MXPA98008430A - Preparation of molding materials modified with acrylic rubber and molding materials obtained from this man - Google Patents

Abstract

An elastomeric acrylate copolymer containing, as polymerized units, comonomers having chemically reactive groups, is prepared for the preparation of molding materials having good weather resistance, improved impact resistance and good flow properties. This copolymer dissolves or sponges into monomers such as styrene and acrylonitrile, forming hard graft covers. After the addition of monomers and / or polymers having chemically reactive groups and, if required, after the addition of a chemically reactive crosslinking agent, the resultant monomer / copolymer mixture is subjected to graft polymerization, which is carried carried out up to a conversion of more than 15% by weight of the monomers, by solution or mass polymerization of free radicals or thermal. The molding materials can be used as delustrant or matte agents for polymer blends

Description

PREPARATION OF MOLDING MATERIALS MODIFIED WITH ACRYLIC HOLE AND MOLDING MATERIALS THAT ARE OBTAINED IN THIS MANNER The present invention relates to a process for the preparation of molding materials modified with acrylic rubber by polymerization of monomers, which form the graft cover in the presence of an acrylic rubber that dissolves or sponges in the monomers and contains monomers that have chemically reactive groups. The preparation of modified rubber molding materials has been known for a long time. In addition, the use of elastomeric acrylate polymers having vitreous transition temperatures of less than 0 ° C, preferably below -10 ° C (acrylic rubber), for molding materials modified in this manner, has been known for almost 40 years. The weather resistance has improved compared to molding materials prepared using diene rubbers. In modified multi-phase molding materials, rubber domains are embedded in a thermoplastic matrix, the domain structure plays a major role in determining the mechanical properties of the resulting molding materials. The resistance of the molding materials results from increased energy absorption during deformation to fracture, the energy is consumed for microcavity formation or for the initiation of sliding processes of the polymer chains on matrix. The character of multiple phases is therefore an essential pre-condition to achieve high impact resistance. There is a considerable need for molding materials modified with acrylic rubber and in particular styrene / acrylonitrile copolymers modified with acrylic rubber (ASA molding materials), which have high impact strength and good flow properties and give shaped articles with reduced gloss in the surface. The preparation of ASA molding materials in emulsion is described in many patent publications (see for example DE A 19 11 882, DE-A 28 26 925, DE-A 31 29 378, DE-A 31 29 472, DE-A 31 49 046, DE-A 31 49 358, DE-A 32 06 136, DE-A 32 27 555). The disadvantage of this preparation is the need to remove auxiliaries during processing in the molding materials, in order to avoid subsequent problems during processing (discoloration, staining, corrosion). In particular, however, the impact resistance, tensile strength and gloss properties of shaped articles produced therefrom are unsatisfactory.

DE_B 11 82 811 published more than 30 years ago, describes the polymerization of the acrylate with an entanglement monomer in solution for the preparation of acrylic rubber, the styrene and acrylonitrile monomers to be grafted are added after conversion of only 20 to 40% in weight of the monomers and polymerize in solution or in bulk. Due to the variant composition in the grafting reaction and due to the incorporation of rubber units in the graft cover by polymerization, this leads to a reduction in the Vicat softening temperature, and a deterioration of additional mechanical properties of the grafting materials. resulting molding. An object of the present invention is to prepare molding materials that are modified with acrylic rubber and can be processed into shaped articles having improved impact resistance, good flow properties and low surface gloss. We have found that this goal is achieved by a process for the preparation of molding materials modified with acrylic rubber, if monomers are incorporated that have chemically reactive groups in the acrylic rubber by polymerization, the completely polymerized acrylic rubber dissolves or sponges completely in the monomers forming the graft shell, and monomers and / or polymers containing chemically reactive groups capable of reacting with the chemically reactive groups contained in the acrylic rubber (A2) or capable of bonding with these, with the help of an aggregate entanglement agent (AMV) are added to the mixture. The aggregate entanglement agent (AMV) can react with both the chemically reactive groups in the acrylic rubber (A2) and with the chemically reactive groups of the monomer and / or aggregate polymer. The graft polymerization can then be carried out in one or more stages, at least the first stage of the polymerization is carried out, at a conversion greater than 15, preferably from 20 to 40% by weight of the monomers, by polymerization mass, by free radicals or thermal (preferably) or by solution polymerization. The present invention in this way relates to a process for the preparation of a molding material (A) modified with acrylic rubber, by (a) polymerizing a mixture (A2M) of (at) at least one monomer of the formula CH2 = CR1 - COOR2 wherein R1 is hydrogen or methyl and R2 is alkyl having 1 to 32 carbon atoms, (a2) at least one olefinically unsaturated copolymerizable monomer (A2m2), containing a chemically reactive group (A2m2x) and (a3) if required, at least one olefinically unsaturated copolymerizable monomer. 5 additional (A2rt? 3), the sum of the amounts of the monomers (A2m2) and (A2m3) is less than the amount of the monomer (A2ml), to give an acrylic rubber (A2) having a vitreous transition temperature to minus 0 ° C, 10 (b) dissolution or swelling of the completely polymerized acrylic rubber (A2), with or without the addition of an inert solvent, in one or more olefinically unsaturated monomers (Alm) forming a graft cover hard (Al) and whose polymers or copolymers have a glass transition temperature of at least + 20 ° C, and addition of a minor amount of a monomer (Almf) and / or a polymer (AlPf) compatible or partially compatible with the monomers (Alm) to the monomers (Alm), (Almf) and (AlPf) containing at least one chemically reactive group that is capable of reacting with the chemically reactive groups (A2m2x) of the acrylic rubber (A2) or that, with the aid of an entanglement agent (AMV) added to the mixture (AM), allows coupling of the chemically reactive group to a chemically reactive group (A2m2x) of the acrylic rubber (A2), and (c) graft polymerization of the resulting mixture (AM) in one or more steps to give a molding material (A), at least the first stage of the polymerization of the mixture (AM) is carried out, until a conversion more than 15% by weight of the monomers, by solution or mass polymerization by free radicals or thermal. The present invention furthermore relates to molding materials prepared by the novel process and to their use as opacifying or delustranting agents. Although the novel process is described as a 3-step process for reasons of clarity, the process however is also employed when only the third stage is carried out, ie the monomers (Alm) are polymerized as established in the presence of the acrylic rubber defined dissolte or sponge (A2). Alkyl acrylates and / or methacrylates (A2ml) suitable for the preparation of the acrylic rubber (A2) are those of the formula CH2 = CR1 -COOR2, wherein R1 is hydrogen or methyl and R2 is alkyl with 1 to 32, in particular 1 to 12 carbon atoms. Acrylates of a linear or most branched alkyl alcohol in a simple manner with 4 to 12 carbon atoms are preferred. Esters of n-butanol and of alcohol-2-ethylhexyl alcohol are preferred. For a given content of certain monomers (A2m2) and (A2m3), the glass transition temperature (T) of the resulting acrylic rubber (A2) can be established by the selection of acrylates, methacrylates or their mixtures, and the glass transition temperature g it should be less than 0 ° C, in particular lower than -10 ° C, preferably less than -20 ° C. The establishment of the vitreous transition temperature in this way is based on the fact that the vitreous transition temperature of the acrylate and methacrylate polymer initially decreases as the length of the side chains increases, passing through a minimum of 7-atom alkyl of carbon acrylate or C10 alkyl methacrylate and then increased again. In general, the content of alkyl methacrylate or acrylate in the mixture (A2M) is at least 50, preferably at least 80% by weight, based on the amount of monomers in the mixture (A2M). The mixture (A2M) further contains at least one copolymerizable olefinically unsaturated monomer (A2m2) containing a chemically reactive group (A2m2x).

Examples of these chemically reactive groups are epoxy, amino, amido, hydroxyl, carboxylic anhydride and carboxyl groups. Monomers of this type are known and commercially available. Examples of comonomers (A2m2) are glycidyl esters and unsaturated glycidyl ethers, such as glycidyl (meth) acrylate, aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides, such as N, 2-aminoethylmethacrylamide or aminohydroxypropyl methacrylate, 2-hydroxyethyl (met ) acrylate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamides, esters and ethers thereof, such as N-methoxymethyl (meth) acrylamide, maleic anhydride, acrylic acid, methacrylic acid and crotonic acid. The mixture (A2M) contains the monomers (A2m2) in general in an amount of 1 to 25, in particular 3 to 15,% by weight, based on the total amount of monomers in the mixture (A2M) used for the preparation of acrylic rubber. For the preparation of acrylic rubber (A2), additional olefinically copolymerizable unsaturated monomers (A2m3) may be present in a small amount, the sum of the amounts of the monomers, (A2m2) and (A2m3), is generally less than the amount of alkyl acrylate and / or alkyl methacrylate (A2ml). These additional monomers (A2m3) are in particular monomers having at least two olefinically unsaturated double bonds, such as allyl methacrylate or acrylate, 1,4-butanediol dimethacrylate or diacrylate, divinylbenzene, triallyl cyanurate or dihydrodicyclopentadienyl methacrylate or acrylate. Preferred among these are monomers having unconjugated double bonds, in particular allyl methacrylate and acrylate and dihydrodicyclopentadienyl methacrylate and acrylate. The mixture (A2M) contains from 0 to 20, in particular from 0.3 to 15, preferably from 0.3 to 12% by weight, based on the total amount of monomers in the mixture (A2M), of these crosslinking monomers or monomers which support the grafting of the monomers (bn). The content of these monomers in the mixture (A2M) depends to a large extent on the reactivity of the two C = C double bonds of the monomers. If both are very reactive and if both are incorporated in the polymer chain during the polymerization of the mixture (A2M), then increasing the entanglement of the acrylic rubber copolymer (A2) is carried out as the monomer concentrations increase. have at least 2 double bonds C = C. If, on the other hand, only one C = C double bond is easily polymerizable, such as when dihydrodicyclopentadienyl acrylate is used, the difunctional monomer can then be used in a larger amount and results in increased grafting of the monomers (Alm) on the rubber acrylic (A2) in the polymerization of the mixture (AM) in step c) of the process. The increased grafting of acrylic rubber (A2) can also be achieved by additional use of a comonomer having a group that forms free radicals as a result of thermal decomposition, for example comonomers having peroxy or azo groups. Examples of these comonomers are tert-butyl-3-isopropenylcumyl peroxide, tert-butyl peroxy-tonate and tert-butyl monoperoximeleate. In the case of the last monomers, the preferred amount is from 0.3 to 5% by weight of the monomers in the mixture (A2M). The copolymerization of the monomers (A2ml) with (A2m2) and if required, (A2m3), can be carried out in known manner, in particular as solution or emulsion polymerization, and preferably starting with free radical initiators. The chemically reactive groups (A2m2x) of the monomers (A2m2) must be substantially maintained. After finishing the polymerization and any necessary removal of residual monomers or isolation of the acrylic rubber (A2), that is, according to the invention, it dissolves or at least completely sponges in the monomers (Alm), subsequently forming the graft cover and possibly the polymer matrix, with or without the addition of required amounts of a solvent or mixture of suitable inert solvents and with stirring and / or heating of the mixture. In particular, the amount of solvent added is not more than 50% by weight of the sum of the amounts of monomers (Alm) and acrylic rubber (A2). Examples of suitable monomers (Alm) which subsequently substantially form the hardening graft cover are: styrene, alpha methylstyrene, styrene alkylated in the core and preferably having alkyl radicals with 1 to 4 carbon atoms, acrylonitrile, methacrylonitrile, acrylamide , methacrylamide, N-phenylmaleimide and alkyl acrylates and methacrylates wherein the alkyl radicals have 1 to 4 carbon atoms, in particular methyl methacrylate. Monomers and mixtures of monomers giving a polymer or copolymer with glass transition temperature greater than + 20 ° C, preferably greater than + 50 ° C, are used. A mixture of an alkenyl benzene monomer, such as styrene, and acrylonitrile, wherein the alkenyl benzene monomers are preferably present in an amount of 50 to 80% by weight and acrylonitrile in an amount of 20 to 50% by weight, based on the amount of the mixture, employees such as monomers (Alm) are particularly preferred.

The amount of monomers (Alm) in the mixture (AM) depends in particular on the desired content of acrylic rubber (A2) in the resulting molding materials (A).

In general, the amount by weight of the monomers (Alm) in the mixture (AM) is from 2/3 to approximately 100, in particular from 3 to 20 times the amount of acrylic rubber (A2) present. Before, during or after the dissolution or swelling of the acrylic rubber (A2) in the monomers (Alm), a monomer (Almf) and / or a polymer (AlPf) compatible or partially compatible with the monomers (Alm), each of which contains at least one chemically reactive group which is capable of reacting with the chemically reactive groups (A2m2x) introduced by the comonomer (A2m2) in the acrylic rubber (A2) or which, with the aid of an added polyfunctional entanglement agent ( AMV), allows coupling with the chemically reactive groups (A2m2x) of the acrylic rubber (A2), is mixed with these monomers (Alm) in a smaller amount, in particular an amount of 25% by weight of the amount of the monomers ( Alm) in the mixture (AM). In this way, by adding an entanglement agent (AMV) that has at least two chemically reactive groups that can react with the chemically reactive groups in the acrylic rubber (A2) and the chemically reactive groups in the monomer (Almf) and / or polymer (AlPf), in particular during the polymerization reaction, the acrylic rubber (A2) can be ligated or entangled with the monomers (Almf) and / or polymers (AlPf) leading to a higher degree of grafting. A suitable entanglement agent (AMV) for example is a diamine or polyamine, having at least two primary or secondary amino groups such as alkylene diamines, preferably ethylene diamine. If the acrylic rubber (A2) contains, for example, epoxy groups, it is useful to add monomers (Almf) and / or polymers (AlPf) containing, for example, amino groups (preferably primary or secondary amino), hydroxyl, amido, carboxyl or carboxylic anhydride, for example beta-hydroxyethyl (meth) acrylate, their copolymers, aminoalkyl (meth) acrylamides, their copolymers, maleic anhydride and their copolymers and (meth) acrylic acid and its copolymers. If the acrylic rubber (A2) contains, for example, primary or secondary amino groups, it is useful to add to the mixture (AM) monomers (Almf) and / or polymers (AlPf) containing, for example, epoxy groups, carboxylic anhydride or carboxyl, for example glycidyl (meth) acrylate, glycidyl (meth) acrylate copolymers, maleic anhydride and maleic anhydride copolymers, etc. Literature of relevant polymers provides sufficient information for the selection of suitable reagents.

The amount of chemically reactive monomers (Almf) that are added and / or chemically reactive polymers (AlPf) depends, among other things, on the proportion of chemically reactive groups and on the amount of acrylic rubber (A2) and the calculated amount of the epoxy, amino, carboxylic anhydride or carboxyl groups linked.

Depending on the type and reactivity of these groups in the acrylic rubber (A2) and the monomers (Almf) or polymer (AlPf), the molar concentration of the chemically reactive groups in the added monomer (Almf) and / or polymer (AlPf) must correspond to at least the calculated molar concentration of the epoxy, amino, hydroxyl, amido, carboxylic anhydride or carboxyl group in the acrylic rubber (A2) or must substantially exceed said concentration. The polymerization of the monomers (Alm) in the presence of acrylic rubber (A2) dissolved or foamed in the monomers (Alm) and if required, added solvent and in the presence or absence of the polymer (AlPf) (AM mixture) preferably it is carried out as free radical or thermal polymerization from room temperature to 200 ° C, in particular from 50 to 160 ° C. The polymerization can be carried out in one or more stages. At least the first stage of the polymerization is carried out at a conversion greater than 15, preferably by more than 20 to 40% by weight of the monomers, by free radical or thermal polymerization or by solution polymerization. After this first step, the polymerization can, if desired, then be continued and completed by another polymerization method, advantageously by suspension polymerization in the presence of known initiators and stabilizers for suspension polymerization. The molding material (A) obtained after the polymerization of the mixture (AM) which constitutes or includes monomer graft polymerization (Alm) in the acrylic rubber (A2), generally contains from 1 to 60, in particular from 5. to 40% by weight of acrylic rubber (A2). The upper limit of the content of acrylic rubber (A2) arises from the need for the molding material (A) which has sufficient strength despite the embedded domains derJT rubber. The lower limit is essentially determined by the fact that sufficient energy is absorbed before deformation of the molding material. The molding materials (A) prepared according to the invention have improved impact resistance and notched impact resistance and good flow behavior. Conformed articles that are produced from them also have the main advantage that their surfaces in general are tarnishing or almost tarnishing. They can also be used advantageously as delustrants for other compatible or partially compatible polymer molding materials. The examples and comparative experiments that They continue, they illustrate the invention. Parts and percentages are given by weight unless otherwise stated. The polyvinylpyrrolidone used was from BASF AG and had a K value of 90 (according to Fikentscher, Cellulosechemie 13 (1932) 58). The polyvinyl alcohol used (Moviol 30-92 from Hoechst AG) had a degree of hydrolysis of 92% mol and the aqueous solution at 4% had a viscosity of 30 mPa.s at 20 ° C. The values for impact resistance in kJ / m2 were determined in accordance with DIN 53 453-K, 5/75 edition. The values for the impact resistance notched in kJ / m2 were determined in accordance with DIN 534534 R, S / 75 edition. Impact resistance and notched impact resistance are measured using small standard bars that were injection molded at a plastic melting temperature of 240 ° C and a mold temperature of 60 ° C. The flow behavior and therefore the processability were estimated based on the melt volume index in ml / 10 min which is measured according to DIN 53 735 at 200 ° C and under a load of 21.6 kg. The gloss is estimated using circular discs with a thickness of 2 mm, which were injection molded at a plastic melting temperature of 220 ° C and a mold temperature of 60 ° C. The vitreous transition temperature is determined by the DSC method (K.H. Illers, Makromolekulare Chemie 127 (1969), 1). Example 1 (a) Preparation of the acrylic rubber (A2) (according to the invention) 1868 g of toluene, are introduced into a flask and heated to 75 ° C under nitrogen and with stirring and 41 g of a mixture of monomers comprising 89.7% n-butyl acrylate (A2ml), 2.3% allyl methacrylate (A2m3) and 8% glycidyl methacrylate (A2m2), and 41 mg azobisisobutyronitrile as an initiator, were then added. 787 g of a monomer mixture of the same composition and 777 mg of azobisisobutyronitrile were then metered in over the next 4 hours. After a further polymerization time of 4 hours, the polymerization batch is cooled and stabilized with 19 g of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant. The conversion was 92%. b) + c) Preparation of a molding material containing the acrylic rubber (A2), without the concomitant use of monomer (Almf) or polymer (AlPf). (Comparative experiment) The toluene and any residual monomer present from step a) were removed under reduced pressure on a rotary evaporator and replaced by a certain amount of styrene, after which acrylonitrile is added in an amount such that a mixture of 69.2% styrene (Alml), 23% acrylonitrile (Alm2) and 7.8% acrylic rubber (A2). In this way, the acrylic rubber (A2) is dissolved in a mixture * of styrene / acrylonitrile. 1923 g of this solution were then placed in a 5 liter capacity steel kettle and heated to 123 ° C with stirring. At a 20% monomer conversion, 1.49 g of tert-butyl mercaptan and 2.31 g of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant were added. At a conversion of the monomer of 33%, 1.9 g of dicumyl peroxide, 1900 g of water, 20 g of polyvinyl pyrrolidone, 1.0 g of tetrasodium diphosphate and 59.8 g of a solution of aqueous polyvinyl alcohol with a concentration of 10% were added.

The polymerization batch is polymerized to completion by 3 hours at 110 ° C, for 3 hours at 130 ° C and for 6 hours at 140 ° C.

It is then cooled, and the polymer is separated by filtration and dried. The properties of the conventional molding material are illustrated in Table 1. Example 2 (comparative experiment) The experiment was as in Example 1, except that a conventional acrylic rubber comprising 97.7% n-butyl acrylate and 2.3% is used. of allyl methacrylate. The properties of the conventionally prepared molding material are illustrated in Table 1.

Example 3 (according to the invention) The procedure was as in Example 1, except that 7.8% of the established monomer mixture comprising styrene (Alml) and acrylonitrile (Alm2) is replaced by a copolymer of 73.5% styrene , 24.5% acrylonitrile and 2% maleic anhydride (polymer AlPf).

The properties of the molding material prepared according to the invention are illustrated in Table 1. Example 4 (according to the invention) The procedure was as in Example 1, except that 10.4% of the established monomer mixture comprises styrene ( Alml) and acrylonitrile (Alm2) was replaced by a copolymer of 73.5% styrene, 24.5% acrylonitrile and 2% maleic anhydride (polymer AlPf). The properties of the molding material prepared according to the invention are illustrated in Table 1. Example 5 (according to the invention) The procedure was as in Example 4, except that 11% of the styrene / acrylonitrile monomer mixture (Alm) is replaced by the styrene / acrylonitrile / maleic anhydride copolymer (AlPf polymer) established therein. The properties of the molding material prepared according to the invention are illustrated in Table 1. Table 1 Example 1 2 3 4 5 Comparison according to the invention Impact Resistance 23 ° C (k < l / m2) 22 25 37 35 35 Notched Impact Resistance 23 ° C (kJ / m2) 1.8 1.8 2.6 2.1 2.9 Melt Volume Index (ml / 10 min) 5.1 3.0 7.4 14.0 8.3 Matte matte gloss Example 6 (according to the invention) (a) Preparation of acrylic rubber (A2) 1685 g of toluene are introduced into a flask and heated to 75 ° C under nitrogen and 5% each of the feeds 1 and 2 then are then taken initially with agitation. Feeding 1 Feeding 2 750 g of n-butyl acrylate 8 1 8 mg of azobisisobutyronitrile (A2ml) (A1BN) 17.6 g of allyl methacrylate 40 ml of toluene (A2m3) 60 g of hydroxypropyl methacrylate (A2m2) 40 ml of acetone The rest of the feeds 1 and 2 are then dosed continuously over the course of the next 4 hours. After a total polymerization time of 8 hours at 75 ° C, the batch is cooled and stabilized with 0.12% (based on the amount of monomers) of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. The conversion was 95% b) + c) Preparation of rubber-modified molding material. The toluene and acetone and any residual monomer present in batch (a) are removed under reduced pressure in a rotary evaporator and replaced by monomers such that the mixture (AM) of 1272 g of styrene (Alml) results, 424 g of acrylonitrile (Alm2) and 77g of maleic anhydride (A2m2), wherein 150 g of the acrylic rubber (A2) from step (a) was present in solution. This mixture (AM) is introduced into a steel kettle and heated to 123 ° C with stirring. After conversion approximately 20%, 1.49 g of tert-butyl mercaptan and 2.31 g of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant, and after a total conversion of 30 %, 1.93 g of dicumyl peroxide are added. After a total conversion of 33.9% of the monomers, 1900 g of water, 2.0 g of tetrasodium diphosphate and 20 g of polyvinylpyrrolidone and 59.8 g of a 10% polyvinyl alcohol solution were added. This mixture is then polymerized to completion for 3 hours at 110 ° C, for 3 more hours at 130 ° C and for 6 hours at 140 ° C. The mixture is then cooled and the polymer is filtered off and dried. It was possible to produce shaped articles having a mat surface from the modified rubber molding material (A). Example 7 (according to the invention) 1753 g of cyclohexane are introduced into a flask and heated to 75 ° C under nitrogen, and 5% of each of feeds 1 and 2 set out below, then taken initially with stirring . Feeding 1 Feeding 2 750 g of n-butyl acrylate 8 1 8 m g of azobisisobutyronitrile (A2ml) (AIBN) 6.51 g of allyl methacrylate 40 ml of toluene (A2m3) 22.5 g of maleic anhydride 40 ml of acetone (A2m2) The rest of feeds 1 and 2 are then dosed continuously over the course of 4 hours and, After a total polymerization time of 8 hours, the batch is cooled and stabilized with 0.12 g of octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant. The monomer conversion was 95%. b) + c) Preparation of rubber-modified molding material. The acetone, cyclohexane, toluene and any residual monomer present were removed under reduced pressure in a rotary evaporator and then replaced with monomers, such that a mixture of 150 g of the acrylic rubber (A2) of a) was present in a form dissolved or swollen in a mixture of 1247 g of styrene (Alml) and 416 g of acrylonitrile (Alm2). 110 g of a 72% styrene copolymer, 24% acrylonitrile and 4% maleic anhydride, as reactive polymer (AlPf), and then 9.3 g of ethylenediamine as the entanglement agent (AMV) are added to this mixture. The resulting mixture (AM) is placed in a steel kettle and heated to 123 ° C with stirring. After a conversion of approximately 20% of the monomers, 1.49 g of ter-dodecyl mercaptan and 2.31 g of octadecyl 3- (3,5-di-tert-butyl-4-hydroxy-nyl) propionate, as an antioxidant, and after from a conversion of 30% of the monomers, 1.7 g of dicumyl peroxide was added. After a total conversion of 33%, 1900 g of water, 2.0 g of tetrasodium diphosphate, 20 g of polyvinylpyrrolidone and 20 g of a solution of aqueous polyvinyl alcohol with a concentration of 10% were added and the mixture was polymerized to 3-fold termination. hours at 110 ° C, for 3 hours at 130 ° C and for 6 hours at 140 ° C. It was possible to produce shaped articles having a mat surface from the resulting rubber modified molding materials.

Claims (12)

1. - A process for the preparation of a molding material (A) modified with acrylic rubber, by (a) polymerizing a mixture (A2M) of (at) at least one monomer (A2ml) of the formula CH2 = CR1 - COOR2 wherein R1 is hydrogen or methyl and R2 is alkyl with 1 to 32 carbon atoms, (a2) at least one copolymerizable olefinically unsaturated monomer (A2m2), which contains a chemically reactive group (A2m2x) and (a3) if requires, at least one additional copolymerizable olefinically unsaturated monomer (A2m3), the sum of the amounts of the monomers (A2m2) and (A2m3) is less than the monomer amount (A2ml), to give an acrylic oxide (A2) having a vitreous transition temperature at minus 0 ° C, (b) dissolution or swelling of the fully polymerized acrylic rubber (A2), with or without the addition of an inert solvent, in one or more olefinically unsaturated monomers (Alm) forming a cover of hard graft (Al) and whose polymers or copolymer Grouts have a vitreous transition temperature of at least + 20 ° C, and addition of a minor amount of a monomer (Almf) or a polymer (AlPf) compatible or partially compatible with the monomers (Alm) to the monomers (Alm), (Almf) and (AlPf) which contain at least one chemically reactive group that is capable of reacting with the chemically reactive groups (A2m2x) of the acrylic rubber (A2) or that, with the aid of an entanglement agent (AMV) added to the mixture (AM), allows coupling of the chemically reactive group to a chemically reactive group (A2m2x) of the acrylic rubber (A2 ), and (c) graft polymerization of the resulting mixture (AM) in one or more stages to give a molding material (A), at least the first stage of the polymerization of the mixture (AM) is carried out, up to a conversion of more than 15% by weight of the monomers, by polymerization in solution or mass by free radicals or thermal.

2. Method according to claim 1, characterized in that the copolymerizable olefinically unsaturated monomer (A2m2) in the mixture (A2M) contains an epoxy, amino, amido, hydroxyl, carboxylic anhydride or carboxyl group.

3. Method according to claim 1 or 2, characterized in that the mixture (AM) contains, in addition to an acrylic rubber (A2) having chemically reactive groups and the monomers (Alm), at least one monomer (Almf) or polymer (AlPf) having a chemically reactive group that is capable of reacting with the chemically reactive groups (A2m2x) introduced by the comonomer (A2m2) in the acrylic rubber (A2).

4. - Method according to any of claims 1 to 3, characterized in that the acrylic rubber (A2) contains epoxy groups and the chemically reactive monomer (Almf) or the chemically reactive polymer (AlPf) in the mixture of (AM) contain amino groups primary or secondary, hydroxyl, amido, carboxylic anhydride or carboxyl.

5. - Method according to any of claims 1 to 4, characterized in that the mixture (AM) contains an entanglement agent (AMV) having at least two chemically reactive groups that are capable of reacting with the chemically reactive groups in the acrylic rubber (A2) and with the chemically reactive groups of the monomer (Almf) or the polymer (AlPf).

6. - Method according to any of claims 1 to 5, characterized in that the mixture (AM) contains as interlacing agent (AMV) a diamine or polyamine having at least two primary or secondary amino groups.

7. - Method according to any of claims 1 to 6, characterized in that styrene, acrylonitrile, methyl methacrylate or a mixture thereof is used as monomer (Alm) in the mixture (AM).

8. Method according to any of claims 1 to 7, characterized in that the amount of monomer (A2m2) is from 1 to 25% by weight of the total amount of the monomers in the mixture (A2M).

9. - Procedure according to any of claims 1 to 8, characterized in that the mixture (A2M) contains as monomer (A2m3), a monomer having i two non-conjugated double bonds C * = C in an amount from 0.1 to 12% by weight of the total amount of the monomers in the mixture ( A2M).

10. - A molding material that is obtained by a process according to any of claims 1 to 9.

11. - molding material modified with acrylic rubber and obtained by graft polymerization in one stage or multiple stages of a mixture (AM) containing (i) an acrylic rubber (A2) having a vitreous transition temperature of less than 0 ° C and is a fully polymerized copolymer (A2) comprising (at) at least one monomer (Allyl) of the formula CH2 = CR1-COOR2 wherein R1 is hydrogen or methyl and R2 is alkyl having 1 to 32 carbon atoms, (a2) an olefinically unsaturated monomer (A2m2) having a chemically reactive group (A2m2x) and (a3) if at least one additional olefinically unsaturated monomer is required in an amount which is less than the amount of monomer (A2ml), and (ii) (ii) one or more olefinically unsaturated monomers (Alm) forming the hard graft cover and with which is mixed from 1 to 25%, based on the weight of the monomers, of a monomer (Almf) or polymer (AlPf) containing at least one chemically reactive group which is capable of reacting with chemically reactive groups of the acrylic rubber (A2) or, with the aid of an entanglement agent aggregate, (AMV), allows coupling with the chemically reactive groups (A2m2x) of the acrylic rubber (A2), (iii) at least the first stage of the graft polymerization of the mixture (AM), after dissolution or fluffing of the rubber acrylic (A2) in the monomers (Alm) and if required, after addition of an entanglement agent (AMV), is carried out, at a conversion of more than 15% by weight of monomers, by polymerization in solution or mass by free radicals or thermal.

12. Use of the molding material according to claim 10 or llf as a delousing or matte agent for other compatible or partially compatible polymer molding materials.