polymer in a vinyl halide resin is incompatible, which can be seen in particular from the fact that a transparency impairing Material occurs on the surface of the products of these examples. Comparative example 4 shows a vinyl halide, which contains both an MBS polymer and a block polymer, but in which the ratio of these both additives is outside the range claimed according to the invention. With the material of this latter For example, the impact strength of the product is

909883/0574

temperature despite the simultaneous presence of both the MBS polymer and the block polymer in the Vinyl halide polymers not synergistically increased. Furthermore, the polymer components of the product are Example 4 incompatible with each other, which is reflected in the solid material deposited on the surface of the product of example 4 manifested.

Examples Io to 16

Using the procedure of Example 1, a series is made essentially as described therein of comparative examples Io to 16 carried out, as indicated in the above examples 1 to 9, with the difference that a commercially available radial styrene / 1,3-butadiene block polymer is used as the block polymer, the about 30 weight percent styrene and about 70 weight percent 1,3-butadiene contains (and under the name Solprene 411-P from the Phillips Petroleum Co.). The results obtained with these examples are shown below Table II given.

909883/0574

TABLE II example

«Ο O CO

Amount of MBS polymer (%, based on the weight of the total resin mass)

Amount of block polymer (% based on the weight of the total resin composition)

Notched Izod impact strength values

(kg-cm / cm (ft-lbs / inch)) ^{Room temperature -28.9 0} C (-2o ° F)

Appearance of the molded object

Λ1

Ί3

(Comparative example)

14th

(Comparative example)

15th

(Comparative example)

16

(Comparative example)

5.5

4, ο

2.5

5.5 7, ο

8.5

lo, o 5.8 8.6

lo, 9

51.7 (9.5)

81.6 (15, o)

18, ο (3.3)

12, ο (2.2)

7, o8 (1.3)

8.71 (1.6)

7, o8 (1.3)

4.63 (o.85)

3.76 (o.69)

3.27 (o.6o)

3.37 (o.62)

3.32 (o.61)

3.48 (o.64)

3.59 (o.66)

Transparent; essentially colorless; no perspiration on the surface

Essentially transparent (with very little haze); essentially colorless; no sweat cast material on the surface

Essentially 'transparent (with little haze); essentially colorless; no Exuded material on the surface

Transparency impaired by significant haze; essentially colorless; the surface shows a solid exuded material, which is the incompatibility of the polymers used as components.

Table II above shows that the compositions according to the invention, that is to say the products of the examples, 11 and 12 (which have a ratio of block polymers to MBS polymers from about 1: 1 to about 4: 1 and a styrene / butadiene ratio in the block polymer of about 1: 2.3) have an increased impact strength at room temperature compared to the values that are available (at appropriate concentrations) with polyvinyl halide / methacrylate polymer masses, which do not contain any block polymer (as indicated by the comparative examples above 5 and 6), polyvinyl halide block polymer compositions, which do not contain any MBS polymer (the products of comparative examples 14 to 16) or polyvinyl halide compounds, which contain both an MBS polymer and a block polymer, however, in a ratio which is outside the range of the range claimed according to the invention (like the product of Comparative Example 13) reached-Die Polyvinyl halide compositions given in Table II above, which are the block polymer but not an MBS polymer contain (the products of the comparative examples up to 16) and the polyvinyl halide mass, which contains the MBS polymer and the block polymer in a ratio lying outside the range claimed according to the invention contained (product of Comparative Example 13) have, as can be seen, inferior optical properties in comparison to the products according to the invention of Examples 10, 11 and 12. Furthermore, the polymer components of the products of the comparative examples 13 to 16 are incompatible with each other, which is reflected in the presence significant solid materials exuded on the surface of the products.

Examples 17-22
In Examples 17, 19 and 21, the results of which in the

909883/0574

Table III below, the procedure of Example 1 is essentially in the Repeatedly described above, using various commercially available block polymers of a monoalkenyl-substituted Arene and an alkadiene can be used according to the invention (the particular block polymers used are described in the footnotes of the table). Examples 18, 20 and 22 (their results also are listed in Table III) are comparative examples which correspond to the above-mentioned Examples 17, 19 and 21 and those on the MBS polymer component was waived.

909883/0574

TABLE III

O
'-*"* Example Amount of MBS
Polymers (%, be
moved to the Ge
weight of the whole
Resin mass) Amount of block
polymers (%, be
moved to the Ge
weight of the whole
Resin mass) Notched Izod impact
(kg cm / cm (f
Room temperature (18.2) toughness values
t-lbs / inch))
-28.9 ° C (-2o ° F) (o, 83) Appearance of the
Molded article 17th
(Footnote 1) 5.5 5.5 99.1 (2.6) 4.52 (o, 92) Translucent, essentially color
go, no sweaty material on
the surface 18th
(Comparative
example)
(Footnote 1) 0 lo, 9 14.2 (16.2)
(1.8) 5, oil (o, 72)
(o, 73) Cloudy, essentially colorless; the
Surface has a solid _t
sweaty material 19th
(Footnote 2)
2o
(Comparative
example)
(Footnote 2) 5.5
0 5.5
lo, 9 88.2
9.8o (16.3) 3.92
3.97 (o, 83) Essentially transparent (with low
low turbidity), essentially colorless,
no perspiration on the
surface
Translucent (not transparent),
essentially colorless, the upper
surface has a firm, sweaty appearance
Material on 21
(Footnote 3) 5.5 5.5 88.7 (3, o) 4.52 (o, 92) Essentially transparent (with low
low turbidity), essentially colorless,
no perspiration on the
surface 22nd
(Comparative
example)
(Footnote 3) 0 lo, 9 16.3 5, oil Translucent (not transparent), im
essentially colorless, the surface
exhibits a solid exuded matter
on <°
O

TABLE III (continued)

Footnotes:

1. The block polymer component is a commercially available three block., Polymer comprising styrene and isoprene in a ratio of about 1: 6, that is, 14 wt .-% styrene and 86 wt .- % isoprene, which of Shell Chemical Company under the name Kraton Ilo7.

2. The block polymer component is a commercially available three block polymer of styrene and 1,3-butadiene in a ratio of about 1: 3, that is, of 25% by weight styrene and 75% by weight 1,3-butadiene from Shell Chemical

15 Company under the name Kraton Hol " will.

3. The block polymer component is a commercially available two-block polymer of styrene and 1,3-butadiene in a ratio of about 1: 3, that is to say that consists of 25% by weight of styrene and 75% by weight of 1,3-butadiene and of the Phillips Petroleum Company under the name Solprene 1205.

25 The products illustrating the invention, which are shown in the

given in Table III above, that is, the products of Examples 17, 19 and 21 in which the ratio from block polymer to MBS polymer is about 1: 1, have improved optical properties (i.e.

3o they are transparent or translucent) compared to the products of the corresponding comparative examples 18, 2o and 22, in which the MBS polymer is omitted became. The products of the latter comparative examples also have a solid surface on their surface.

Sweaty material, which is essentially the case with the products

309B83./3574

of Examples 17, 19 and 21 does not occur. These results further substantiate the incompatibility of the block polymer used according to the invention with the vinyl " halide polymers, if the MBS polymer is omitted will. ..

If one compares the determined values of the impact strength at room temperature of the products of Examples 17, 19 and 21 with those of the corresponding vinyl halide polymer compositions which contain the MBS polymer but no block polymer (that is, the products of Comparative Examples 5 and 6 given above) with those of the corresponding ones Vinyl halide compositions which contain the block polymer but no MBS polymer (i.e. the products of the corresponding Comparative Examples 18, 20 and 22), it can be seen that the impact strength of the products of the examples 17, 19 and 21 is synergistically improved at room temperature.

2o B e i s ρ i e 1 23

The rollers are fed to a mixing device (Farrell Mill) which is operated under the following conditions:

Front roller temperature 182 ° C (36o ° F) Rear roller temperature 116 ° C (24o ° F) Roller speed 14.6 m / min (48 ft / min)

with a particulate solid mixture of 100 parts by weight of a vinyl chloride Horaopolymeren, which by a Liquid phase polymerization has been produced in the mass and has a notched Izod impact strength (according to the ÄSTM test D-256) in the range given in example 1 owns; 6.5 parts by weight of a commercially available ABS polymer {Acrylonitrile / 1,3-butadiene / styrene polymer), such as

909883/0574

it is commonly used to improve the impact strength of vinyl halide polymers (and from the Marbon Division, Borg Warner Corporation under the name Marbon Blendex 4ol); 6.5 Parts by weight of a commercially available radial styrene / 1,3-butadiene block polymer as illustrated in Example 1 is; 2.85 parts by weight of an acrylic polymer processing aid, which contains about 13% by weight ethyl acrylate monomer residues and 87% by weight methyl methacrylate monomer residues

Io and which was also used in Example 1; 1.14

Parts by weight of a commercially available short-chain paraffin wax; 0.23 parts by weight of a commercially available wax derivative commonly used as an external lubricant is used in vinyl halide polymer molding compositions and which is described in Example 1; and 1.8 parts by weight of the commercially available methyltin mercaptide heat stabilizer illustrated in Example 1.

After melting, the mixture remains for about

5 minutes on the mixing rollers until the appearance of the mixture on the rollers is satisfactory. The mixture is peeled off the roller in the form of a sheet, which is cooled to about room temperature (to about 20 ° C) leaves.

The polymer mixture obtained is molded by compression molding to sample bars 15.2 cm (6 inches) long, 15.2 cm (6 inches) wide, and thick o.32 cm (1/8 inch) using a large mold

press (Carver Press) pressed and essentially according to the procedure of Example 1 at room temperature and at -28.9 ° C (-2o ° F) for their notched Izod impact strength examined. The results of this examination and the appearance of the molded test bars are shown in the next

35 compiled in Table IV.

909883/0574

• _ 4-Q _

Examples 24 to 3o

In Examples 24 to 25, the procedure of the Example 23 was essentially repeated in the manner described, except that those indicated below were used different block polymers used:

Example 24: the radial block polymer is used

from 7o wt .-% 1,3-butadiene and 3o wt .-% Styrene as described in Example Io

is;

Example 25: the three-block one is used

Polymers of 86% by weight isoprene and 14% by weight styrene, as indicated in Example 17

give is.

In Comparative Examples 26 to 30, the procedure of Example 23 is essentially as described Repeated manner, with either the ABS polymer or the block polymer being dispensed with. In example 26 the proportion of ABS polymer is varied, while in Examples 28 to 3o the amount of block polymer is varied. The block polymer used in Comparative Examples 28, 29 and 3o corresponds to that in block polymers used in Examples 23, 24 and 25, respectively. The results of these examples are along with those of Example 23 is given in Table IV below.

9 {J9 «83/0574

TABLE IV

■ Example

Amount of ABS polymer (%, based on weight of the entire resin mass)

Amount of block polymer (%, based on the weight of the total resin mass)

Notched Izod Impact Strength Values (kgcm / cm (ft-lbs / inch)

Room temperature

-28.9 ° C (-2o ° F)

Appearance of the
Form object

CO
O
CO
OO

oo 24

(Comparison example)

(Comparative example)

28

(Comparative example)

29

(Comparative example)

3o

(Comparison example)

5.5

5.5

5.5 lo, 9

5.8

none none none

5.5

62.1 (11.4)

4,3o (o.79)

5.5

5.5

none none lo, 9 lo, 9 lo, 9

13.1 (2.4)

61, o (11.2)

6.53 (1.2)

5.28 (o.97)

8.71 (1.6)

7, o8 (1.3)

14.2 (2.6)

3.81 (o.7o)

3.48 (o.64)

2.72 (ö, 5o)

2.72 (0.5o)

4.19 (o.77)

3.59 (o.66)

.5, ol (o, 92)

Substantially (slight turbidity) transparent, substantially colorless weak, an attractive blue tint, no out schwitztes material surface on the upper ¹

Essentially transparent (low
Turbidity), essentially colorless,
no blue cast, no perspiration
Material on the surface

Translucent, essentially colorless, no blue cast j no perspiration Material on the surface

Essentially transparent and colorless <, no exuded material on the surface

Essentially transparent and colorless, no perspiration on the material the surface

Very cloudy, colorless, rough surface with considerable perspiration on the surface

Very cloudy, colorless, rough surface with considerable perspiration on the surface

Cloudy, rough surface with significant exuded material on the surface.

σι O

TABLE IV (continued)

Footnote: The exuded material described above

on the 'surface of the molded products
Comparative Examples 28, 29 and 3o. Occurs at

Forms the masses on and appears in the form of
small solid lumps on the surface of the
Products that give the product surface a rough feel.
Io

If one compares the results of the determination of the impact strength at room temperature of Example 23 (which the
Composition according to the invention illustrated) with those of Comparative Examples 26 to 28, it can be seen that the
Impact strength of the composition according to the invention is synergistically increased by the simultaneous presence according to the invention of both the block polymer and the ABS polymer.

The comparative examples 28 to 3o further illustrate the fact that the block polymer additive as such in a vinyl halide resin is incompatible with the vinyl halide resin as it results in the formation of a solid exudate Material on the surface of the products

25 these examples can be recognized.

Example 31

A small heated mixer (Protex Henschel
Mixer) operating at about 38oo min "and at a temperature
of 54.4 ° C (130 ° F), with 1500 g of a vinyl chloride / polyolefin graft polymer (containing the
Graft polymers of 9% by weight), in which the polyolefin is an ethylene / propylene / ethylidene norbornene terpolymer which is produced by free radical liquid phase polymerization

909883/057 ^

■ - S2 -

has been prepared in bulk in substantially the manner described in the aforementioned U.S. patent application Ser. 746 o46 is described. After mixing for 5 minutes, the temperature of the mass is 65.6 ° C (15 ° F) and 45 g of a commercially available tribasic lead sulfate monohydrate stabilizer commonly used for vinyl halide polymers (manufactured by National Lead Co. under the name Tribase AG) and 15 g of a commercially available dibasic lead stearate stabilizer commonly used for vinyl halide polymers (and sold by National Lead Co. under the Name DS-2o7 is added) After mixing is continued for an additional 2 minutes, the temperature of the mixture is about 71.1 ° C (160 ° F) and 30 grams of a commercially available processing aid in the form of an ethyl acrylate is added (13% by weight) / methyl methacrylate (87% by weight) copolymers, which was also used in Example 1. After mixing has been continued for a further 5 minutes, b eträgt the temperature of the mixture 87, .8 ⁰ C (19o F) and they were mixed with 15 g of a commercially available organic lubricant, as it is usually used as external lubricant for vinyl halide polymers (and that of the company American Hoechst Corp. is manufactured under the designation XL-165). After mixing for an additional 3 minutes, for a total mixing time of 15 minutes, the temperature of the mixture is 98.9 ° C (210 ° F) and the mixture is discharged from the mixer and allowed to cool to room temperature.

The mixture obtained is divided into three equal portions, which are made using the following conditions be processed in a roller mixer:

A roller mixer (Farrell Mill) is charged, the is operated under the following conditions;

Front roller temperature 18o to 182 ° C 5 .- (355 to 36o ° F)

Rear roller temperature 166-169 ° C

{33o to 335 ° F)

-1
Roller speed 48 min

with 25 g of the commercially available one used in Example Io radial thermoplastic block elastomers made from 1,3-butadiene and styrene. The elastomer is ground for 5 minutes and then puts one of the portions of the mixture described above on the roller mixer. The mixture is ground for about 5 minutes and then carried out of the roller mill in the form of a sheet the end. Repeat this process of grinding with the two remaining portions of the mixture that you are using the mixer described above (Prodex-Henschel mixer), so that a total of 75 g of the block elastomer mixed with the vinyl chloride graft polymer.

The leaves obtained by milling are combined and pulverized in a comminution device (rapid granulator). Then you determine the dimensional stability of the obtained mixture in the heat at 18.2 bar (264 psi) using ASTM protocol test D-648. Farther is determined in a suitable measuring device (Brabender Plastograph) which is operated at 2o4 ° C. and 63 minutes becomes, the equilibrium torque and the thermal stability of the molten mixture.

An injection molding device (Arburg 200 Injection Molding Machine) is charged with the following cylinder temperature settings is operated: Zone 3 = 16o ° C (32o ° F),

909883/0574

Zone 2 = 177 ° C (35o ° F) and Zone 1 = 188 ⁰ C (37o °: f) with the powdery! Mix and shape these at a mold temperature of 37.8 ° C (loo ° F) and an injection pressure of Io34 bar (15,000 psi) into impact strength test bars with a length of 12.7 cm (5 inches), a width 1.27 cm (1/2 inch) and o.32 cm (1/8 inch) thick. Some of the samples are immediately tested (according to the notched Izod impact test according to ASTM regulation D-256) both at room temperature (i.e. at about 20 ° C) and at a temperature below room temperature (i.e. at -28, 9 ° C (-2o ° F)) examined for their impact strength. The remaining rod samples are aged at an accelerated rate by heating them to 65 C in a forced-air oven for about 48 hours. The aged bars are then tested for impact strength at -28.9 ° C (-2o ° F) according to the procedure described above. The results of this example are shown in Table V below.

2o example 32

The measures of Example 31 are repeated essentially in the manner described there, with the difference that that the thermoplastic block elastomer is the commercially available radial block copolymer of 1,3-butadiene and styrene, as described in Example 1, is used. The results of this example are along with those of Example 31 are listed in Table V below .

Example 33

The measures of Example 31 are repeated essentially in the manner described there, with the difference that that the thermoplastic block elastomer is what is

909883/0574

the available three block isoprene / styrene copolymers of Example 17, which contains 86% by weight isoprene and 14% by weight styrene. The results of this Examples are given in Table-V below, along with those of Examples 31 and 32.

Example 34 (comparative example)

The procedures of Example 31 are essentially repeated in the manner described there, with the difference that the thermoplastic block elastomer is dispensed with. The results of this example are also given in Table V below.

15 Example 35 (comparative example)

In this comparative example, the measures of Example 31 are essentially repeated in the manner described there, with the difference that, instead of the thermoplastic block elastomer of Example 31, a commercially available three-block thermoplastic elastomer made from 1,3-butadiene and styrene is used, which has been selectively hydrogenated to remove the ethylenic unsaturation in the block composed of butadiene residues (so that the elastomer is in fact a three block polymer which is a three block polymer, the polystyrene end blocks and as a result of the hydrogenation has a middle block of an I-butylene / ethylene copolymer). This hydrogenated thermoplastic block elastomer (the structure of which is shown in "The Encyclopedia of Polymer Science and Technology" Supplement Vol. 2, page 131, FIG. 7, loc. Cit.) Is sold by Shell Chemical Company under the name Kraton GX- 6521 manufactured. The results of this example are

"'- 56 -

also given in Table V below. Examples 36 to 38 (comparative examples)

The steps in the example are essentially repeated in the manner described, with the difference that the thermoplastic block polymer of Example 31 replaced by various thermoplastic elastomers that do not have a block structure, namely: ■ Io

Example 36 used a commercially available cross-linked acrylonitrile / 1,3-butadiene copolymer containing 41 wt -% of acrylonitrile and contains commonly used as an additive for vinyl halide polymers.

(and from B. F. Goodrich Chemical Co. under the name Hycar 1411 will be produced);

Example 37: A commercially available acrylonitrile / 1,3-butadiene copolymer is used which

contains about 33% by weight acrylonitrile (and supplied by B. F. Goodrich Chemical Co. manufactured under the name Hycar 1452P-5o); and

Example 38: a commercially available one is used

Acrylonitrile / styrene copolymer (available from Dow Chemical Co. under the name Tyril is manufactured).

The results of these comparative examples are shown below, along with the results of Examples 31 to 35 Table V listed.

909883/0574

TABLE V

at
game Elastomer
Additive Equiv
weight
Torque
U / g) Heat stability
capacity (min) Form-permanent
speed in the
Warmth ( ⁰ C) Notched Izod impact strength
(ft-lbs / inch))
Without aging
Room temperature- -28.9 ⁰ C
temperature (-2o ° F) speed (kg'cm / cm
After aging
-28.9 ⁰ C (-2o ° F) Increase or decrease in
Izod -Carb impact toughness
at -28.9 ⁰ C (-2o ° F) at
Aging (X) 31 Solprene
411-P 957 12-13 6o, o Io6,7 6, o4
(19.6) (1.11) 7, o8 (l, 3o) Increase - 17.2% 32 Solprene
414-P 927 13-14 62.3 94.2 5.99
(17.3) (l, lo) 6.53 (l, 2o) Increase - 9.1% 33 Kraton
Ilo7 844 13-14 59, ο 94.7 4.35
(17.4) (o, 8o) 4.52 (o.83) ' Increase in e - 3.8% 34 None 916 15-16 62.5 lol, 8 7.35
(18.7) (1.35) 4.79 (o.88) Decrease ¹ - 35% 35 Kraton G
X-6521 855 16-17 62.5 113.2 4.84
(2o, 8) (o, 89) 4.68 (o.86) Decrease - 3.4 % 36 Hycat 1411 lloo 12-13 58, ο 94.7 4.84
(17.4) (o.89) 4.57 (o.84) Decrease -5.6% 37 Hy c ar
1452-P-So 938 12-13 53, ο 82.2 5.93
(15.1) (I, o9) 4.68 (o.86) Decrease - 21% 38 Tyril 942 12-13 61.5 71.8 4.79
(13.2) (o.88) 4.57 (o.84) Decrease - 4.5 %

Footnotes: 1. All molded products have a similar appearance, that is, they are cream-colored, cloudy, have a smooth surface without roughness or solid exuded materials on the surface.

2. All elastomer additives that are specified in the 2nd vertical column of the table are in one Amount of 5 parts by weight per 100 parts by weight of the vinyl halide / polyolefin 'graft polymer contain what an amount of about 4.76 weight percent based on the total weight of the elastomer additive and the vinyl halide graft polymer is equivalent to.

3. The percentage of increase or decrease in low-temperature impact strength with aging, which is given in the last vertical column of the table, is calculated by taking the difference in low-temperature impact strength between the unaged sample and the aged sample divide the & t low-temperature impact strength of the unaged sample and multiply the result by loo.

CO

QO 09

eat

OO

A comparison of the results of the examples according to the invention, that is, of Examples 31 to 33, with Comparative Example 34 (in which an unmodified vinyl ' halide graft polymer is used) reveals that, despite the fact that the addition according to the invention of a thermoplastic block elastomer to the vinyl halide graft polymer to an initial reduction the low-temperature impact strength compared with that of the graft polymer causes the low-temperature impact strength of the compositions according to the invention in accelerated aging (which essentially corresponds to aging at room temperature during a month or more) increases. Comparing the results of the above examples with those of Comparative Examples 35 to 38, it can be seen that the other thermoplastic elastomer additives (which do not contain any Block polymers or a block polymer whose structural properties differ from those of the invention Additives differ, as is the case with the block elastomer additive of Example 35) no improvement in Cause low-temperature impact strength of the graft polymer composition on aging, as is the case with the 'used according to the invention thermoplastic block elastomer additive is the case.

The comparison of the data in the vertical columns of Examples 33, 34 and 35 with the corresponding values of the

Comparative Example 34 shows that the melt time and heat stability (those in the Brabender Plastograph mixer were determined) and the dimensional stability in the heat of the graft polymer is not significantly affected the admixing of the thermoplastic block elastomer according to the invention to which graft polymers are adversely affected. A comparison of the impact strength of the products of the examples with those of the product of the comparative example at room temperature illustrates the fact that the invention the additive used does not have any significant

Impairment of the impact strength of the graft polymer Caused room temperature when it is mixed according to the invention with the graft polymer.

909883 / Q5T4

Claims (1)

Patent attorneys Dipl.-Ing. H. Weickm.? nn, Dipl.-Phys. Dr. K. Fincke Dipl.-Ing. F. A. WEICKMANN, Dipl.-Chem. B. Huber Dr. Ing.H. Liska 8000 MUNICH 86, DEN '£ ^. U "p; k jq ^ q POST BOX 860820"""''"· MÖHLSTRASSE 22, CALL NUMBER 98 39 21/22 HtM / cb 4o27 / 4o28 / 4o82 HOOKER CHEMICALS & PLASTICS CORP. Niagara Falls _r New Yorkl43o2, USA Vinyl halide polymer compositions with improved impact strength. Claims 1. Vinyl halide polymer mass that becomes impact resistant can be deformed and a mixture of a vinyl halide polymer, which is the main component of the Has monomer units vinyl halide monomer residues, and a polymeric impact modifier for the Polyvinyl halide selected from the group that 1) Polymers with methyl methacrylate, 1,3-butadiene and styrene residues as the main part of the monomer units Have io, and 2) includes ABS polymers, 909883/0574 comprises, characterized in that the mixture additionally comprises a thermoplastic block elastomer contains, which is the majority of the monomer units residues of a monoalkenyl-substituted arene compound of Benzene or naphthalene series with 8 to 20 carbon atoms and a conjugated alkadiene hydrocarbon with 4 to 10 carbon atoms, which is block elastomer is normally incompatible with the vinyl halide polymer, with the vinyl halide polymer as the main component and the polymeric impact modifier and the block elastomer together as. smaller component are included in the mixture, provided that the weight ratio of the block elastomer to the modifier is about 5: 1 to about 1: 5 when the polymer 15 impact modifier a methyl methacrylate / 1,3-butadiene / styrene polymer is. 2. Composition according to claim 1, characterized in that net that the ratio of alkenyl arene residues to conjugated Alkadiene residues in the block elastomer is about 1: 1 to about 1: Io. 3. Composition according to claim 2, characterized in that the alkenyl arene residues of a hydrocarbon 25 substances of the benzene series are that the weight ratio of block elastomer to methacrylate modifier is about 4: 1 to about 1: 4 that the weight ratio of Block elastomer to ABS modifier about 5: 1 to about 1; 5 and the ABS modifier is about the same 3o refractive index like the vinyl halide polymer. 4. Composition according to claim 3, characterized in that net that the block elastomer has styrene units and 1,3-butadiene units or isoprene units, the amount of polymeric impact modifier and the block 909883/05 Ik elastomers in mass ranging from about 5 to 2o % By weight, based on the weight of the mixture, and the weight ratio of block elastomer to ABS Modi-, is about 4: 1 to 1: 4. 5 5. Composition according to claim 4, characterized in that it is used as a vinyl halide polymer contains a vinyl chloride homopolymer and the amount of the methacrylate modifier and the styrene block elastomer Io in the mass about 8 to about 15 wt .-%, based on the Weight of the mixture. 6. Composition according to claim 5, characterized in that it is a vinyl chloride polymer contains vinyl chloride polymer polymerized in the mass. 7. Composition according to claim 6, characterized in that it is a styrene / - Contains 2o 1,3-butadiene block elastomer. 8. Composition according to claim 7, characterized in that the block elastomer is styrene and 1,3-butadiene in a weight ratio in the range of about 25 contains 1: 1.5 to about 1: 3. 9. Composition according to claim 8, characterized in that it is used as a polymeric impact strength modifier contains a methacrylate modifier. 10. Composition according to claim 9, characterized in that it is a block elastomer one two Polymer containing blocks of styrene and 1,3-butadiene monomer residues in a weight ratio of about 1: 3 and the weight ratio of block polymer 809883/0574 rem to methacrylate modifier is about 1: 1. 11. Composition according to claim 9, characterized in that it is a three block elastomer Polymer containing blocks of styrene and 1,3-butadiene monomer residues in a weight ratio of about 1: 3 and the weight ratio of block polymer to methacrylate modifier is about 1: 1. 12. Composition according to claim 9, characterized in that it is a radial block elastomer Block elastomer from styrene and 1,3-butadiene monomer residues in a weight ratio of about 1: 2.3 contains and the weight ratio of the block elastomer to the methacrylate modifier in the range of about 1: 1 up to about 4: 1. 13. Composition according to claim 9, characterized in that it is a radial block elastomer Block elastomer made from styrene and 1,3-butadiene monomer residues in a weight ratio of about 2: 3 and the weight ratio of block polymer to methacrylate Modif izer is about 1: 1 to about 4: 1. 14. Composition according to claim 8, characterized in that it is used as a polymeric impact strength modifier contains an ABS modifier. 15. Composition according to claim 14, characterized in that g e k e η η, that as a block elastomer it is a radial block elastomer composed of styrene and 1,3-butadiene monomer residues in a weight ratio of about 1: 2.3 and the weight ratio of block elastomer. to the ABS modifier about 1; 1 is. ' 909883/0574 2307840 16. Composition according to claim 14, characterized in that it is a radial block elastomer Block elastomer made from styrene and 1,3-butadiene monomer residues in a weight ratio of about 1: 1.5 and the weight ratio of block polymer to ABS modifier is about 1: 1. 17. Composition according to claim 6, characterized in that g e k e η η, that as a block elastomer it is a styrene / Io contains isoprene block elastomer. 18. Composition according to claim 17, characterized in that it is a three block elastomer Elastomer comprising blocks of styrene and isoprene monomer residues in a weight ratio of about 1: 6 and the weight ratio of block elastomer to the polymeric impact strength modifier about 1: amounts to. 19. Impact-resistant molded article, consisting of the mass according to claim 1, 20. More impact resistant, substantially more transparent or translucent molded article consisting of the mass 25 according to claim 3. 21. Vinyl halide / hydrocarbon polyolefin graft polymer which can be shaped into impact-resistant objects, characterized in that it contains a thermoplastic block elastomer which, as the main part of the monomer units, contains residues of a monoalkenyl arene of the benzene or naphthalene series with 8 to 20 carbon atoms and a conjugated alkadiene - Lemtfassstoffs with 4 to 10 carbon atoms in an amount of about 1 to 20 %, based on the total weight 909883/0574 the graft polymer and the block elastomer. 22. Composition according to claim 1, characterized in that it contains 1,3-butadiene or isoprene as conjugated alkadiene and a hydrocarbon vinylarene of the benzene series as alkenylarene, the ratio of alkenylarene monomer residues to conjugated alkadiene monomer residues in the block elastomer is about 1: 1 ■ to about 1: Io and the vinyl halide / hydrocarbon polyolefin graft polymer is the product of the free radical liquid phase bulk polymerization of a vinyl halide monomer alone or in combination with up to 5o %, based on the total weight of the monomers, of another ethylenically unsaturated Monomers which can be copolymerized with the vinyl halide, and about 0.05 to about 20 %, based on the vinyl halide monomer, of a core polymer which consists essentially of an olefin polymer having a weight average molecular weight of about 50,000 to about l.ooo.ooo consists and consists of 2o the group is selected that A) Homopolymers of aliphatic hydrocarbon-olefin monomers with 2 to 8 carbon atoms, B) Copolymers of 2 or more of these olefin mono-25 meren, and C) Polymers of at least one of these olefin monomers and up to about 15 %, based on the weight of the polymer, of a non-conjugated aliphatic hydrocarbon polyene with 4 to 18 carbon 3o lenstoffatomen in which all carbon-carbon double bonds do not represent a conjugate system, wherein the olefin polymer is in the polymerization reaction medium is soluble, partially soluble or dispersible. 909883/0574 23. Composition according to claim 22, characterized in that it contains the block elastomer in an amount of about 1 to about 15 %, contains 1,3-butadiene as conjugated alkadiene and styrene as vinylarene and the ratio of styrene residues to 1,3-butadiene residues in the block polymer is about 1: 1.5 to about 1: 2.3. '. ' 24. Composition according to claim 23, characterized in that g e k e η η, that it contains the block elastomer in an amount of about 2 to about 10% and the vinyl halide graft polymer by polymerization in the presence of about 1 to about 20 percent of an olefin core polymer with a weight average molecular weight of about 50,000 until about 3oo, ooo has been formed. 25. Composition according to claim 24, characterized in that it is a core olefin polymer Copolymer of two aliphatic hydrocarbon Contains 2o olefin monomers. 26. Composition according to claim 25, characterized in that it is a core olefin polymer Contains ethylene-propylene copolymer. 27. Composition according to claim 24, characterized in that it is a core olefin polymer Polymer of at least one aliphatic hydrocarbon -olefin monomer and a non-conjugated ali- Contains 3o phatic hydrocarbon polyene. 28. Composition according to claim 27, characterized in that it is a core olefin polymer Terpolymer made from two aliphatic hydrocarbon olefin monomers and the non-conjugated polyene, 909883Λ0574 wherein the trunk polymer as non-conjugated polyene contains a diene in an amount of up to about 6 %, based on the weight of the trunk polymer. 29- mass according to claim 28, characterized in that it is an ethylene / Contains propylene / ethylidene norbornene terpolymer. • 3o. A mass according to claim 29, characterized in that g e k e η η, that the block elastomer is a radial styrene / 1,3-butadiene block elastomer with a styrene / 1, 3-butadiene ratio of about 1: 2.3 or a radial styrene / 1,3-butadiene block elastomer with a Styrene / 1,3-butadiene ratio of about 1: 1.5 lightens .. 15th 31. Shaped article consisting of the composition according to claim 21. 909883/0574