DE2432372A1 - COMPATIBLE POLYMERIZE MIXTURE - Google Patents

Description

Patent attorneys:
Dr. Ing.Walter Abltz
Dr. Dieter F. Mo'rf
Dr. Hans- ^ TBrauns

B Itünchan BS ₁ Plenzenauerstr. 28 5 July 19 7 ² y

1313 GT-561-F - Add.

Additional registration to P 23 * »2 219.7

THE GENERAL TIRE & RUBBER COMPANY One General Street, Akron, Ohio 44-329, V. St. A.

Compatible polymer mixture

Previous efforts to identify a specific set of physical properties in a particular type of polymeric product have shown that the best individual properties can be promoted in homopolymers seem, and that every effort to create a combination with optimal physical properties by adding copolymers are produced from monomers whose homopolymers have a specific, desired physical property own, easily leads to copolymers whose physical properties represent a compromise. this was found even in the production of block copolymers. Efforts to find the best features of two or more Combining polymers in mixtures usually resulted in products whose properties are not related with the change in the proportions of the polymer components stood, and in many cases the properties were desirable all polymer components have been lost, especially in mixtures of homopolymers. During this

- Λ - 5 0 98 8 A / 1 1 Oh

Failures first, inadequate mixing methods for dispersing of the one polymer were ascribed to the other, it now appears that such failures almost are entirely due to the inherent incompatibility of the polymers to be mixed.

Incompatibility in polymer mixtures is sometimes necessary, to develop desired physical properties in such mixtures. One of a whole Number of examples of this phenomenon is the improvement of the impact resistance of a composition of matter on the basis of a particular type of resinous homopolymer by adding a different, incompatible polymer inflicts. Experimental investigations have shown that the two polymers must be incompatible in order to achieve the to achieve the best result. In this case the term "incompatible" extends to materials, their mixture separately and clearly the characteristic of the glass phase transition temperature (or freezing temperature) of each of incompatible materials in the mixture.

Various combinations of resinous polymers and rubbery ones Polymers were tried in an effort to find new materials with some combination of the desirable ones To create properties of the constituent parts with a minimum of undesirable properties of the constituent parts. Under The combinations that were tried would be combinations of polymers of the styrene type and of polymers of the Butadiene type, especially combinations in which high proportions of styrofoam polymers were used to make tough To produce polystyrene molding compounds.

Block copolymers of the type AB, ABA, (AB) ₁₁ and (AB) ₁₁ A have already been prepared, and in certain systems there are already well-defined block copolymers in combination with

- 2 -
509884/1104

NachQERITiOMT

P 24 3.2 372.6 September 3, 1974

The General Tire & Ruober Company

. ^. 24323/4

polym-erisi exten conjugated dienes, polymerized styrenic ones Polymers and combinations of two such polynters, sometimes used with the use of additional ingredients. Among other things, the polymers like them are known in U.S. Patents 2,727,878 and 2,755,270 and in British Patent 1 092 296. To the state of the art are also of interest U.S. Patents 3,231,635, 3,251,905, 3,322,856, 3,377,404, 3,429,951, 3,441,530, 3,464,850 and 3,476,829, JA-PS 27 866/71; NL application 03 376/66; FR-PS 1 457 763 and GB-PGen 1 053 596, 1 120 404 and 1 145 923.

The present invention relates in particular to three-component mixtures, in which one component is a polystyrene, the other component a polybutadiene and the other Component a graded AB / v-styrene / ButadieriZ-styrene block copolymer represents. Of the above-mentioned references, the one which relates to the subject matter of the invention closest, U.S. Patent Application 3,476,829, in which a combination of 40 to 95 and - preferably 60 to 90% by weight of polystyrene, 4.5 to 39.5 and preferably 9 to 30% by weight of a rubbery conjugated diene polymer and 0.5 to 25, and preferably 1 to 20 weight percent of a solution polymerized Block copolymers of indefinite structure, however 50 to 98 and preferably 70 to 90 wt.% Contains polymerized styrene, is shown, the composition of substances 5 t> is 40 and preferably 8 to 35 wt.% of rubber, both as a homopolymer and as a mixed polymer, contains. This citation teaches that hardening is also used in order to achieve the desired properties Peroxide is necessary; however, there is a simple disclosure of such a composition of matter which is brief in the course of the production of a set of substances falling within the scope of the citation was free of peroxide. No properties or usefulness are given for the peroxide-free composition of substances.

- new description page 3 5 09884/1104

No value is placed there on the particle size of the rubber-like polymer, nor does the teaching indicate that the structure of the block copolymer is somehow critical. The specifically disclosed interpolymers appear to be graded AB-styrene-butadiene interpolymers with styrene-butadiene weight ratios of 50:50, 75:25, 88:12, and 90:10.

DT-OS 20 09 407 also belongs to the prior art. This DT-OS relates to a mixture with excellent properties at low temperatures and at room temperature, consisting of

(A) a basic substance (matrix) of polymers made from at least 90% by weight vinyl aryl monomers, any other monomers are other ethylenically unsaturated monomers, these polymers have a Average molecular weight from about 50,000 to

500,000;
are dispersed in this matrix

(B) Polymers which are conjugated from at least 60% by weight Serve, 0 to 40 wt% monovinyl substituted monocyclic aryl compounds and 0 to 10 wt% others Ethylenically unsaturated monomers with not more than 3% by weight of non-conjugated di-unsaturated compounds have been prepared, the particle size of this component being at least 0.01 / u and the average molecular weight of these polymers at least 100,000 is; and

(C) block copolymers of the type ABA, in which each Segment A is a polymer segment which is defined like component (A) and is compatible with it, and in which each segment B is a polymer segment, which is defined as component (B) and with this

- 4 509884./11(U

• W *

XJT_69, i) -F Add

is tolerable, the weight ratio of total A to B being in the range from 20:80 to 90:10 and the average molecular weight of these block copolymers being at least 100,000; wherein components (A) and (B) are present in a molar ratio of at least about 1: 1 and are so incompatible that the finished mixture clearly shows the glass phase transition temperature of both components and component (C) in the mixture in an amount of about 3 to 25 wt. of the total mixture is present and all monovinyl monoeyclische aryl units in the components (A), (B) and (C) 75 to 95 wt -.% of the total units in these components account.

The main object of the present invention is to create a new mixture of incompatible polymers, Preferably homopolymers, using a special type of block copolymer as an alloying (mixing) Agent or as polymer-polymer surface treatment agent, to bind the incompatible polymers to one another while maintaining a high degree of phase separation is maintained, but a link is formed between the two phases. Another goal is provision novel polystyrene masses with good impact strength values, which are well balanced properties from room temperature to -AO, 0 C, compare

509884 / 11CU

P 2H 32 372. 6 »fc * October 31, 1974

The General Tire & Rubber Co. GT-8O8-F

with currently available polystyrene compositions. Another object is to provide such compositions which are prepared by melt mixing under shear stress, as well as by methods ^f of mixing in solution without loss of desired properties könnem Both these objectives as well as others which can be deduced from the description, are represented by the realizes the present invention.

The invention is now a further embodiment of the

Mixture according to the main patent (DT-OS 2 3 ^ 2 219),

which consists essentially of

(A) a base substance (matrix of polymers produced from at least 90% by weight vinylary! _{Monomers 3} any other. Monomers are other ethylenically unsaturated monomers; these polymers have an average molecular weight of about 50,000 to 50000;

(B) polymers, the conjugate of at least 60 wt .- # dienes, east to 40 wt -.% Monovinyl substituted monocyclic aryl compounds, and 0 to -10 · .Gew. -% ■ other äthyleniseh unsaturated monomers with not more than 3 wt. non-conjugated diunsaturated compounds have been prepared, the number average molecular weight of these polymers being at least 100,000; and ^; -

(C) graduated block copolymers of the type ABA, 'in which each segment A is a polymerisation segment is defined as component (A). and is compatible with this, and in which each segment B A polymer segment is defined as a component (B) and is compatible with this, whereby - the

- Neue-Seitö 5 ä - '

ORIGINAL! NSPECTED

GT-8O8-P ^.

G. weight ratio of total A to B in the range of 45:55 to 60:40 and the number average molecular weight of these block copolymers is at least 150,000 and the graduated block copolymers has two major glass phase transition temperatures between about -90 C and about +90 C;

where components (B) and (C) in component (A) dispersed as mycelia with maximum dimensions ranging from 0.2 to 5 microns, the components (A) and (B) are in a molar ratio of at least about 1: 1 and are so incompatible that the finished product The mixture clearly shows the glass phase transition temperature of both components and the component (C) in the Mixture is present in an amount of about 3 to 25 percent by weight of the total mixture and all monovinyl monocyclics Aryl units in components (A), (B) and (C) 75 to 95% by weight? of the entire units make up in these components, characterized in that the mixture as a constituent

(B) non-crosslinked, conjugated, contain aliphatic diene polymers which comprises at least 60 wt .-% 1,3-butadiene addition and 0 to 40 wt -.!% Of interpolymerized, monovinyl substituted monocyclic Ary compounds from 0 to 10 wt. -? other copolymerized, ethylenically unsaturated monomers are prepared; and as a component

(C) contains graded block copolymers of the ABA type, in which each Α segment is a polymer segment which is defined substantially like component (A) and is compatible with it, and each B segment is a polymer segment that is essentially

- New page 5b -

509884/1 104

GT-8O8-F

as the component (B) is defined and is compatible with it, wherein the number average molecular weight of said block copolymers is from 150,000 to 500,000 and the stepped block copolymers referred to have a glass transition head temperature of about -90 C + _ 5 ° C;

components (B) and (C) as a discontinuous phase being dispersed in said component (A) as particles at least 70 % by weight of which have diameters in the range of 0.2 to 5 microns.

The invention therefore includes mixtures of otherwise incompatible Polymers, in particular homopolymers of a conjugated aliphatic hydrocarbon diene, such as butadiene or isoprene, as a discontinuous phase in a matrix of homopolymers of a monovinyl-substituted, monocyclic aromatic hydrocarbon such as styrene. The discontinuous phase becomes homogeneous in the matrix, through the use of graded block copolymers of the general Configuration ABA, dispersed, in which A and B polymeri *

■ New page 5c -

ORIGINAL-INSPECTED-

50988Λ / 1104

Represent satsegmente, which are compatible with the polymers to be mixed. The block copolymers act as polymer-polymer surface treatment agents in that they alloy or mix otherwise highly incompatible polymers. For the system of the styrene-butydiene type, the block copolymers ABA are such that in each case A represents a polymer segment which is compatible with the polymer of the styrene type and B represents a polymer segment which is compatible with the polymer of the diene type. These mixtures can be satisfactorily prepared by mixing in solution, mixing on roll mixers or on high shear mixers such as a Banbury mixer, or any continuous mixing apparatus, with sufficient care being taken to mix the components together.

The mixtures according to this invention provide one Improvement of some physical properties of the continuous polystyrene-like phase without a substantial one Decrease in the other physical properties occurs. The improvement in properties, however, depends to a considerable extent on the particle size of the discontinuous Phase consisting of particles of the ABA graded block copolymer and the diene type polymer. The most effective particles must each have a particle diameter in the range of 0.2 to 5 microns, although Particles outside this range have no detectable effect. As a result, at least 70% by weight and preferably 85 or more percent by weight of the discontinuous phase present as particles with the defined particle size range. The physical state of the diene-like polymers and the graded ABA block copolymers plays before the Incorporation into the styrenic polymer only plays a role insofar as it is the particle size of the discontinuous phase influenced in the finished mixture, with the named partial

- 6-

509884/110 4

size is also directly influenced by the shear force, acting on the system during mixing. '

The mixtures of the invention are particularly useful for Highly impact-resistant polystyrene film material, which is used, for example, for refrigerator interiors and for injection molding Manufactured parts, for example vacuum cleaner housing, is used.

It has been found that one can obtain an impact-resistant polystyrene with an excellent balance of properties can be made by blending polystyrenes and polydienes with graded ABA-type block copolymers, in that each Α block is essentially polymerized styrene with the remainder of each such block being polymerized Is diene, and each B block is essentially polymerized diene with the remainder of said block is polymerized styrene and the weight ratio of A to B ranges from 45:55 to 60:40.

Similar studies are carried out on mixtures of polystyrene, polyisoprene and AB block copolymers of styrene and Isoprene has been made; compare "European Polymer Journal, 1968, Volume 4, pages 175-205, Pergamon Press (England) ". However, these investigations showed that the presence of the polyisoprene was not as important as the presence of the block copolymer.

The polymers (A) of the styrene type, which are used as basic substances (Matrix) can be used in the mixtures of the present invention, simple homopolymers of styrene or α-methyl styrene or similar vinyl aryl monomers or copolymers containing at least about 90% by weight of such Contain monomers, preferably monocyclic ^ yinyl aryl monomers, which is at least 35% by weight copolymerized

: - 7 -

GT-561-F - Add.

**> * 24323/2

Include styrene. The polymers of the styrene type can also contain up to about 10% by weight of other copolymerized, contain ethylenically unsaturated "compounds, including mono-unsaturated compounds and conjugated di-unsaturated Compounds, such as A cry! Compounds, such as acrylic acid and methacrylic acid '; Esters, amides and nitriles of the type of methyl methacrylate, ethyl acrylate, methaeryl amide, Fumaric acid nitrile and acrylonitrile, cyclically unsaturated Compounds such as the nuclear chlorostyrenes, vinyl naphthalene, Vinyl carbazole, acenaphthylene; and conjugated, unsaturated, such as butadiene, isoprene, chloroprene, 2,3-chlorobutadiene, Piperylene and the like. In bulk polymerization, these resins are usually made by the styrene and comonomer heated to temperatures in the range of 100 to 200 ° C, if necessary using of pressure to bind the monomers. The polymerization can also be carried out by adding peroxidic catalysts generate free radicals, such as benzoyl peroxide, acetyl peroxide, Di-t-butyl peroxide and the like can be carried out at lower temperatures. The polymerization can also be carried out in suspension, to obtain a dry powder, or be carried out in emulsion, usually resulting in a polystyrene latex which either coegulates into solid, powdery polystyrene or as such for blending with either or both the other ingredients can be used in the form of latices. The polymerization can also be carried out in solution the product, if desired, precipitating by normal methods such as steam stripping will.

The most important variable in the polystyrene component is its molecular weight. The vinyl aromatic or plastic polymer should have an average molecular weight between about 50,000 and 500,000, preferably in the range from 100,000 to 300,000, whereby these values indicate the numerical mean,

- 8 509884 / 11OA

The polymers of diene type (B) used in the discontinuous phase in the mixtures according to the invention are non-crosslinked homopolymers of 1,3-butadiene or non-crosslinked random copolymers containing at least 60% by weight 1,3-butadiene and preferably at least 90% by weight conjugated dienes, 0 to 40% by weight styrene or cc-methylstyrene and no more than 10% by weight of other ethylenic unsaturated compounds that can be polymerized into it included. It goes without saying that the above percentages are based on the weight of the copolymers. Suitable monomers for interpolymerization with butadiene include, for example, vinyl aromatics, such as the various ones mono- and poly-nuclear chlorinated styrenes, vinyl naphthalene, Vinyl carbazole and the like; Vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether and the like, methyl isopropenyl ketone, isopropenyl acetate and the like, <x, β-unsaturated Acy! compounds, such as Acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, Ethyl acrylate, diet ethyl mal eat, maleic anhydride and the like., and conjugated, unsaturated compounds such as isoprene, 2,3-dimethyl-i, 3-butadiene and the like.

The polymers used in the mixtures according to the invention of the service type can be any of those well known Polymerization systems are prepared as in Hasse, solution, or emulsion polymerization systems.

The conjugated diene or rubber polymer should be a Average molecular weight between 100,000 and a few million, preferably in the range from 250,000 to 500 OQQ own. It is also important that the conjugated diene o & er rubber polymer sufficiently incompatible with the basic substance (Matrix) in which to be dispersed should, so that a mixture without a block copolymer clearly the glass transition or freezing temperature of the Eaut-

S03884 / 1T04

Schukpolymeren shows.

With a similar mixture as it is according to DT-OS 20 09 4-07 "is known, the ratio of the monomers in the block copolymers is 20:80 to 90:10 based on weight. According to the present invention, however, this ratio should be 4-5:55 to 60:40. Because outside of this relatively narrow range, the desired, precisely balanced properties are not achieved.

The graded ABA block copolymer types (C) used in the mixtures according to the invention are such that the graded segments A are compatible with the polymer of the styrene type and the graded segments B are compatible with the polymer of the diene type. At the same time, each segment A should be incompatible with the diene-type polymer and each segment B should be incompatible with the styrene-type polymer, as the term incompatible has been used above. The monomer which was used as the main component in the preparation of the styrene-type polymer and the monomer which was used in the preparation of the respective segment A of the block copolymer are preferably the same. Also, the monomer which was used as a main component .for the preparation of the polymer diene type monomers and that of the block interpolymer used in the production of the respective segment B, also preferably ^j are the same.

The block copolymers according to the present invention differ from the pure block copolymers ABA, which are also referred to as "graded" or "graduated" ABA block copolymers because they with otherwise the same molecular weights, some of the A-mononation, generally about 20% by weight of the total amount Α monomer, included in the B block, while some of the B monomer appears in the Α block. On the other hand, exist in the

- 10 509884/1 1 OA

GT-56I-P - Add.

In pure ABA block copolymers, the Α blocks all consist of A monomers, while the B block consists entirely of B monomers. This fact is manifested _{3 by the} fact that there is a difference in the glass transition temperatures between pure block copolymers and graded block copolymers with essentially the same molecular weight. For styrene-butadiene-styrene Bloekcopolymere the pure block copolymers show a glass transition temperature of about -105 ⁰ C for the polybutadiene block B and a glass transition temperature of about 105 ° C for the polystyrene block A, while the corresponding, according to the invention, the stepped block copolymers have a glass transition temperature of about - Show 90C + _ 5C for the graduated polybutadiene block. The glass transition temperature of the styrene blocks in the graduated block copolymers according to the invention can generally be recognized by thermal analysis; but it is not essential.

In pure block copolymers, the main or larger Α blocks should have number average molecular weights between 25 and 50 % of the calculated number average molecular weight of the continuous polystyrene phase. In graded block copolymers, however, because of the styrene monomer combined with the main polybutadiene blocks, the calculated number average molecular weight of the polystyrene in the polystyrene blocks in the graded block polymer is closer to 30 to 70 % of the calculated number average molecular weight of the continuous polystyrene phase. That is, for a continuous polystyrene phase with a number average molecular weight of 120,000, each of the graduated Α blocks in the block copolymer should have a calculated number average molecular weight of 36,000 to 84,000 and that in the main blocks the actual number average molecular weights in the range from about 30,000 to 60 000 lie. For

- 11 509884/1104

graduated block copolymers with an A: B ratio of 45:55 to 60:40 can be the total calculated number average molecular weight range from about 120 QOO "to about 375,000. However, it has been found that the graduated Block copolymers have a number average molecular weight in the range from 150,000 to 500,000, preferably from should have about 200,000 "to 300,000, in the case of the inventive Crowds.

The initial particle size in the ABA graded block copolymers and the diene polymers are not particularly critical. What is important, however, is the particle size of the discontinuous phase in the mixtures according to the invention. In order to achieve an optimum of advantageous properties in the finished mixtures according to the invention with particular emphasis on impact resistance, it is necessary that at least 70% by weight and preferably 85% by weight or more of the defined and stressed particles in the finished mixtures according to the invention each have a particle diameter in the range of 0.2 to 5 microns. A minor amount, that is, not more than 30 wt.% Of the particles in any fertiggstellter mixture but may outside the defined range are _·% carry those particles whose Grossen below the defined range, not essential to improve the physical properties of the mixtures, if one compares the properties of the blends with those of polystyrene alone, and those parts whose sizes are above the defined range, tend to have a negative influence on the surface design when manufacturing vacuum-formed objects, although otherwise apparently, the physical properties in the blends compared to a pure one. Polystyrene _{t are} improved.

This is the production of ABA graduated block copolymers.

- 12 SQ9884 / 1104

GT-561-F - Add. r ,, "rv ₀

Ife / 4343/2

known from US Pat. No. 3,287,333 and will also be used below shown in example 1. The preferred solvents for such manufacturing processes are hexane and cyclohexanes

The processing conditions have a major influence on the molecular weight of all components and on the Particle size of the discontinuous phase. Mix with high shear forces easily sets the particle size of the discontinuous Phase down. For the purposes of the present invention, particle sizes of the dispersed phase, once they have been reduced below the specified minimum values, they are no longer corrected. from The particle sizes of the dispersed particles of the ready-mixed product are of greatest importance. The particle size was determined optically or with an electron microscope.

The polymer mixtures of the present invention can contain polymers of type A and B as described above in a molar ratio of about 1 : 1 to 100: 1 or higher, but the molar ratio is preferably in the range of about 2: 1 to about 5 ^: 1 · dies is equivalent to a weight ratio of about M-: 1 to about 10: 1 in a polystyrene-polybutadiene mixture. The block copolymer is used in an amount of about 3 to 25% by weight of the total mixture, preferably in about 5 to 15% by weight. When Butadieri polystyrene mixture, the graded ABA block copolymer ^r used, it was found that the Gesamfcgehalt of vinylaromatics z. B. styrene, both as a homopolymer and as a mixed polymer in the range of 75 to 95 wt *% of the total mixture, preferably in the range of about 80 to about 90 wt.

Of particular interest are mixtures in which the used Monomers in all components on styrene and

- 13 50 9 8 S 4/11 OU originally inspected

Butadiene are restricted. You can get through such mixtures Establish proper mixing in the melt using shear forces without any significant decrease the physical properties compared to similar mixtures made in solution systems.

The mixtures according to the invention can be prepared according to customary methods known from the prior art, such as those mentioned in the aforementioned patents, for example, produce. Melt blending using shear forces, for example in Banbury mixers, mills and / or continuous ones Mixing apparatus has proven to be successful for the mixtures according to the invention.

The following examples are intended to illustrate the best methods and the alternative methods for making those of the present invention Illustrate compositions without thereby limiting the invention. Unless otherwise stated, refer the quantitative measurements on the weight.

example 1

The block copolymer M used in this example was a graded ABA block copolymer, in which each A is essentially a polymerized portion of styrene and B is essentially a portion of polymerized butadiene represent, the total polymerized styrene being 60% by weight of the block copolymer and the total butadiene polymerized to a total of 40% by weight of the block copolymer amount to. The present copolymer was prepared with stirring in an n-hexane solution, wherein sufficient η-hexane was present so that a solution with about 15% by weight of pesticides was present at all times. Monomer Styrene and a sufficient amount of butadiene to achieve the desired 60/40 styrene / butadiene weight ratio,

_ 14- 509884/11 (K

-F - Add.

were dissolved in η-hexane at room temperature and then heated to 6515 ° C. A 1% solution of n-butyllithium in η-Hexane was added slowly "at 65.5 ° C" until an easy exothermic reaction was evident, indicating that all

Impurities had reacted and the subsequent polymerization were no longer bothering you. Then that much dilithium-polyisoprene catalyst was added and the mixture heated to 65.5 ° C for about 4 hours so that a graded ABA block copolymer is achieved 'with an average number molecular weight from about 225,000 to 250,000, the one contained central part which was rich in polybutadiene and terminal parts which were rich in polystyrene. The still active (living) copolymer was deactivated or "killed" by adding isopropanol until the solution became colorless. An antioxidant (2,6-di-t-butyl-pcresol) was added as a solution in isopropanol with 0.01 g of antioxidant per milliliter of isopropanol added, so that about 1% by weight of antioxidant, based on the initial weight of the butadiene, was present.

The solution of the graded ABA block copolymer can be used for Mixing in solution can be used or the hexane (and isopropanol) can be stripped off with steam, being then the ABA block copolymer as a fine crumbly mass obtained, which can be mixed in solid form.

The block copolymer M in benzene solution at 30 ° C was in solution with a technical polystyrene with an average molecular weight of 120,000 and a technic see polybutadiene with an average molecular weight in the range of 250,000 to 300,000 mixed in amounts, so that the result was a mixture containing 72.5% by weight of pure polystyrene, 12.5% by weight of block copolymer M and 15% by weight contained pure polybutadiene. The block copolymer and polybutadiene formed particles, of which at least 70% by weight

- 15 509884/1104

Ranged in diameter from 0.2 to 5 microns. The total styrene content in the mixture is 80% by weight. The "polymer mixture" is best isolated by adding the benzene solution to stirred isopropanol. The polymer precipitates in the process. The resulting white polymer mixture is then in one Yakuumofen dried to constant weight at 50 ° C.

Test samples of the polymer blend were prepared by placing the polymer blend between two polytetrafluoroethylene coated plates and heating at 154 ° C for 1 minute to convert the polymer blend into a molten disc which was cut into strips and kept at 188 ° C for 10 minutes long at 1410 kg / cm ² (20,000 ρsi) into test bars of 6.35 x 15.24 χ 0.318 cm (2.5 x 6 χ 0.125 inches) and 2.858 χ 15 * 24- χ 0.318 cm. Test specimens were cut from the test bars and used in a number of tests including determination of flexural modulus according to ASTM, test method 2418, determination of notched impact strength, and determination of dimensional stability under heat (C) when the test samples were subjected to a load of 18.58 kg / cm 0.254 mm and 1.52 mm were deflected.

The test samples showed a flexural modulus of 19,500 kg / cm, a notch impact strength of 0.420 mkg / cm notch (7.54-lbs. / inch notch), a deflection at 85 ° C of 0.254 mm and a deflection at 98 ° C of 1.52 mm.

Test samples prepared in the same way from a technical high impact polystyrene and a technical polystyrene, with a high flexural modulus showed flexural

modules of I5 940 and 26 840 kg / cm, notch impact strengths of 0.087 and 0.0625 mkg / cm notch, 0.254 mm deflection at 79 ° C and 75 ° C and 1.52 mm deflection at 88 ° C and 84 ° C, respectively.

- 16 -

509884/1104

GT- 561 -Έ

Example 2

A block copolymer M from dry crumbs was in one High speed Banbury mixer with commercial grade Polystyrene and commercial polybutadiene, as used in Example 1, mixed for about 4 minutes at 204 ° C. The block copolymer and polybutadiene formed particles, of which at least 70% by weight in diameter between 0.2 and 5 microns.

Test pieces from the mixtures obtained, which were produced and tested according to the method according to Example 1,

showed a flexural modulus of 17,500 kg / cm, a notched impact strength of 0.425 mkg / cm notch and at 81 ° C a deflection of 0.254 mm.

B e i s ρ i e 1 5

A polymer blend was prepared following the procedure of Example 1 produced using the block copolymer M and of the commercially available polystyrene and commercially available polybutadiene used in Example 1 in those given below Amounts. The block copolymer and the polybutadiene formed particles of which at least 70% by weight diameter were between 0.2 and 5 microns. Test specimens made from these mixtures prepared and according to the example 1 The following procedures show that the methods described have been tested Characteristics:

% By weight Hurry 2432372 77.5
10.0
12.5 tab Polystyrene
Polybutadiene
Block copolymer M 20 680 (294 000) Flexural modulus kg / cm (psi) • 0.345
(6.29) Notched impact strength
mkg / cm notch
(ft.Ibs./inch notch) Dimensional stability (C) 80
92 0.254 mm (10 mil)
1.52 mm (60 mil)

A similar mixture, which was prepared according to Example 2 and tested in the same way, showed one Flexural modulus of 21,600 kg / cm, a notched impact strength of 0.238 mkg / cm notch and a 0.254 mm bend at 85 ° C.

Example 4

A polymer blend of 7 ^^ 5 parts of the polystyrene from Example 1, 16.5 parts of the polybutadiene from Example 1 and 9 parts of a block copolymer M was prepared by milling and mixing in the absence of a solvent at 163 ° C. for 10 minutes. The block copolymer and the polybutadiene formed Particles at least 70% by weight of which were between 0.2 and 5 microns in diameter.

Test specimens from this polymer mixture, which were produced and tested according to the methods described in Example 1, showed a flexural modulus of 18,500 kg / cm, a notched impact strength of 0.314 mkg / cm notch. The dimensional stability temperature was 77 ° C (0.254 mm bend) and 95 ° C (1.52 mm bend).

- 18 509884/110

Example 5

A polymer blend of 72.5% by weight of that used in Example 2 commercial polystyrene, 15% by weight of the commercial polybutadiene used in Example 1 and 12.5 % By weight of a block copolymer M was obtained by mixing and grinding of the components in the absence of a solvent at 163 ° C in a period of 10 minutes. Test rods this polymer mixture, which were prepared and tested according to the method according to Example 1, showed a Flexural modulus of 19,300 kg / cm, a notched impact strength of 0.318 mkg / cm notch and. a dimensional stability of 88 ° C (0.254 mm bend) and 96 ° C (1.52 mm bend).

Similar good results are obtained when using polymer mixtures obtained by extrusion and / or injection molding have been manufactured.

Example 6

A block copolymer N is prepared according to that in Example 1, but using the same Amounts of styrene and butadiene.

A mixture of 18.8 parts of the block copolymer N, 118.1 parts of the commercial polystyrene according to Example 1 and 13.1 parts of the commercially available polybutadiene according to Example 1 and 0.3 parts of a standard antioxidant was prepared according to the procedure described in Example 2. The block copolymer and the polybutadiene formed particles at least 70% by weight of which were between 0.2 and 5 microns in diameter.

Test specimens that were produced as described in Example 1

den, showed a flexural modulus of 20 800 kg / cm, a notch

- 19 509 884 / 1.104

Impact strength of 0.296 mkg / cm notch and dimensional stability of 81 ° C (0.254 mm bend) and of ° / 1 ° C (1.52 mm bend).

The blends of this invention are of particular interest because of their excellent properties at low temperatures as well as at room temperature. For example shows a polymer mixture according to the invention with a total styrene content of 80% by weight and a notched impact strength of 0.348 mkg / cm notch at tree temperature, a notched impact strength of 0.265 mkg / cm notch or 0.166 mkg / cm notch at -29 ° C or -40 ° C. This shows that the polymer mixture at -40 C had a better notched impact strength than other commercially available high-impact polystyrenes at the same temperature or even at room temperature,

For the purposes of the present invention, the discontinuous Phase dispersed in the continuous phase or matrix as particles, of which at least 70% by weight Particles have diameters in the range of 0.2 to 5 microns as measured by the "Zeiss Particle Size Analyzer". This analyzer and its use are described in "New Techniques of Particle Analysis" by D. W. Montgomery in Rubber Age, February 1964.

Claims (20)

The General Tire & Rubber Co. IzI-öuö-j? New Pat entari sprue hl Further training of the mixture according to the main patent (DT-OS 2 342 219), which consists essentially of (A) a base material (matrix) of polymers prepared from at least 90 wt -.% Vinyl aryl monomers, any other monomers are other ethylenically unsaturated monomers, these "polymers have an average molecular weight of about 50,000 to 500,000; . (B) polymers composed of at least 60 wt -.% Conjugated dienes, 0 to 40 wt -.%. Monovinyl substituted monocyclic Ary compounds and 0 to 10 wt -% other ethylenically unsaturated monomers have not been more produced than 3 wt .- / S non-conjugated di-unsaturated compounds, wherein the number average molecular weight of these polymers is at least 100 000.!.; and (C) Graduated block copolymers of the type ABA, in which each segment A is a polymerization segment which is defined as component (A) and is compatible with it, and in which each segment B is a polymer segment which is defined as component (B) and is compatible with this, wherein the weight ratio of total A to B is in the range from 45:55 to 60:40 and the number average molecular weight of these block copolymers is at least 150,000 and the graduated block copolymer has two main glass phase transition temperatures between about - 90 ⁰ C and about +90 ⁰ C; ■ '-! - "- 509884/110 4 P 2k 32 372.6 '' AS. ^lh ' ^November The General Tire & Rubber Co. GT-808-F where components (B) and (C) in component (A) dispersed as mycelia with maximum dimensions ranging from 0.2 to 5 microns, components (A) and (B) in a weight ratio of from about 4: 1 to about 10: 1 are present and so incompatible that the finished mixture clearly has the glass phase transition temperature shows both components and component (C) in the mixture in an amount of about 3 to 25 wt .- # the Entire mixture is present and all monovinyl monocyclic aryl units in components (A), (B) and (C) 75 to 95 wt -.% Of the total units in these components make up, characterized in that the mixture comprises as constituent (B) non-crosslinked, conjugated, contain aliphatic diene polymers which comprises at least 60 wt -.% Of 1,3-butadiene and 0 to 40 next to Ge \ i .-% of interpolymerized, monovinyl substituted monocyclic Ary compounds from 0 to 10! wt -.% of other mischpolymerisierter ethylenically unsaturated monomers sindjund prepared as a constituent (C) contains graded block copolymers of the type ABA, in which each Α segment is a polymer segment which is defined essentially like component (A) and is compatible with it, and each B segment is a polymer segment which is essentially as the component (B) is defined and is compatible with it, wherein the number average molecular weight of said block copolymers is from 150,000 to 500,000 and which have stepped block copolymers mentioned a glass transition head temperature of about -90 ⁰ C + _ 5 ⁰ C; where components (B) and (C) as a discontinuous phase in said component (A) as particles dis- - new page 2 50988Λ / 1 1 (K GT-8O8-F are pergiert, of which at least 70 wt -% have diameters in the range of 0.2 to 5 microns.. (Claims 2 to 20 in the fit of July 5, 197 ¹ O 509884/1 10 GT-561-1? - Add. 2. Mix after. Claim. 1, characterized in that the Polymers in the component. (A) at least 35% by weight contain polymerized styrene and the polymers at least 90% by weight polymerized in component (B), contain conjugated dienes. 3. Mixture according to claim 2, characterized in that the polymers in component (A) have a number average molecular weight from 100,000 to 300,000 have the polymers in component (B) have an average molecular weight of 250,000 to 500,000 and the copolymers in component (C) have an average molecular weight of 200,000 to 300,000. 4. Mixture according to claim 3, characterized in that the number average molecular weight in the A blocks in the copolymers of component (C) is between 25 and 50 % of the calculated number average molecular weight of the polymers in component (A). 5. Mixture according to claim 4, characterized in that the Polymers in component (A) are polymerized monovinyl-substituted monocyclic aryl compounds and the polymers in component (B) are polymerized conjugated dienes having 4 to 5 carbon atoms. - 22 - 509884/1 6. Mixture according to claim 5 »characterized in that the graded block copolymers in component (C) are copolymers of styrene and butadiene. 7. Mixture according to claim 6, characterized in that component (A) consists essentially of polystyrene and component (B) consists essentially of polybutadiene and components (A) and (B) in a molar ratio of about 2: 1 to about 5 ^: 1 are available. 8. Mixture according to claim 7, characterized in that component (C) is present in an amount which is 5 his 15% of the total mix and that the components (A) and (B) are present in proportions such that the total proportion of polymerized styrene in the total mixture is in the range from 80 to 90% by weight. 9. Process for the production of resins with excellent Impact strength, flexural modulus and heat deformation resistance, especially at low temperatures, characterized in that one is a mixture which consists essentially of - (A) a basic substance made of polymers consisting of at least 90% by weight vinyl aryl monomers, with any other copolymerized monomers being other ethylenically are unsaturated monomers, and wherein said polymers have a number average molecular weight of about 50,000 to 500,000; (B) non-crosslinked, conjugated, aliphatic diene polymers which are produced from at least 60% by weight of conjugated dienes, 0 to 40% by weight of copolymerized monovinyl substituted monocyclic aryl compounds and 0 to 10 % by weight of other copolymerized, ethylenically unsaturated monomers , the number average molecular weight of said - 25 - 509884/1104 GT-561-ί ¹ - Add. λ ^, Polymers is at least 100,000; and (C) graded block copolymers of the type ABA ₁ in which each Α-segment is a polymer segment which is defined essentially as component (A) and is compatible with it, and each B-segment is a polymer segment which is essentially as component (B) is defined and compatible with it, the weight ratio of the total components (A) to (B) ranging from 45 J 55 to 60:40, the number average molecular weight of the block copolymers mentioned ranging from 150,000 to 500,000 and the graded block copolymers have a main glass transition temperature of about -90 ° C + 5 ° C; wherein components (B) and (C) as a discontinuous phase are dispersed in said component (A) as particles, of which at least 70% by weight have diameters in the range from 0.2 to 5 microns, components (A) and (B) are in a molar ratio of at least about 1: 1, component (C) is present in the mixture in an amount of about 3 "to 25% by weight of the total mixture, and all of the monocyclic monovinyl aryl units in the components (A), (B) and (C) make up 75 to 95% by weight of the total units in the components mentioned, mixed. 10. The method according to claim 9j, characterized in that the mixture is prepared in a common solvent, and then precipitated from the solvent will. 11. The method according to claim 9, characterized in that the mixture is heated to a temperature of at least 15 ^, 5 ° C is produced. - 24 - 509884/1 1 GT- 561 -ϊ ¹ - Add. ~ 30 »ο / on 07? 12. The method according to claim 9 »characterized in that the polymers in component (A) consist of at least 35% by weight of polymerized styrene and the polymers in component (B) consist of at least 90% by weight of polymerized conjugated dienes. 13 · The method according to claim 12, characterized in that the polymers in component (A) have a number average molecular weight of 100,000 to 300,000, the polymers in component (B) have a number average molecular weight of 250,000 to 500,000 and the copolymers in component (C) have a number average molecular weight of 200,000 to 300,000. 14. The method according to claim 13, characterized in that the number average molecular weight in the A blocks in the copolymers in component (C) between 25 and 50% by weight of the calculated number average molecular weight of the polymer in component (A). 15. The method according to claim 14, characterized in that the polymer in component (A) is a polymerized monovinyl-substituted monocyclic ^ aryl compound and the polymers in component (B) are polymerized conjugated dienes having 4 to 5 carbon atoms. 16. The method according to claim 15i, characterized in that the block copolymer in component (C) is a copolymer s is made from styrene and butadiene. 17. The method according to claim 16, characterized in that component (A) consists essentially of polystyrene, component (B) essentially consists of polybutadiene and components (A) and (B) in a molar ratio of about 2: 1 until about 5 ^: 1 are available. - 25 - 509884/1104 GT-561-F - Add. ^ ·? Δ? 7 ^ 7 9 18. The method according to claim 17 »characterized in that component (C) is present in an amount that is equivalent to 5 to 15 % of the total mixture and components (A) and (B) are present in such proportions that the content of total polymerized styrene in the total mixture is between 80 and 90% by weight. 19 · blend according to claim 7 »characterized in that the components (B) and (C) as a discontinuous phase i _n of said component (A) are dispersed as particles, of which at least 85 wt.% Diameter in the range of 0.2 to 5 microns. 20. The method according to claim 17, characterized in that that components (B) and (C) as a discontinuous phase in said component (A) as particles Are dispersed, of which at least 85 wt.% Diameter in the range of 0.2 to 5 microns. - 26- 509884/1104