DE2722403A1 - MIXTURES OF RUBBER WITH GRAFT MIXED POLYMERISATES - Google Patents

Description

5090 Leverkusen, Bayerwerk E / Rz

16. m \ Wi

Mixtures of rubber with graft copolymers

The invention relates to rubber mixtures, which are characterized in that one Rubber (A) is admixed with a graft polymer (B) in amounts of 1 to 80% by weight, the monomers of (B) being used as the graft are used, are identical or compatible with the monomers of the rubber (A) used for the mixture.

Mixtures of rubber with other rubbers or thermoplastics are known in almost all conceivable variations and are described in the relevant specialist literature (Rubber Chem. Techn. 47 (3) 481-50, 1974; Rubber Chem. Techn. 49 (1): 93-104 (1976).

Their application generally serves to achieve a balanced relationship between processing properties and usage behavior and costs. For the usage behavior, for example, this means that in many cases a specific type of rubber is used for a certain one Application as unsuitable, while another property of the same rubber is highly desirable. Certain rubbers are therefore blended with one another in order to achieve desired properties in addition and undesired ones To weaken properties.

Due to the generally known, more or less severe intolerance of the polymers with one another, there are a number of restrictions in the production of polymer blends (Kolloid-Zeitschrift u. Zeitschrift f. Polymers Vol. 213, 1966 Lothar Bonn; J. Macromol. Sei.-Revs. Macromol. Chem., C7 (2), 251-314 (1972)).

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Existing intolerances usually lead to deterioration in the technological properties of rubber-rubber mixtures (e.g. decrease in tensile strengths in the case of mixtures of polybutadiene with polychloroprene or nitrile rubber) or rubber-thermoplastic mixtures (e.g. decrease in elongation at break for mixtures of polyethylene and natural rubber or polystyrene and polybutadiene). This is also the case with mixtures, for example of thermoplastic styrene-butadiene three-block polymers with polybutadiene or polyethylene, considerable losses in tensile strength and tear strength observed.

In general it can be stated that with compatible polymers the properties of the mixtures change somewhat linearly with the composition, but compatible mixtures are the exception are. When mixing incompatible polymers with one another, this can only be done to the extent that it is essential Properties of the polymer to be modified are not impaired too much.

It has now been found that rubber (A), preferably diene and olefin rubbers or their copolymers, can then be mixed with other polymers can be mixed, if one determines the mixture Graft polymers (B) in amounts from 1 to 80 wt .- # used, the basis of the graft polymer (B) with Monomers is grafted that are identical or compatible with the monomers of the rubber (A) and in the mixture with the Rubber (A) can be crosslinked together. Different monomers can also be used as grafts. In this way, a new type of rubber is obtained in which a regular, locally fixed distribution of graft polymer particles is present in a rubber.

The invention thus provides a mixture of rubbers (A) and graft polymers (B) in amounts of from 99 to 20 percent by weight (A) and 1 to 80 parts by weight (B), the basis of the graft polymer (B) is grafted with monomers which are identical or compatible with the monomer units of the rubber (A). Another subject matter is a process for producing the above mixture.

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In contrast to all previous rubber mixtures, one of the mixing conditions (roller, internal mixer, solution) is largely successful to produce independent morphology of a multiphase rubber system.

Diene rubbers are particularly suitable as rubbers (A) for blending such as natural rubber, polybutadiene, polyisoprene, polychloroprene, Butadiene-styrene copolymers, isoprene-styrene copolymers, Butadiene-acrylonitrile copolymers, butadiene-isobutylene copolymers, isoprene-isobutylene copolymers, but also rubbers such as ethylene-propylene copolymers, polyisobutylene, ethylene-vinyl acetate copolymers or acrylate rubbers, polybutadienes, polyisoprenes, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers are preferred, Isoprene-isobutylene copolymers, ethylene-propylene copolymers and polychloroprenes.

The graft base for the graft polymer (B) is preferred Diene rubbers such as polybutadiene, polyisoprene, polychloroprene or their copolymers, natural rubber, styrene-butadiene copolymers, Acrylonitrile-butadiene copolymers, styrene-isoprene copolymers, polystyrene , Styrene-acrylonitrile copolymers, ethylene-propylene copolymers, Ethylene-propylene-diene termonomers, polyisobutylene, isobutylene Isoprene copolymers, polyacrylates such as methyl, ethyl, propyl, buty! Polyacrylate or poly-methy! Methacrylate, ethylene-vinyl acetate copolymers, Polycarbonate, polyethylene, polypropylene, polyvinyl chloride, cellulose ester. As a graft base Mixtures of these polymers can also be used.

As monomers for producing the graft of the graft polymer (B) are preferred:

Butadiene, isoprene, chloroprene, butadiene / styrene, butadiene / acrylonitrile, Isoprene / styrene, isoprene / isobutylene, methyl, ethyl, propyl, Butyl acrylate, isoprene / butadiene, chloroprene / butadiene, chloroprene / isoprene, Isoprene / acrylonitrile. To improve compatibility, three or more monomers can also be grafted in a mixture will.

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For a more detailed explanation, the following mixtures are listed as examples:

For mixing with polychloroprene as rubber (A), the following polymers can be grafted with chloroprene: polychloroprene, Polybutadiene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, styrene-isoprene copolymers, polystyrene, styrene-acrylonitrile copolymers, Ethylene-propylene copolymers; Preferably, the following are used for mixing with polybutadiene as rubber (A) Polymers grafted with butadiene and / or isoprene:

Polystyrene, acrylonitrile-butadiene copolymers, polychloroprene, styrene-acrylonitrile copolymers, ethylene-propylene copolymers;

are preferably used for mixing with butadiene-acrylonitrile copolymers as rubber (A) the following polymers are grafted with isoprene or butadiene and acrylonitrile:

Polybutadiene, polyisoprene or polystyrene or their copolymers , Ethylene-propylene copolymers;

are preferred for mixing with polyisobutylene as rubber (A) the following polymers grafted with isobutylene:

Polystyrene, styrene-acrylonitrile copolymers, polychloroprene;

The following polymers with isoprene and / or butadiene are preferred for mixing with ethylene-propylene copolymers as rubber (A) and / or isobutylene or chloroprene grafted with isoprene and / or butadiene and / or isobutylene:

Polystyrene, polybutadiene, polyethylene, polycarbonate and butadiene-acrylonitrile copolymers, Styrene-acrylonitrile copolymers.

Different rubbers (A) can also be mixed with one another by admixing one or more graft copolymers (B) be made. The listed examples can of course only part of the many possibilities of this method Reproduce the production of compatible mixtures.

The graft polymers (B), which are composed of one or more of one another different graft polymers can exist

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the rubber (A) in amounts of 1 to 80% by weight, preferably 5 to 30% by weight added. The monomer edition of the Graft polymers (B) can be between 10 and 80 wt .- #, preferably 30 to 60% by weight, based on the basis.

The molecular weight of the chain length of the graft branches can be between 5,000 and 1,000,000, preferably between 20,000 and 150,000 (measured by light scattering) lie.

The graft can be crosslinked, a smaller one is preferred Degree of networking. The graft base can be crosslinked or uncrosslinked networking is preferred.

The particle size of the graft polymer (B) is 0.1-2 / um, preferably 0.1-0.8 µm.

The preparation of the graft polymers (B) can be carried substance, suspension or emulsion, regardless of the initiator free radical at temperatures from -20 ⁰ C to 120 ° C in solution. The process is expediently chosen in which the graft polymer is obtained in the form in which it is beneficial with the rubber

(A) can be mixed. Should e.g. a solution polymerization Manufactured rubber (A) such as cis-1,4-polybutadiene or an ethylene-propylene copolymer with a graft polymer

(B) are mixed, one will use a graft polymer (B), which has been prepared in a solution which is identical or identical to the solvent used in the production process for rubber (A) can be mixed with it.

If, for example, a rubber (A) produced by emulsion polymerization, such as emulsion-styrene-butadiene copolymer or polychloroprene or butadiene-acrylonitrile copolymer, is to be mixed with a graft polymer B, then it is advisable to use an emulsion process to produce the graft polymer (B). For the production of graft latices, bases with an average particle size of 0.05 to 1 Ai, preferably 0.1 to 0.4 / u, are used.

If graft polymers (B) are to be produced whose basis UA 18 040 - 5 -

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normally does not contain double bonds, hydrogen or heterogeneous groups that are suitable for grafting, bases are synthesized by copolymerization with certain comonomers suitable for graft polymerization (e.g. styrene is polymerized with isoprene or butadiene in amounts of 5 to 20 % c ©).

A large number of desired technological properties can be established by suitable mixtures of rubber (A) and graft polymer (B). For example, chloroprene-grafted polystyrene or styrene / acrylonitrile copolymers can be used improve the strength, modulus and processability of polychloroprene rubbers accordingly. By mixing chloroprene-grafted polybutadiene with polychloroprene, e.g. Cold flexibility increased. By mixing chloroprene-grafted butadiene / acrylonitrile copolymer with polychloroprene its oil resistance is improved. By mixing polystyrene grafted with butadiene or isoprene with polybutadiene or ethylene-propylene rubbers, their strength and processability are improved. By mixing with isoprene or Butadiene and acrylonitrile-grafted butadiene or isoprene increases the low-temperature flexibility of butadiene / acrylonitrile copolymers elevated.

These examples can be expanded as required. What matters is always that due to the compatibility of the graft copolymers with the rubbers brought about by grafting targeted change of certain technological properties is achieved without affecting the characteristic properties of the base rubber (A) can be significantly influenced in an undesired direction.

The mixing of the rubber (A) with the graft polymer (B) can be carried out in various ways:

For example, it is possible to use the corresponding latices at To mix room temperature or elevated temperature and then by adding salts, acids or alcohols coagulate or freeze the rubber mixture to fell. It is also possible to use those in solution

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To mix polymers (A) and (B) and work up the solution by stripping, spray drying or precipitation with, for example, alcohol. For the sake of completeness, a possible mixture of latex with solution should be mentioned. Mechanical mixing on the roll, in the internal mixer or in the screw press at 20 to 120 ^° C. is also possible.

During these mixing processes, fillers and extenders can be used at the same time and vulcanizing aids are mixed in.

The mixtures of rubber (A) and graft polymer (B) can be prepared in a customary manner in the presence of sulfur or peroxides to be vulcanized.

The method according to the invention is illustrated by the following examples explained in more detail:

A. Production of graft polymers

B. Production of graft polymer-rubber mixtures.

Regarding A.: The graft polymers used for mixing with rubber are either in emulsion, suspension or in solution with the aid of radical initiators manufactured.

EXAMPLE A 1:

A 6 liter flask is charged with: 1,600 g of polybutadiene latex (solids 54.4%, mean particle size 0.4, u) and 1,640 ml of deionized water. Thereafter, purged with nitrogen, and 63 - 65 ⁰ C heated. After heating, a solution of 4.5 g of potassium persulfate in 200 ml of water is added.

At 63-65 ⁰ C are added dropwise separated from each other within 4 hours at the same 540 g of chloroprene, and a mixture of 375 g water and 12 g emulsifier of the type alkyl sulfonate.

The subsequent stirring time is 4-6 hours at 63-65 ⁰ C.

After degassing, the latex is filtered and used directly for mixing experiments with rubber latices or solutions.

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EXAMPLE A 2: AO

A 6 liter flask is charged with: 1,600 g of butadiene-acrylonitrile copolymer latex (38 % acrylonitrile, Defo hardness 1,000, solids concentration 49.5 %, particle size 0.2 / u) and 1,640 ml of deionized water.

Thereafter, purged with nitrogen, and 63 - 65 ⁰ C heated. After heating, a solution of 4.5 g of potassium persulfate in 200 ml of deionized water is added.

At 63-65 ⁰ C are added dropwise separated from each other within 4 hours at the same 540 g of chloroprene and a mixture of 375 g water and 12 g emulsifier of the type alkyl sulfonate. The subsequent stirring time is 4-6 hours at 63-65 ⁰ C. After the devolatilization of the latex is filtered.

EXAMPLE A 3;

The following are placed in a 6 liter flask: 2,260 g of polychloroprene latex (concentration 35.2 %, executed Mooney ML-4 100 40, mean particle size 0.2 / u) and 1,000 ml of deionized water.

Thereafter, purged with nitrogen, and 63 - 65 ⁰ C heated. After heating, a solution of 4.5 g of potassium persulfate in 200 ml of water is added.

At 63-65 ⁰ C are added dropwise separated from each other within 4 hours at the same 540 g of chloroprene and a mixture of 375 g water and 12 g emulsifier of the type alkyl sulfonate.

The subsequent stirring time is 4-6 hours at 63-65 ⁰ C. After the devolatilization of the latex is filtered.

EXAMPLE A 4:

In a 6 l flask are placed: 1,600 g of polybutadiene latex (solids 54.4 %, mean particle size 0.4 / u) and 1,640 ml of deionized water.

Thereafter, purged with nitrogen, and 63 - 65 ⁰ C heated. After heating, a solution of 4.5 g of potassium persulfate in 200 ml of water is added.
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At 63-65 ° C., a mixture of 378 g of isoprene and 162 g of acrylonitrile is simultaneously separated from one another within 4 hours and 375 ml of water and 12 g of emulsifier of the alkyl sulfonate type were added dropwise.

The subsequent stirring time is 4-6 hours at 63-65 ° C. After degassing, the latex is filtered.

EXAMPLE A 5 t

The following are placed in a 6 liter flask: 1,600 g of a butadiene-acrylonitrile copolymer latex (33 % acrylonitrile, Defo hardness 1,000, solids concentration 49.3 %, mean particle size 0.19 / u) and 1,640 ml of deionized water.

It is then flushed with nitrogen and heated to 63-65 ° C. At 63-65 ⁰ C are added dropwise separated from each other within 4 hours at the same time a mixture of 475 g styrene and 65 g of acrylonitrile and 375 ml of water and 12 g emulsifier of the type alkyl sulfonate.

The subsequent stirring time is 4-6 hours at 63-65 ⁰ C. After the devolatilization of the latex is filtered.

EXAMPLE A 6;

A 6 liter flask is charged with: 1,970 g of styrene-isoprene copolymer latex (10 % isoprene, solids 40.8 % _t mean particle size 0.15 / u) and 1,260 g of deionized water.

Thereafter, purged with nitrogen, and 63 - 65 ⁰ C heated. At 63-65 ⁰ C are added dropwise separated from each other within 4 hours at the same 540 g of chloroprene, and a mixture of 375 g water and 12 g emulsifier of the type alkyl sulfonate.

The subsequent stirring time is 4-6 hours at 63-65 ⁰ C. After the devolatilization of the latex is filtered.

EXAMPLE A 7:

In 4 l of toluene, 250 g of cis-1,4-polybutadiene (7 = 240 ml / g)

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given and stirred until everything is dissolved. Afterward 200 g of chloroprene, 200 g of isoprene and 12 g of benzoyl peroxide are added and the mixture is stirred at 60 ° C. for 18 hours.

EXAMPLE A 9:

5.2 liters of η-hexane and 320 g of ethylene-propylene terpolymer (EN type, Mooney ML 4-100 90, 12 C = C double bonds per 1,000 C atoms) are placed in a 10 1 autoclave and so long stirred until all of the rubber has dissolved. Then 480 g of chloroprene and a solution of 15.2 g of dibenzoyl peroxide in 100 ml of benzene are added and the mixture is stirred ^{at 60 ° C. for 18 hours.}

For B.: Rubber and graft polymer are in latex form, Solution or in solid form, mixed with one another on a roller or in an internal mixer. The latex mixtures are worked up by precipitation and the solution by stripping in a known manner.

(E) first of conventional carbon black mixtures are prepared from the graft polymer mixtures according to the ISO standard 2475-1975 prepared therefrom pressed shaped bodies and these respectively 20, 40 and 60 minutes cured at 15O ⁰ C in the press long. The required shaped bodies are cut from the plates or flaps obtained. The strength (F), elongation (D) and tension values (S; at 100/300 % elongation) are tested on the standard ring I according to DIN 53504, the Shore hardness A (H; at 20 and 70 ⁰ C) according to DIN 53305 and that of the rebound resilience (E) according to DIN 53512. The compression set is measured in accordance with DIN 53517. The polymer viscosity and the viscosity curve difference is min.- 1 and between the 4-min.-value in Mooney unit at 100 ⁰ C (ML-4) according to DIN 53523 and the Defo plasticity to the used raw graft polymer mixtures Measured based on the earlier DIN 53514. The gel content is determined by centrifuging a solution in toluene.

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A selection of manufactured and tested graft polymer mixtures (I - XX) is compiled in Tables 1 a and 1 b and is characterized there in more detail. Test data for the vulcanizates are given in Table II.

EXAMPLE B 1: (Table 1 a)

Polymer mixtures of 90 (I) or 80 (II) parts by weight of a chloroprene homopolymer with 10 or 20 wt. TIn of a polystyrene grafted with chloroprene show in comparison to the pure Chloroprene homopolymer (V) has a significantly higher gel content and viscosity gradient value, which results in better processing behavior knock down.

The products also show high strengths in the vulcanizates, Structural strengths and hardnesses.

EXAMPLE B 2; (Table 1a)

Polymer mixtures of 90 (III) or 80 (IV) parts by weight of a chloroprene homopolymer with 10 or 20% by weight of a chloroprene-grafted butadiene-acrylonitrile copolymer with 38 % acrylonitrile also show in comparison with the pure chloroprene -Homopolymer (V) has a higher gel content and viscosity curve as well as better processing behavior: when extruding a round cord, the delivery rate is higher and the injection swelling is lower.

After hot air aging (100 ° C / 21 days) the hardness and tension values increase of the vulcanizates with the polymers according to the invention are lower, i.e. they are more resistant to aging. aside from that the vulcanizates with the polymers according to the invention are essential more resistant to ASTM oils, as shown by storage at 100 ° C.

EXAMPLE B 3; (Table 1 a)

Polymer mixtures of 85 (VI) or 70 (VII) TIn by weight of one Chloroprene homopolymer with 15 or 30 wt. TIn one with Chloroprene-grafted polybutadienes also have a much higher gel content than the pure homopolymer (V) and viscosity history value, which are also at a very high level

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lead good processing behavior.

In the vulcanizates they show higher values than the comparison material Hardness, tension values and elasticities.

EXAMPLE B 4: (Table 1a)

Polymer mixtures of 90 (VIII) or 80 (IX) parts by weight of a Chloroprene homopolymer with 10 or 20 wt. TIn one with Chloroprene-grafted styrene-isoprene copolymers show in comparison to the pure chloroprene homopolymer (V) higher gel and viscosity gradient values, which in this case also lead to better processability of the mixtures.

EXAMPLE B 5: (Table 1 a)

A polymer mixture of 80 parts by weight of a chloroprene homopolymer With 20% by weight of a chloroprene-grafted polychloroprene (X), compared to the ungrafted comparative sample (V), likewise higher gel and viscosity values which cause better processing behavior. in the Vulcanizate, higher tension, hardness and elasticity values are achieved.

EXAMPLE B 6; (Table 1 a)

Polymer mixtures of 90 (XI) or 80 (XII) parts by weight of one Sulfur-modified polychloroprenes with 10 or 20 parts by weight of a polybutadienes grafted with chloroprene show opposite the ungrafted comparative sample (XIII) as well as the products in the preceding examples have higher gel and viscosity values which cause rapid roll sheet formation. In the carbon black mixtures, the products tend to have a lower roll tack and more rapid vulcanization, which leads to a higher crosslinking density with higher tension, hardness, elasticity s and compression set values.

EXAMPLE B 7; (Table 1a)

The polymer mixture of 80 parts by weight of a chloroprene homopolymer with 20 parts by weight of a chloroprene-grafted butadiene-acrylonitrile copolymer with 38 % acrylonitrile (IV b)

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shows a Mooney viscosity ML-4/100 C = 58 ME and a gel content from 16 96.

It is comparable to a so-called pre-crosslinked polychloroprene type (IV a), which is produced by mixing benzene-soluble Homo- or copolymers of chloroprene with benzene-insoluble, generally using diesters known process (Brit. Patent 1.158.970) produced copolymers of chloroprene, obtained and specifically used there where particular emphasis is placed on good processing behavior. With equivalent processing properties However, IV b versus IV a results in higher strengths and better compression for the polymer mixture according to the invention Set and found a better aging behavior.

EXAMPLE B 8: (Table 1 b)

The polymer mixture of 90 (XIV) or 80 (XV) parts by weight of one Chloroprene homopolymer with 10 or 20 wt. TIn one with Chloroprene-grafted 1.4-polybutadiene shows a Mooney viscosity ML-4/100 ° C of 58 and 68 and a gel content of 8 and 20%.

The vulcanizate values show excellent strength and elongation, good flexibility at low temperatures and low compression Set.

EXAMPLE B 9: (Table 1b)

The polymer mixture of 80 parts by weight of a chloroprene homopolymer with 20 wt. TIn of an ethylene-propylene terpolymer grafted with chloroprene Compared to the pure homopolymer (V), (XVI) has a higher gel content and viscosity curve value on, which leads to a very good processing process. The vulcanizates have an increased resistance to aging.

EXAMPLE B 10; (Table 1 b)

The polymer mixture of 85 (XVII) or 70 (XVIII) parts by weight of a nitrile rubber with 15 or 30 parts by weight of a polybutadiene grafted with isoprene / acrylonitrile exhibits good strengths Le A 18 040 - 13 -

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and stretching increased cold flexibility with reduced compression Set.

EXAMPLE B 11 (Table 1 b)

The polymer mixture of 90 (XIX) or 80 (XX) wt. Tin of a lithium polybutadiene with 10 or 20 wt. TIn of a polystyrene grafted with isoprene showed, with good strengths and elongations, extraordinarily improved processability compared to the pure polybutadiene.

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Taballa 1 a

b niachungan I. II III IU V UI UII > Chloroprene homopolymerate 90 BO 90 80 100 B5 70 -k chloroprene bapfropftea polyatyrene according to A 6 10 20th ⁰⁰ chloroprene grafted butadian acrylonitrile 1 η on O copolynerate according to A 2 C ^ chloroprene beofroDftee polybutadiene according to A 1 15th 30th Raw material properties
Gel content (%) Hooney-Viekoeitat HL-A (IOO C) (ME) 10.0 20.0 9.0 18.3 0.6 16.5 32.1 61/10 70/13 58/10 62/10 71/2 69/8 82/14

niachunoen Ulli IX X XI XII XIII Chloroprene homopolymer
Chloroprene-grafted polybutadiene according to A 1
Chloroprene-grafted polyatyrene according to A 6
Chloropran-bapfropftaa polychloroprene according to A3
Sulfur modified homopolychloroprene 90
10 BO
20th 80
20th 10
90 20th
BO 100 Raw material properties
Gel content (Ji)
Ilooney quality PIL-4 (100 ° C (PlZ)
Oafo plasticity 9.7
60/10
675 19.3
62/12
900 21, B.
69.6
900 10.7
38/8 21.3
40/6 0.4
40/6

food IUa IUb Chloroprene homopolymerate
Pre-crosslinked polychloroprene
Chloropran-Bapfropftaa Butadiene-Acrylnltril-Copoly-
nerieat according to A 2 100 80
20th Raw material outlets 15.9
54 16
5B Galga content (%)
noonav-Uiakoaitlt PIL-4 (100 C) (ΠΕ)

Taballa 1 b

_ * Mixtures XIU 58 XV XWI XUII XUIII XIX XX ⁰⁰ chloroprano homopolyester 90 8th 80 80 O chloroprene-grafted cis-1,4-polybutadiene according to A 7 10 20th Q Chloropran-bapfropftaa Ethylen-Propylen-Terpol. according to A 9 20th Iaopran / acrylonitrile graftedaa polybutadiene according to A 4 15th 30th Acrylonitrile-butadiene copolymer (38 % ACN, Oefo hardness 1800) 85 70 Ieoprene-grafted polystyrene (10 % Iaopran in polystyrene MG 100000) 10 20th Polybutadiene (Li-BR) ( 1 200 ML / G) 90 80 Adhesive raw tartarial egg
Iiooney-Viekoeitat ML-4 (100 ° C) (PIE) Gelled (%) 68 120 108 115 50 60 20th 25th 20th 35 9 18th

Table 2 : Vulcanizate properties

mixture F.
(riPa) 0
(*) m (ioo56)
(NPa) H Shore A
20/70 C El.
00 structure
(N) CS70 / 22 "
100 ° / 70 « Brittle
ness
Pdht ^C I. 18.2 340 3.2 69/65 50 146 23/31 II 17.6 300 4.4 76/68 43 164 34/35 III 17.5 370 2.3 64/62 51 134 11/32 -34 IU 17.0 370 2.4 65/62 59 116 12/31 -34 V 17.8 440 2.2 62/61 49 168 / 27 -30 VI 15.0 330 2.5 65/64 56 104 11/29 VII 13.0 270 3.1 68/67 56 90 11/26 VIII 17.5 400 3.2 70/68 45 160 / 27 -30 IX 17.3 310 4.3 76/67 42 140 - / 28 -30 X 17.5 400 2.4 64/62 50 - / 27 XI 17.2 540 2.0 64/63 48 18 / - XII 15.0 460 2.3 66/63 49 19 / - XIII 15.6 540 2.3 66/64 43 25.3 / - XIV 17.0 560 2.1 63/62 49 18 / - -35 XV 16.5 500 2.2 64/63 50 19 / - -35 XVI 16.0 320 2.5 68/67 53 20 / - -30 XVII 10.9 365 2.8 66/63 58 27.2 / -16 XVIII 9.5 315 2.9 67/64 59 26.2 / -18 XIX 13.0 430 2.5 63/61 49/52 156 XX 15.2 400 3.0 70/68 47/51 141 IVa 16.3 390 2.3 64/61 51 37 / IVb 17.8 495 2.1 62/58 45 29 /

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Claims (18)

Claims 1. Rubber mixtures, characterized in that a graft copolymer B is mixed into a rubber A in amounts of 1-80% , the graft monomers of B being identical to the monomers of the rubber A used for the mixture. 2. Rubber mixtures, characterized in that a graft copolymer B is mixed into a rubber A in amounts of 1-0 % , the graft of B being compatible with the rubber A. 3. Rubber mixtures according to 1 and 2, characterized in that the Rubber A can be co-vulcanized with the graft of the graft copolymer from B. is. 4. Rubber mixtures according to 1 and 2, characterized in that the Rubber A is a diene or olefin rubber or their mixed polymer 1st. 5. Rubber mixtures according to 1 and 2, characterized in that the Rubber A Polybutadiene, polyisoprene, natural rubber, butadiene-styrene copolymer or polychloroprene. 6. Rubber mixtures according to 1 and 2, characterized in that the Rubber A is a butadiene-acrylonitrile copolymer. 7. Rubber mixtures according to 1 and 2, characterized in that the Rubber A is an ethylene-propylene terpolymer or an isobutylene-ioprene copolymer is. 8. Kautaohuk-Miechungen according to 1 and 2, characterized in that the graft copolymer B from a basis of polybutadiene, polyisoprene, poly styrene, polychloroprene, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, isobutylene polymer, isobutylene-isoprene copolymer, Ethylene-vinyl acetate copolymer, butadiene-styrene copolymer or acrylate polymer and a layer of polychloroprene, polyieoprene, butadiene-acrylonitrile copolymer, isoprene-acrylonitrile copolymer, isobutylene or butadiene-styrene copolymer . Le A 18 040 - 18 - 809848/0077 9. Rubber mixtures according to 1 and 2, characterized in that latex bases with a particle size between 0.1 and 1 μ are used to produce the graft copolymer B. 10. Rubber mixtures according to 1 and 2, characterized in that there is a statistically fixed distribution of 1-80% graft copolymer particles in a rubber matrix. 11. Rubber mixtures according to 10, characterized in that the proportion of graft polymer particles is 1-30 % . 12. Rubber mixtures according to β, characterized in that the graft base is crosslinked. 13. Keutechuk-Miechungen according to 8, characterized in that the polymer chains the graft have a molecular weight between 2,000 and 500,000. 14. Kautechuk mixtures according to 13, characterized in that the polymer chains the graft have a molecular weight between 5000 and 150,000. 15. Rubber mixtures according to 8, characterized in that the basis of the graft copolymer B is uncrosslinked. 16. Rubber mixtures according to 8, characterized in that the graft copolymer B is prepared by grafting in benzene, toluene, xylene or mixtures thereof with the aid of free radical initiators. 17. Rubber mixtures according to 8, characterized in that the graft copolymer B by grafting in aliphatic solvents such as hexane, Pentane, cyclohexane or mixtures thereof with the aid of free radical initiators will be produced. 18. Rubber mixtures according to 8, characterized in that the graft copolymer B by grafting in a mixture of aliphatic and aromatic solvents with the help of free radical initiators. Le A 16