DE102005022632A1 - Preparation of a particle-forming rubber, useful in the preparation of a rubber-like grafted-copolymer, comprises agglomeration of a particle-forming substrate rubber in an emulsion by means of a particle-forming agglomerated latex A - Google Patents

Abstract

Preparation of a particle-forming rubber (I) comprising at least a fraction of agglomerated particle, where at least a fraction exhibits a defined non-uniformity, comprises agglomeration of a particle-forming substrate rubber that is present in an emulsion by means of at least one particle-forming agglomerated latex A exhibiting a defined non-uniformity of = 0.65. Independent claims are included for: (1) a particle-forming rubber that is produced by the process; (2) an agglomerated lattice A with a defined non-uniformity produced by emulsion polymerization of one or more hydrophobic monomer followed by emulsion polymerization of a monomer mixture comprising hydrophobic and hydrophilic monomer in the presence of an alkali salt of an acid, a sulfate or sulfonate with 10-20C aliphatic residue as an emulsifier; (3) use of an agglomerated lattice A for the manufacture of the particle-forming substrate rubber in emulsion for the production of particle-forming rubber containing at least a fraction of agglomerated particle, where at least a fraction exhibits defined non-uniformity of less than 1; (4) a rubber-like graft-copolymer (p1) formed from 30-99 (preferably 30-90) wt.%, based on p1, of a particle-forming rubber obtained from the above process, as a graft substructure; 1-70 (preferably 10-70) wt.%, based on p1, of a graft substructure grafted coating (p2) with a glass transition temperature of more than 50[deg]C, preferably formed from 50-100 wt.%, related on (p2), of at least one vinyl-aromatic monomer (p21), 0-50 wt.%, based on (p2), of at least a polar, copolymerizable comonomer (p22), preferably acrylonitrile, methacrylnitrile, ester of (meth)acryl acid with 1-4C alkyl, malein acidanhydride and its imide, (meth) acrylamide and vinylalkylether with 1-8C alkyl; 0-40 wt.%, based on (p2), of one or more further monoethylenic unsaturated monomer (p23), where (p21), (p22) and (p23) constitutes to 100 wt.%; or (p24) 50-100 wt.-%, based on (p2), (p25) 0-50 wt.%, based on (p2), of at least a further copolymerizable monomer, preferably styrol, (meth)acrylnitrile or ester of acrylic acid, where the (p24) and (p25) constitutes to 100 wt.%; (5) a thermoplastic molded mass comprising a rubber-like grafted-copolymer (t0) and matrix polymer (t2), preferably polymer obtained from styrol-acrylnitrile, (alpha -methylstyrol-acrylnitrile)-, styrolmaleinimide and styrol-maleinic acid anhydride and/or (t2) partial-crystalline, preferably linear, polyamide such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 or partial-crystalline copolyamide; and/or (t3) polyester like polymethylmethacrylate; and/or (t4) aromatic aliphatic polyester, preferably polybutyleneterephthalate, polypropyleneterephthalate, polyethylenenaphthalate or polyethyleneterephthalate; and/or (t5) polyoxyalkylene e.g. polyoxymethylene; and/or (t6) polycarbonate; and/or (t7) polyarylenesulfide, preferably polyphenylenesulfide; and (t8) optionally fiber-or particle-forming fillers or their mixtures; and (t9) optionally other additives; (6) a molded mass obtained from thermoplastic molded mass; and (7) a procedure for the control of non-uniformity of at least an agglomerated fraction of particle-forming through agglomeration agent of agglomerated lattice A producing rubber, where the agglomerated lattice A is particle-forming, comprising emulsion polymerization of at least a hydrophobic monomer followed by a monomer mixture extensively hydrophobic and hydrophilic monomer in the presence of an emulsifier, and with a particle-forming substrate rubber that is present in the emulsion.

Description

The present invention relates to a process for the preparation of a particulate rubber K comprising at least one fraction F of agglomerated particles, the at least one fraction F having a defined nonuniformity U _F , by agglomeration of a particulate substrate rubber S present in an emulsion by means of at least one particulate agglomerate A A, wherein the Agglolatex A has a defined nonuniformity U _A. Furthermore, the present invention relates to a particulate rubber K preparable by the process according to the invention and a Agglolatex A with a defined nonuniformity U _A producible by emulsion polymerization. Furthermore, the present invention relates to the use of Agglolatex A according to the invention for the agglomeration of an emulsion-present particulate substrate rubber S for the preparation of a particulate rubber K. The present invention further relates to a rubbery graft copolymer P, which is composed inter alia of the particulate rubber K according to the invention, and the use of the particulate rubber K of the invention as a grafting base for the preparation of a rubbery graft copolymer. The present invention further relates to a thermoplastic molding composition T containing inter alia a rubbery graft copolymer according to the invention and a process for the preparation of the novel thermoplastic molding compositions and their use for the production of films, moldings, foams and fibers, as well as moldings obtainable using the thermoplastic molding compositions according to the invention. In addition, the present invention relates to a method for controlling the non-uniformity U _{F of} at least one agglomerated fraction of a particulate agglomerated Agglomeration by means of an Agglolatex A rubber K, the Agglolatex A itself being particulate and obtainable by emulsion polymerization.

rubber latexes, as with a usual Homo- or copolymerization of butadiene incurred in general Particle diameter in the order of magnitude from about 0.05 to 0.1 μm. ABS polymers made using such rubbers generally show moderately low toughness. It is known that ABS polymers obtained with more favorable properties can be if in the graft polymerization for the preparation of ABS polymers rubber latices with larger particles starts. It is also known that the particles in emulsion prepared or brought into emulsion after its preparation Rubber by adding a second suitable rubber dispersion be enlarged can (Agglomeration).

H.-G. Keppler et al., Angew. Makromol. Chem. 2, 1968, pages 1 to 25 concerns a study on the Agglomeration of polymer latices. In the experiments carried out by way of example As a substrate "S" is a butadiene rubber and used as agglomerating agent "A" is a copolymer of butadiene, styrene and methacrylic acid. According to Keppler et al. become in the agglomeration of the rubber latices in general obtained bimodal distributions. A maximum of differential Distribution function with small particle diameters contains the part of the primary particles, which have not been agglomerated. A second maximum includes by agglomeration of the primary particles resulting secondary particles. Furthermore, in Keppler et al. mentioned that the distribution of offspring typically "quite often is narrow. "Regarding one Control of particle size distribution within the individual fractions of the agglomerated rubber latex contains Keppler et al. No statement.

Of the Agglolatex itself can be prepared by various methods be and have a very different structure. According to Keppler et al. can serve as agglomerating agent all dispersions by incorporation hydrophilic monomers are sufficiently hydrophilic. Agglomerated all dispersions containing no or only very few hydrophilic groups in the polymer.

EP-A 0 517 539 relates to impact Polymer compositions and process for their preparation. to Preparation of the polymer compositions is first agglomerated rubber latex. This one is by adding a polymeric latex containing at least 30% by weight of a carboxylic acid monomer contains and has an average particle diameter of 100 nm to 300 nm, to a synthetic rubber latex having a middle Particle diameter of 50 nm to 200 nm. The middle Particle size of the agglomerated Rubber latex is in the range of 200 nm to 1000 nm. EP-A 0 517 539 contains no information regarding a particle size distribution the agglomerated particles of the agglomerated rubber latex or in terms of a control of this particle size distribution.

EP-A 0 433 710 relates to a process for the preparation of polybutadiene with an increased mean Particle size. According to EP-A 0 433 710, butadiene is agglomerated with an acrylic latex, the acrylic latex preferably being a polyalkyl acrylate latex or a polyalkyl methacrylate latex. This acrylic latex is added according to EP-A 0 433 710 already during the polymerization of the polybutadiene rubber in an amount sufficient to increase the average particle size of the polybutadiene latex. With regard to a particle size distribution of the agglomerated polybutadiene particles and a control of the particle size distribution, EP-A 0 433 710 contains no information.

According to US 4,419,496 Agglolatices having a core-shell structure are disclosed. These agglomerates have an elastomer core with an average particle size in the range of 60 to 250 nm. The shell is based on alkyl acrylate and an unsaturated carboxylic acid. It is disclosed that selected particle sizes and selected particle size distributions can be achieved in the agglomerated rubber. For this purpose it is recommended to change the pH, to vary the acid content and / or the glass transition temperature of the Agglolatex. In addition, according to US 4,419,496 Agglomerates having a small particle diameter to agglomerate rubbers having larger particle diameters more.

EP-A 0 144 081 relates to thermoplastic compositions containing a excellent impact resistance and heat resistance. These thermoplastic compositions are obtained starting from an agglomerated rubber, the by agglomeration of the particles of a diene rubber passing through Emulsion polymerization was obtained, with a copolymer latex, made of an unsaturated acid monomer and an alkyl acrylate. According to EP-A 0 144 081 describes that the particle size of the used as Agglolatex Copolymer has a significant influence on its ability to to agglomerate another rubber.

In WO 97/21770 describes agglolatices containing 5 to 25% by weight an unsaturated one Contain acid. In their preparation, alkali metal salts of higher fatty acids are added as emulsifying agents. The type of addition of the emulsifier can be according to WO 97/21770 the particle size of Agglolatex to adjust. To produce rubbers with bimodal particle size distribution, become according to WO 97/21770 two Agglolatices differing in particle size from each other, added.

DE-A 196 54 783 relates to a process for the preparation of a polybutadiene latex, the reaction times in the polymerization of butadiene and in the agglomeration of polybutadiene in the production of polybutadiene latex shorten as well as an agglomerating agent for effective agglomeration of polybutadiene latexes and a method of making this Agglomerating. The agglomerating agent is mixed with an alkyl acrylate, an ionic comonomer, an anionic surfactant and an anionic initiator. The agglomeration of polybutadiene takes place in the presence of the surfactant and in the presence of an electrolyte, the particle size and the Distribution of the particle size of the polybutadiene latex controlled and for the stability the polybutadiene latex provides.

DE-A 24 27 960 relates to a process for the production of impact-resistant thermoplastic molding compositions, preferably ABS polymers, by Graft polymerization using an agglomerated rubber latex. The rubber latex used is an acrylic ester polymer, preferably a copolymer of 96% ethyl acrylate and 4% methacrylamide. According to DE-A 24 27 960 is in the agglomeration process disclosed in DE-A 24 27 960 only part of the rubber particles agglomerated, leaving a bimodal or wide distribution arises.

US 5,470,895 relates to a process for the agglomeration of an elastomeric latex using high molecular weight polyoxyethylene copolymers as Agglolatex. This Agglolatex preferably has a monomodal particle size distribution. If one uses this Agglolatex with monomodal particle size distribution, agglomerated latices are obtained with bimodal particle size distribution. On the other hand, if an agglomerate with a polymodal particle size distribution or a mixture of different monomodal agglolatices is used, agglomerated latices having a broad and controlled particle size distribution are obtained.

It has thus been known from the prior art that the agglomeration of rubbers by the choice of various factors also influences, inter alia, the type and size distribution of agglomeratex and substrate rubber. In particular, it was known that by means of agglomeration it is possible to produce particulate rubber latices with bimodal or multimodal particle size distribution. However, the problem of controlling the particle size distribution within the individual fractions has not yet been solved. In a bimodal distribution, for example, two fractions are obtained, namely particles belonging to the fraction having a smaller average particle diameter and those belonging to the fraction having a count larger average particle diameter. If the difference between the smallest particle of the second fraction and the largest particle of the second fraction is very large, there is a risk that the substrate will not be grafted sufficiently uniformly well in a subsequent grafting reaction. Furthermore, too wide non-uniformity (U _F ) of the agglomerated fraction (F) can cause the large particles in this fraction to be insufficiently grafted. This in turn can be expressed in the finished product by quality losses such as lack of optical and mechanical properties. It is further known that the presence of graft rubbers having a wide nonuniformity in thermoplastic molding compositions can have a detrimental effect on the gloss of articles made from these molding compositions.

Consequently the object of the present invention is to provide a Method by means of which it is possible to determine the particle size distribution in the agglomeration of a rubber latex within the individual to control the fractions obtained.

This object is achieved by a method for producing a particulate rubber K comprising at least one fraction F of agglomerated particles, the at least one fraction F having a defined non-uniformity U _F , by agglomeration of a particulate substrate rubber S present in an emulsion by means of at least one particulate Agglolatex A , wherein the Agglolatex A has a defined non-uniformity U _A of ≤ 0.65.

The ratio of the nonuniformity U _{F of} the at least one fraction F to the nonuniformity U _{A of} the at least one particulate Agglolatex A in the process according to the invention is preferably 0.75 to 1.50.

With Help of the method according to the invention is a targeted production of agglomerated particulate rubbers K possible, its particle size distribution the agglomerated particles of the rubber K targeted can be. Thus, with the aid of the method according to the invention the production of tailor made particulate Rubbers K possible, the desired one Properties, e.g. As mechanical properties are adjusted can.

For the purposes of the present application, "defined nonuniformity U _F " means that the nonuniformity of the at least one fraction F of agglomerated particles of the particulate rubber K can be adjusted in a targeted manner by selecting an agglomerate A with a certain nonuniformity U _A.

It has surprisingly been found that the particle size distribution of the at least one fraction F of agglomerated particles of a particulate rubber (nonuniformity U _F ) is determined by the particle size distribution of the at least one agglomerate A used (non-uniformity U _A ).

rubber substrate S

When Substrate rubber is generally an acrylic ester polymer, which is preferably at least partially crosslinked, and / or a diene polymer used. In the case of mixtures of the acrylic ester polymer and the diene polymer, the mixing ratio is not critical but generally in the range of 4: 1 to 1: 4, preferably from 1: 2 to 2: 1. Preferred as the substrate rubber S is a diene polymer used.

• (s₁) einem zumindest teilweise vernetzten Acrylesterpolymerisat gebildet aus (s₁₁) 50 bis 99,99 Gew.-%, bezogen auf (s₁), mindestens eines Alkylacrylats mit 1 bis 10 Kohlenstoffatomen im Alkylrest, (s₁₂) 0,01 bis 5 Gew.-%, bezogen auf (s₁), mindestens eines polyfunktionellen vernetzend wirkenden Monomeren, und (s₁₃) 0 bis 49,9 Gew.-%, bezogen auf (s₁), mindestens eines weiteren mit (s₁₁) copolymerisierbaren Monomeren, bevorzugt ausgewählt aus der Gruppe bestehend aus Vinylalkylethern mit 1 bi 8 Kohlenstoffatomen im Alkylrest, Butadien, Isopren, Styrol, Acrylnitril, Methacrylnitril und Methylmethacrylat, Acrylsäure, Methacrylsäure, Itaconsäure und Maleinsäureanhydrid, und (s₁₄) 0 bis 5 Gew.-% Gruppen, die von den gegebenenfalls bei der Herstellung des Substratkautschuks S eingesetzten Reglern, Initiatoren und/oder Emulgatorsystemen stammen; und/oder
• (s₂) einem Dienpolymerisat, aufgebaut aus (s₂₁) 60 bis 100 Gew.-%, bezogen auf (s₂), mindestens eines Diens und (s₂₂) 0 bis 40 %, bezogen auf (s₂), weiterer polymerisierbarer Monomere, bevorzugt ausgewählt aus der Gruppe bestehend aus Alkylacrylaten mit 1 bis 10 Kohlenstoffatomen im Alkylrest, Vinylalkylethern mit 1 bis 8 Kohlenstoffatomen im Alkylrest, Styrol, Acrylnitril, Methacrylnitril, Methylmethacrylat, Acrylsäure, Methacrylsäure, Itaconsäure und Maleinsäureanhydrid, und (s₂₃) 0 bis 5 Gew.-% Gruppen, die von den gegebenenfalls bei der Herstellung des Substratkautschuks S eingesetzten Reglern, Initiatoren und/oder Emulgatorsystemen stammen.

The substrate rubber S particularly preferably has a glass transition temperature (T _g ) of below -10 ° C. Most preferably, the substrate rubber S is made up

• (s ₁ ) an at least partially crosslinked acrylic ester polymer formed from (s ₁₁ ) 50 to 99.99% by weight, based on (s ₁ ), of at least one alkyl acrylate having 1 to 10 carbon atoms in the alkyl radical, (s ₁₂ ) 0.01 to 5 wt .-%, based on (s ₁ ), of at least one polyfunctional crosslinking monomer, and (s ₁₃ ) 0 to 49.9 wt .-%, based on (s ₁ ), at least one further with (s ₁₁ ) copolymerizable monomers, preferably selected from the group consisting of vinyl alkyl ethers having 1 to 8 carbon atoms in the alkyl radical, butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile and methyl methacrylate, acrylic acid, methacrylic acid, itaconic acid and maleic anhydride, and (s ₁₄ ) 0 to 5 wt. % Of groups which may be selected from those which may be used in the preparation of the substrate rubber S used regulators, initiators and / or emulsifier systems; and or
• (s ₂ ) a diene polymer composed of (s ₂₁ ) 60 to 100 wt .-%, based on (s ₂ ), at least one diene and (s ₂₂ ) 0 to 40%, based on (s ₂ ), further polymerisable Monomers, preferably selected from the group consisting of alkyl acrylates having 1 to 10 carbon atoms in the alkyl radical, vinyl alkyl ethers having 1 to 8 carbon atoms in the alkyl radical, styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, acrylic acid, methacrylic acid, itaconic acid and maleic anhydride, and (s ₂₃ ) 0 to 5% by weight of groups derived from any regulators, initiators and / or emulsifier systems used in the preparation of the substrate rubber S.

• (s₁₁) 50 bis 99,99 Gew.-%, bevorzugt 55 bis 99,9 Gew.-%, besonders bevorzugt 60 bis 99,85 Gew.-%, bezogen auf (s1), mindestens eines Alkylacrylats mit 1 bis 10 Kohlenstoffatomen im Alkylrest. Bevorzugte Acrylate sind solche mit 2 bis 10 Kohlenstoffatomen im Alkylrest, besonders bevorzugt sind Ethylacrylat, tert.-, iso- und n-Butylacrylat und 2-Ethylhexylacrylat, wobei n-Butylacrylat und 2-Ethylhexylacrylat ganz besonders bevorzugt sind.
• (s₁₂) 0,01 bis 5 Gew.-%, bevorzugt 0,1 bis 4 Gew.-%, besonders bevorzugt 0,15 bis 3 Gew.-%, bezogen auf (s₁), vernetzend wirkender Monomere. Geeignete vernet zend wirkende Monomere sind zum Beispiel polyfunktionelle Monomere mit mindestens 2 olefinischen, nicht konjugierten Doppelbindungen wie Ethylenglykoldiacrylat, Butandioldiacrylat, Hexandioldiacrylat, Ethylenglykoldimethacrylat, Butandioldimethacrylat, Hexandioldimethacrylat, Divinylbenzol, Diallylmaleat, Diallylfumarat, Diallylphthalat, Diallylcyanurat, Tricyclodecenylacrylat, Dihydrodicyclopentadienylacrylat, Diallylphosphat, Allylacrylat, Allylmethacrylat und Dicyclopentadienylacrylat (DCPA), wie beispielsweise in DE-C 12 60 135 erwähnt.
• (s₁₃) 0 bis 49,9 Gew.-%, bevorzugt 0 bis 44,9 Gew.-%, besonders bevorzugt 0 bis 39,9 Gew.-%, bezogen auf (s₁), mit (s₁₁) copolymerisierbare Monomere. Diese sind bevorzugt ausgewählt aus der Gruppe bestehend aus Vinylalkylethern mit 1 bis 8 Kohlenstoffatomen im Alkylrest, zum Beispiel Vinylmethylether, Vinylpropylether, Vinylethylether, Butadien, Isopren, Styrol, Acrylnitril, Methacrylnitril, Methylmethacrylat, Acrylsäure, Methacrylsäure, Itaconsäure und Maleinsäureanhydrid.
• (s₁₄) 0 bis 5 Gew.-%, bevorzugt 0 bis 4 Gew.-%, besonders bevorzugt 0 bis 3,5 Gew.-% Gruppen, die von den gegebenenfalls bei der Herstellung des Substratkautschuks S eingesetzten Reglern, Initiatoren und/oder Emulgatorsystemen stammen, z.B. Mercaptogruppen von Mercaptanen wie t-Dodecylmercaptan oder SO3^–-Gruppen von Sulfaten wie dem Initiator Kaliumpersulfat.

The acrylic ester polymers (s ₁ ) are preferably composed of

• (s ₁₁ ) 50 to 99.99 wt .-%, preferably 55 to 99.9 wt .-%, particularly preferably 60 to 99.85 wt .-%, based on (s1), of at least one alkyl acrylate having 1 to 10 Carbon atoms in the alkyl radical. Preferred acrylates are those having 2 to 10 carbon atoms in the alkyl radical, particular preference is given to ethyl acrylate, tert-butyl, isobutyl and n-butyl acrylate and 2-ethylhexyl acrylate, with n-butyl acrylate and 2-ethylhexyl acrylate being very particularly preferred.
• (s ₁₂ ) 0.01 to 5 wt .-%, preferably 0.1 to 4 wt .-%, particularly preferably 0.15 to 3 wt .-%, based on (s ₁ ), crosslinking monomers. Suitable Vernet zend acting monomers are, for example, polyfunctional monomers having at least 2 non-conjugated olefinic double bonds such as ethylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, Diallylcyanurat, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, Diallylphosphat, allyl acrylate, allyl methacrylate and dicyclopentadienyl acrylate (DCPA), as mentioned for example in DE-C 12 60 135.
• (s ₁₃ ) 0 to 49.9 wt .-%, preferably 0 to 44.9 wt .-%, particularly preferably 0 to 39.9 wt .-%, based on (s ₁ ), with (s ₁₁ ) copolymerizable monomers. These are preferably selected from the group consisting of vinyl alkyl ethers having 1 to 8 carbon atoms in the alkyl radical, for example vinyl methyl ether, vinyl propyl ether, vinyl ethyl ether, butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, acrylic acid, methacrylic acid, itaconic acid and maleic anhydride.
• (s ₁₄ ) 0 to 5 wt .-%, preferably 0 to 4 wt .-%, particularly preferably 0 to 3.5 wt .-% groups of the optionally used in the preparation of the substrate rubber S regulators, initiators and / or emulsifier systems, for example, mercapto groups of mercaptans such as t-dodecyl mercaptan or SO3 ^- groups of sulfates such as the initiator potassium persulfate.

By using the comonomers mentioned above, the property profile of the acrylic ester polymers (s ₁ ) can be controlled, for example, with regard to the degree of crosslinking, which may be desirable in some cases. Processes for the preparation of the acrylic ester polymers (s ₁ ) are known to the person skilled in the art and described in the literature. Corresponding products are in part commercially available. In some cases, production by emulsion polymerization as described in DE-C 12 60 135 has proven to be particularly advantageous. According to DE-C 12 60 135, the preparation of the acrylic ester polymer (s ₁ ) by polymerization of one or more acrylic acid ester (s ₁₁ ), a polyfunctional monomer (s ₁₂ ) and optionally a further copolymerizable monomer (s ₁₃ ) in aqueous emulsion at generally 20 to 100 ° C, preferably 50 to 80 ° C.

In the polymerization, the usual emulsifiers such as alkali metal salts of alkyl or arylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or resin soaps can be used. Preference is given to using the sodium or potassium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms. It is favorable to use the emulsifiers in an amount of from 0.5 to 5% by weight, preferably from 0.5 to 2% by weight, based on the total weight of the monomers used for the acrylic ester polymer (s ₁ ). Generally, a water to monomer ratio of 2: 1 to 0.7: 1 is used.

The polymerization initiators used are, in particular, the customary persulfates, such as potassium peroxodisulfate, but redox systems are suitable. The amounts of initiators, for example 0.1 to 1 wt .-%, based on the total weight of the monomers used for the preparation of the acrylic ester polymer (s ₁ ) depends on the desired molecular weight.

As polymerization auxiliaries, it is possible to use the customary buffer substances which adjust pH values of preferably 6 to 9, for example sodium bicarbonate and sodium pyrophosphate, and generally 0.1 to 3% by weight of a molecular weight regulator such as mercaptan, terpinol or dimeric α-methylstyrene be used.

The exact polymerization conditions, in particular the type, dosage and amount of the emulsifier are chosen within the ranges given above such that the resulting latex of the at least partially crosslinked acrylic ester polymer (s ₁ ) has a d ₅₀ value in the range from about 30 to 1000 nm, preferably in the Range of 50 to 200 nm, more preferably in the range of 55 to 150 nm.

The particle size distribution is in accordance with the present Registration determined by hydrodynamic fractionation (HDF). This is one with solid beads ("Beads" (polystyrene with a uniform surface, 15 μm in diameter)) packed column used, the aqueous medium containing surfactants uninterrupted is flown through (mobile phase). The diameter of the column is about 8 mm. The HDF uses the principle that small particles make the column slower penetrate as larger particles.

A sample of the rubber latex to be measured is diluted to 0.5 g / l. Subsequently, about 20 μl of the diluted sample are injected into the mobile phase at the entrance of the column. There is a fractionation of the sample according to the hydrodynamic diameter of the particles. The effluent from the column is detected by means of a UV detector. The elution time is calibrated before the measurement with a standard latex (mixture of polystyrene latex particles in the range of 20 to 1000 nm). The reproducibility of the measurement cuvette obtained is better than 3% in amplitude and diameter. As a reference method, measurement was carried out by analytical ultracentrifuge (W. Scholtan and H. Lange, Kolloid-Z. And Z. Polymere 250 (1972), pages 782 to 796). Hydrodynamic fractionation devices are known per se and are described, for example, in Emulsion Polymerization and Emulsion Polymers, Chapter 12: EA, Collins, Measurement of Particle Size and Particle Size Distribution, John Wiley, 1997 and GR McGowan, MA Langhorst, J. Coll. A Interface Sci (1982), 92-104. From the HDF, the weight distribution and the d ₅₀ values are obtained.

For the purposes of the present application, the d ₅₀ value of the particle size is defined as usual as the weight-average particle size, as determined by means of HDF. HDF gives the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or below a certain size. The average particle diameter, which is also referred to as the d ₅₀ value of the integral mass distribution, is defined as the value at which 50% by weight of the particles have a smaller diameter and 50% by weight of the particles have a larger diameter than the d ₅₀ Value.

Instead of the acrylic ester polymer (s ₁ ) or in combination with the acrylic ester polymer (s ₁ ), it is also possible to use a diene polymer (s ₂ ) as substrate rubber S.

• (s₂₁) 60 bis 100 Gew.-%, bevorzugt 70 bis 100 Gew.-% eines oder mehrerer Diene, bevorzugt Butadien oder Isopren, und
• (s₂₂) 0 bis 40 Gew.-%, bevorzugt 0 bis 30 Gew.-% weiteren copolymerisierbaren Monomeren, wobei als copolymerisierbare Monomere die vorstehend unter (s₁₁) beschriebenen Alkylacrylate sowie die unter (s₁₃) beschriebenen mit (s₁₁) copolymerisierbaren Monomere geeignet sind; wegen detaillierter Ausführungen wird auf die dortige Beschreibung verwiesen und
• (s₂₃) 0 bis 5 Gew.-%, bevorzugt 0 bis 4 Gew.-%, besonders bevorzugt 0 bis 3,5 Gew.-% Gruppen, die von den gegebenenfalls bei der Herstellung des Substratkautschuks S eingesetzten Reglern, Initiatoren und/oder Emulgatorsystemen stammen, z.B. Mercaptogruppen von Mercaptanen wie t-Dodecylmercaptan oder SO3^–-Gruppen von Sulfaten wie dem Initiator Kaliumpersulfat.

The diene polymers (s ₂ ) are preferably diene polymers (s ₂ ) composed of

• (s ₂₁ ) 60 to 100 wt .-%, preferably 70 to 100 wt .-% of one or more dienes, preferably butadiene or isoprene, and
• (s ₂₂ ) from 0 to 40% by weight, preferably from 0 to 30% by weight, of further copolymerisable monomers, the copolymerizable monomers described above under (s ₁₁ ) being alkyl acrylates and those described under (s ₁₃ ) being (s ₁₁ ) copolymerizable monomers are suitable; for detailed explanations reference is made to the description there and
• (s ₂₃ ) 0 to 5 wt .-%, preferably 0 to 4 wt .-%, particularly preferably 0 to 3.5 wt .-% groups of the optionally used in the preparation of the substrate rubber S regulators, initiators and / or emulsifier systems, for example, mercapto groups of mercaptans such as t-dodecyl mercaptan or SO3 ^- groups of sulfates such as the initiator potassium persulfate.

To prepare the diene polymers suitable as substrate rubber S, the components (s ₂₁ ) and optionally (s ₂₂ ) are polymerized in aqueous emulsion by processes known to those skilled in the art at temperatures of generally from 20 to 100 ° C., preferably from 50 to 90 ° C. It is possible to use the customary emulsifiers, polymerization initiators described above in the preparation of the aryl ester polymer (s ₁ ) and further polymerization auxiliaries, such as buffer substances and molecular weight regulators, in the amounts indicated there.

The exact polymerization conditions for the preparation of a diene polymer (s ₂ ), in particular the type, dosage and amount of the emulsifier are chosen within the ranges given above in detail so that the obtained latex of the diene polymer (s ₂ ) has a d ₅₀ value in the range of generally 50 to 200 nm, as described for example in DE-A 24 27 960.

In a preferred embodiment, the substrate rubber S is a diene polymer (s ₂ ), preferably a butadiene polymer.

The substrate rubber S generally has a d ₅₀ value in the range of 50 to 200 nm, preferably 60 to 180 nm, particularly preferably 65 to 160 nm.

Of the obtained particulate Substrakautschuk present in an emulsion S is according to the inventive method with a particulate Agglolatex A reacted, wherein a particulate rubber K containing at least one fraction F of agglomerated particles is obtained.

Agglolatex A

at in the method according to the invention used Agglolatex is generally a dispersion an acrylic ester polymer.

Prefers is an Agglolatex A, which has a hydrophobic and a hydrophilic Part has.

Especially preferred is the particulate Agglolatex A is a dispersion of an acrylic ester polymer from 90 to 99.9 wt .-% of at least one alkyl ester as hydrophobic Monomer and 0.1 to 10% by weight of at least one hydrophilic monomer, the sum total of hydrophobic and hydrophilic monomers 100 wt .-% results.

In a further preferred embodiment Agglolatex A is a dispersion of an acrylic ester polymer is composed of 45 to 99 wt .-% of at least one alkyl ester as hydrophobic monomer and 0.1 to 25 wt .-% of at least one hydrophilic Monomers, 0 to 40 wt .-% of other monomers, wherein the total of hydrophobic and hydrophilic monomers gives 100 wt .-%.

• (a₁) einem oder mehreren hydrophoben Monomeren (A1) der allgemeinen Formel I CH₂=CHR¹-C(O)-R² worin R¹ H oder CH₃ bedeutet, und R² C₁- bis C₆-Alkyl, bevorzugt C₁- bis C₄-Alkyl wie Methyl, Ethyl, n-Propyl und n-Butyl, besonders bevorzugt Ethyl, bedeutet; bevozugt Methylacrylat oder Ethylacrylat, besonders bevorzugt Ethylacrylat; und
• (a₂) einem oder mehreren hydrophilen Monomeren (A₂) ausgewählt aus der Gruppe bestehend aus Acrylsäure, Methacrylsäure, Itaconsäure, Crotonsäure, Acrylamid, Methacrylamid, Itaconamid, Crotonamid, N-Methylolmethacrylamid und N-Vinylpyrrolidon, bevorzugt Acrylsäure, Methacrylsäure, Acrylamid, Methacrylamid, N-Methylolmethacrylamid und N-Vinylpyrrolidon, besonders bevorzugt Methacrylamid, Acrylsäure und Methacrylsäure;
• (a3) gegebenenfalls weiteren mit (A1) und (A2) copolymerisierbaren Monomeren (A3).

Most preferably, the Agglolatex A is a particulate copolymer composed of

• (a ₁ ) one or more hydrophobic monomers (A1) of the general formula I CH ₂ = CHR ¹ -C (O) -R ² wherein R ^{1 is} H or CH ₃ , and R ^{2 is} C ₁ - to C ₆ -alkyl, preferably C ₁ - to C ₄ -alkyl, such as methyl, ethyl, n-propyl and n-butyl, particularly preferably ethyl; preferably methyl acrylate or ethyl acrylate, more preferably ethyl acrylate; and
• (a ₂ ) one or more hydrophilic monomers (A ₂ ) selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, acrylamide, methacrylamide, itaconamide, crotonamide, N-methylolmethacrylamide and N-vinylpyrrolidone, preferably acrylic acid, methacrylic acid, acrylamide, Methacrylamide, N-methylolmethacrylamide and N-vinylpyrrolidone, more preferably methacrylamide, acrylic acid and methacrylic acid;
• (a3) optionally further with (A1) and (A2) copolymerizable monomers (A3).

Prefers is a particulate Copolymer composed of methyl acrylate or ethyl acrylate, especially preferably ethyl acrylate, as hydrophobic monomer and methacrylamide, acrylic acid and / or methacrylic acid as a hydrophilic monomer.

Especially preferably contains the Agglolatex A is a particulate Copolymer consisting of the abovementioned hydrophobic and hydrophilic Monomers is formed, wherein the particulate copolymer is a core which preferably comprises at least one of the component (A1) called hydrophobic monomers is constructed, preferably from Ethyl acrylate, which core is grafted with a copolymer, that is composed of the components (A1), (A2) and optionally (A3) is.

• (a₁₁) 1 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, besonders bevorzugt 5 bis 20 Gew.-%, bezogen auf die Gesamtmenge des teilchenförmigen Copolymers, eines oder mehrerer hydrophober Monomere (A1) wie bereits vorstehend definiert, wobei Ethylacrylat besonders bevorzugt ist;
• (a₁₂) 20 bis 99 Gew.-%, bevorzugt 50 bis 95 Gew.-%, besonders bevorzugt 80 bis 95 Gew.-%, bezogen auf die Gesamtmenge des teilchenförmigen Copolymerisats, einer auf den Kern aufgepfropften Schale, aufgebaut aus (a₁₂₁) 75 bis 99 Gew.-%, bevorzugt 92 bis 97 Gew.-%, besonders bevorzugt 93 bis 97 Gew.-%, mindestens eines hydrophoben Monomeren (A1) wie vorstehend definiert, bevorzugt Ethylacrylat; (a₁₂₂) 1 bis 25 Gew.-%, bevorzugt 3 bis 8 Gew.-%, besonders bevorzugt 3 bis 7 Gew.-%, bezogen auf die Gesamtmenge der die Schale bildenden Monomeren, mindestens eines hydrophilen Monomeren (A2) wie vorstehend definiert, bevorzugt Methacrylamid, Acrylsäure und/oder Methacrylsäure.

Most preferably, the Agglolatex A thus contains a particulate copolymer composed of

• (a ₁₁ ) 1 to 80 wt .-%, preferably 5 to 50 wt .-%, particularly preferably 5 to 20 wt .-%, based on the total amount of the particulate copolymer, of one or more hydrophobic monomers (A1) as already above wherein ethyl acrylate is particularly preferred;
• (a ₁₂ ) from 20 to 99% by weight, preferably from 50 to 95% by weight, particularly preferably from 80 to 95% by weight, based on the total amount of the particulate copolymer, of a shell grafted onto the core, composed of (a ₁₂₁ ) from 75 to 99% by weight, preferably from 92 to 97% by weight, particularly preferably from 93 to 97% by weight, of at least one hydrophobic monomer (A1) as defined above, preferably ethyl acrylate; (a ₁₂₂ ) 1 to 25 wt .-%, preferably 3 to 8 wt .-%, particularly preferably 3 to 7 wt .-%, based on the total amount of the shell-forming monomers, at least one hydrophilic monomer (A2) as above defined, preferably methacrylamide, acrylic acid and / or methacrylic acid.

Becomes increase the hydrophobicity of the hydrophobic monomers, e.g. through use of Propyl acrylate or butyl acrylate instead of ethyl acrylate, then is a larger amount required on hydrophilic monomers. The same is true when a part of the ethyl acrylate by hydrophobic monomers, e.g. Butadiene, replaced becomes.

• (a₁₁) 10 Gew.-%, bezogen auf die Gesamtmenge des kautschukartigen Copolymers, Ethylacrylat als Kern, und
• (a₁₂) 90 Gew.-%, bezogen auf die Gesamtmenge des teilchenförmigen Copolymerisats, einer auf den Kern aufgepfropften Schale aufgebaut aus (a₁₂₁) 95 bis 97 Gew.-%, bezogen auf die Gesamtmenge der die Schale bildenden Monomere, Ethylacrylat und (a₁₂₂) 3 bis 5 % bezogen auf die Gesamtmenge der die Schale bildenden Monomere, Methacrylamid, Acrylsäure und/oder Methacrylsäure.

Most preferably, an agglomerate A containing a particulate copolymer is composed of

• (a ₁₁ ) 10% by weight, based on the total amount of the rubbery copolymer, ethyl acrylate as a core, and
• (a ₁₂ ) 90% by weight, based on the total amount of the particulate copolymer, of a shell grafted onto the core, composed of (a ₁₂₁ ) 95 to 97% by weight, based on the total amount of the shell-forming monomers, ethyl acrylate and (a ₁₂₂ ) 3 to 5% based on the total amount of shell forming monomers, methacrylamide, acrylic acid and / or methacrylic acid.

Of the in the inventive method used at least one particulate Agglolatex A has a Inconsistency A of ≤ 0.65, preferably ≤ 0.5, particularly preferably ≦ 0.45, most preferably ≤ 0.35 on.

The nonuniformity U in the sense of the present application is a measure of the width of the particle size distribution within a particulate (co) polymer or a fraction of a particulate (co) polymer. The nonuniformity is defined in the sense of the present application as U = (d ₉₀ -d ₁₀ ) / d ₅₀ . The smaller the value U, the narrower the distribution.

The d ₅₀ value is the average particle diameter, according to which 50% by weight of all particles have a smaller diameter and 50% by weight have a larger diameter than the diameter corresponding to the d ₅₀ value. In order to characterize the width of the particle size distribution, in addition to the d ₅₀ value, the d ₁₀ value and the d ₉₀ value are often given. 10% by weight of all particles are smaller and 90% by weight larger than the d ₁₀ diameter. Analog have 90 wt .-% of all particles have a smaller, and 10 wt .-% a diameter larger than that corresponding to the d ₉₀ value. The determination of the d ₅₀ , d ₁₀ and d ₉₀ values takes place by means of hydrodynamic fractionation (HDF), as already stated above.

The agglomerate used in the process according to the invention generally has a d ₅₀ value of 60 to 160 nm, preferably 65 to 160 nm, particularly preferably 65 to 150 nm.

The Preparation of the invention used Agglolatex is carried out by methods known in the art, wherein according to the present Invention, the above emulsifiers are used. in principle is also the use of other than the above emulsifiers possible.

Of the Agglolatex obtained is generally a dispersion of the above said particulate Acrylesterpolymerisats ago. The concentration of at least one particulate Copolymer (Acrylesterpolymerisats) in this dispersion is generally 3 to 60 wt .-%, preferably 7 to 50 wt .-%, particularly preferably 10 to 45 wt .-%.

Of the in the method according to the invention used particulate Agglolatex is preferably prepared by emulsion polymerization. Suitable in the manufacture of Agglolatex A used hydrophobic Monomers (A1) and hydrophilic monomers (A2) and optionally other comonomers (A3) have already been mentioned above. The preferred used amounts of the corresponding monomers are also already mentioned above.

• (i) Emulsionspolymerisation mindestens eines hydrophoben Monomeren (A1) wie vorstehend definiert in einem ersten Schritt und
• (ii) Zugabe eines Monomerengemisches umfassend hydrophobe und hydrophile Monomere (A1 + A2) in einem weiteren Schritt,

wobei die Schritte (i) und (ii) in Gegenwart eines Emulgators erfolgen.For the preparation of the particularly preferred as a particulate copolymer of Agglolatex If core / shell polymers are used, preference is given to emulsion polymerization comprising the steps:

• (I) emulsion polymerization of at least one hydrophobic monomer (A1) as defined above in a first step and
• (ii) addition of a monomer mixture comprising hydrophobic and hydrophilic monomers (A1 + A2) in a further step,

wherein steps (i) and (ii) occur in the presence of an emulsifier.

It has surprisingly been found that an agglomerate A comprising a particulate copolymer having a defined non-uniformity U _A of ≦ 0.65, preferably ≦ 0.5, more preferably ≦ 0.45, most preferably ≦ 0.35, is added by adding an alkali metal salt an acid, a sulfate or sulfonate with an aliphatic radical of 10 to 20 carbon atoms can be selectively prepared as an emulsifier. In this case, the aliphatic radical has a defined number of carbon atoms and is not a mixture containing carbon chains of different chain lengths. However, it is possible to use a combination of, for example, two emulsifiers having aliphatic radicals of different carbon number. The above-mentioned non-uniformity U _{A of} the agglomerate of ≦ 0.65, preferably ≦ 0.5, more preferably ≦ 0.45, very particularly preferably ≦ 0.35, may be used in addition to the use of emulsifiers whose aliphatic radicals have a defined number of carbon atoms can also be obtained by other methods, for example, selection of the stirrer speed or by substantially complete absence of oxygen in the preparation of Agglolatex (by complete inertization).

• (i) eines oder mehrerer hydrophober Monomeren in einem ersten Schritt und
• (ii) eines Monomerengemisches umfassend hydrophobe und hydrophile Monomere in einem weiteren Schritt

in Gegenwart eines Alkalisalzes einer Säure, eines Sulfats oder Sulfonates mit einem aliphatischen Rest mit 10 bis 20 Kohlenstoffatomen als Emulgator.A further subject of the present application is therefore an Agglolatex A with a defined nonuniformity U _A preparable by emulsion polymerization

• (i) one or more hydrophobic monomers in a first step and
• (ii) a monomer mixture comprising hydrophobic and hydrophilic monomers in a further step

in the presence of an alkali metal salt of an acid, a sulphate or sulphonate having an aliphatic radical with 10 to 20 carbon atoms as emulsifier.

The agglomerate A preferably has a nonuniformity U _A of ≦ 0.65, preferably ≦ 0.5, particularly preferably 0.45, very particularly preferably ≦ 0.35.

suitable Alkali salts of an acid, a sulphate or a sulphonate with an aliphatic radical of 10 to 20 carbon atoms are sodium salts and potassium salts. Prefers the aliphatic radical has 10 to 18 carbon atoms. Especially alkali salts of fatty acids with 10, 12, 14, 16 or are preferred 18 carbon atoms used. Furthermore, it is possible to have one Use combination of different emulsifiers, so for example a combination of alkali metal salts, preferably sodium or Potassium salts, of fatty acids with different numbers of carbon atoms, for example a combination a sodium or potassium salt of a fatty acid having 10 carbon atoms and a sodium or potassium salt of a fatty acid having 14 carbon atoms.

With Aid of alkali metal salts, preferably sodium or potassium salts, of acids, Sulfates or sulfonates having an aliphatic radical of from 10 to 20 carbon atoms it is possible the nonuniformity of the particulate polymer of Agglolatex precise adjust.

According to the invention, it has been found that upon agglomeration of a particulate substrate rubber S having a particulate agglomerate A which has a defined nonuniformity U _A , targeted production of a particulate rubber K containing at least one fraction F of agglomerated particles is possible a fraction F has a defined nonuniformity U _F. The at least one fraction F of agglomerated particles preferably has a defined nonuniformity U _F of <1, particularly preferably <0.8, very particularly preferably <0.7.

A further subject of the present application is therefore the use of an agglomerate A according to the invention for agglomerating a particulate substrate rubber S present in emulsion to produce a particulate rubber K comprising at least one fraction F of agglomerated particles, wherein the at least one fraction F has a defined nonuniformity U _F. Preferably, the non-uniformity U _F <1, more preferably <0.8, most preferably <0.7.

Agglomeration of the particulate substrate rubber S with the particulate Agglolatex A for the preparation of the particulate rubber K

The Agglomeration of the particulate Substrakautschuks S can after any suitable, known in the art Method using the particulate Agglolatex used in the invention with a nonuniformity of ≤ 0.65, preferably ≤ 0.5, particularly preferably ≦ 0.45, most preferably ≤ 0.35, carried out become.

The Agglomeration may be in any order of addition of the substrate rubber S and Agglolatex A done. For example, the agglomeration takes place by adding Agglolatex A to the particulate substrate rubber S or by adding the particulate Substrate rubbers S to Agglolatex A. It is also possible that the substrate rubber S and Agglolatex A are mixed continuously. The agglomeration is preferably carried out by adding the Agglolatex A to the particulate Substrate rubber S.

in the Generally, in the agglomeration, 0.2 to 20 parts by weight, preferably 1 to 5 parts by weight of Agglolatex per 100 parts by weight of in emulsion present substrate rubber S, each calculated on the solids used.

The Speed of addition of Agglolatex to that in emulsion particulate substrate rubber S is generally not critical. Usually it takes about to 30 minutes at a temperature of generally 20 to 90 ° C, preferably 30 to 75 ° C.

Under The said agglomeration conditions only a part of the substrate rubber particles S agglomerates to form a particulate rubber K, the non-agglomerated particle and at least one fraction F contains agglomerated particles.

It has surprisingly been found according to the invention that there is a relationship between the nonuniformity U _{F of} the fraction F of the agglomerated particles of the particulate rubber K produced and the nonuniformity U _{A of} the particulate agglomerate A. Thus, when a single particulate agglomerate A having a defined non-uniformity U _{A is} used, a particulate rubber K having a fraction F of agglomerated particles is obtained, the at least one fraction F having a defined nonuniformity U _F , and a fraction of non-agglomerated particles. The obtained particulate rubber K thus has a bimodal particle size distribution. However, when more than one particulate Agglolatex A, for example, Agglolatex A1 having a defined non-uniformity U _A1 and Agglolatex A2 having a defined non-uniformity U _A2 , A1 and A2 having different average particle sizes TG _A1 and TG _A2 , becomes a particulate rubber K containing a fraction F1 of agglomerated particles having a defined non-uniformity U _F1 and a fraction F2 of agglomerated particles having a defined nonuniformity U _F2 and a fraction of non-agglomerated particles. Thus, according to the process of the invention, particulate rubbers having a trimodal particle size distribution are obtained when using two different agglomerates A1 and A2 with different nonuniformities U _F1 and U _F2 .

A further subject of the present application is thus a process according to the present application, wherein a particulate rubber having a bimodal particle size distribution comprising unagglomerated rubber particles and a fraction F of agglomerated rubber particles having a defined non-uniformity U _F by agglomeration by means of a particulate Agglolatex A having a defined non-uniformity U _A of ≦ 0.65, preferably ≦ 0.5, particularly preferably ≦ 0.45, particularly preferably ≦ 0.35 is produced.

A further subject matter of the present application is a process according to the invention, wherein a particulate rubber having a trimodal particle size distribution comprising unagglomerated rubber particles and a fraction F ₁ agglomerated rubber particles with defined non-uniformity U _F1 and a further fraction F ₂ agglomerated rubber particles with a defined nonuniformity U _F2 by Agglomeration by means of two particulate Agglolatices A1 with defined non-uniformity U _A1 and A2 with defined nonuniformity U _A2 , which is different from the non-uniformity U _A1 , the agglolatices A1 and A2 having different mean particle sizes TG _A1 and TG _A2 .

With the aid of the method according to the invention, it is thus possible to produce particulate rubbers K having the defined particle size distributions, for example bimodal or trimodal particle sizes distributions.

To produce a particulate rubber K with trimodal particle size distribution, it is either possible to use the agglomeration by simultaneous addition of two agglolatices A1 and A2 with defined nonuniformities U _A1 and U _A2 with different average particle sizes TG _A1 and TG _A2 or agglomeration A1 and A2 for agglomeration of the substrate rubber S in succession.

• - Menge des Agglolatex: durch Variation der Menge des Agglolatex im Verhältnis zum Substratkautschuk kann die Menge an agglomerierten Teilchen in dem teilchenförmigen Kautschuk K gesteuert werden. Geeignete Mengen des Agglolatex in Bezug auf den Substratkautschuk sind vorstehend genannt.
• - Menge des hydrophilen Monomeren A2 im Agglolatex: durch Variation der Menge des hydrophilen Monomeren A2 bei der Herstellung des Agglolatex und anschließenden Einsatz des Agglolatex bei der Agglomeration des Substratkautschuks ist ebenfalls eine Steuerung der Menge an agglomerierten Teilchen in dem teilchenförmigen Kautschuk K möglich. Mit zunehmender Hydrophilie (Polarität) des Agglolatex steigt die Agglomerationskraft des Agglolatex. Geeignete Mengen des hydrophilen Monomeren A2 in dem Agglolatex A sind vorstehend genannt.
• - Feststoffgehalt des Systems: Durch Variation des Feststoffgehalts des Systems ist ebenfalls eine Steuerung der Menge an agglomerierten Teilchen in dem teilchenförmigen Katuschuk K möglich. Je höher der Feststoffgehalt des Systems vor der Agglomeration ist, desto höher ist die Ausbeute an agglomerierten Teilchen.
• - Zugabe eines oder mehrerer Elektrolyten: Es ist des Weiteren möglich, die Ausbeute an agglomerierten Teilchen in dem teilchenförmigen Kautschuk durch Zugabe eines oder mehrerer Elektrolyten, bevorzugt eines oder mehrerer basischer Elektrolyten, zu erhöhen.

There are various possibilities for influencing the amount of non-agglomerated particles in the desired particulate rubber K, which can be combined or applied separately, for example:

• Amount of Agglolatex: By varying the amount of Agglolatex relative to the substrate rubber, the amount of agglomerated particles in the particulate rubber K can be controlled. Suitable amounts of Agglolatex with respect to the substrate rubber are mentioned above.
• Quantity of Hydrophilic Monomer A2 in Agglolatex: by varying the amount of hydrophilic monomer A2 in the preparation of Agglolatex and subsequent use of Agglolatex in the agglomeration of the substrate rubber, control of the amount of agglomerated particles in the particulate rubber K is also possible. With increasing hydrophilicity (polarity) of Agglolatex the agglomeration force of Agglolatex increases. Suitable amounts of the hydrophilic monomer A2 in Agglolatex A are mentioned above.
• Solid content of the system: By varying the solids content of the system, control of the amount of agglomerated particles in the particulate Katuschuk K is also possible. The higher the solids content of the system prior to agglomeration, the higher the yield of agglomerated particles.
• Addition of one or more electrolytes: It is further possible to increase the yield of agglomerated particles in the particulate rubber by adding one or more electrolytes, preferably one or more basic electrolytes.

When Basic electrolytes are preferred inorganic electrolytes, especially preferred are hydroxides. Very particular preference is given to lithium hydroxide, Sodium hydroxide or potassium hydroxide used. Especially preferred potassium hydroxide is used as the basic electrolyte. It is but also possible Use mixtures of two or more basic electrolytes. Suitable mixtures are, for example, lithium hydroxide with potassium hydroxide or mixtures of lithium hydroxide and sodium hydroxide. It is preferred the electrolyte is used in the form of a dilute aqueous electrolyte solution. The addition of the basic electrolytes can be done before adding the Agglolatex A, simultaneously or separately with the addition of agglolatex A done by this. Under a joint simultaneous addition is to be understood that the basic electrolyte and the Agglolatex be mixed before their joint addition. In a preferred embodiment the addition of the electrolyte takes place before the addition of the Agglolatex A.

Of the pH during the agglomeration is generally 4 to 13, preferably 6 to 13, particularly preferred 8 to 13.

The resulting particulate emulsion rubber has a fraction of non-agglomerated particles and at least one fraction of F agglomerated particles. The at least one fraction of agglomerated particles has a D ₅₀ value of generally> 300 nm, preferably> 350 nm, more preferably> 400 nm. The D ₁₀ value of fraction F of agglomerated particles is generally> 250 nm, preferably> 300 nm, particularly preferably> 350 nm.

One Another subject of the present application is a particulate rubber K, according to the method of the invention can be produced.

The agglomerated particulate rubbers K obtained by the process according to the invention are suitable as grafting base for the preparation of graft polymers P. Because of the possibility of producing particulate rubbers K by means of the process according to the invention, which have at least one fraction F of agglomerated particles with a defined nonuniformity U _F , it is possible to perform a uniform grafting. Due to the uniform distribution of the monomers used for the grafting, a uniform graft shell is obtained whose compatibility with a polymer matrix is improved over graft polymers which have a non-uniformly grafted graft shell. Thus, with the aid of the rubber K obtained according to the process of the invention, graft polymers may protrude the properties are obtained. Thus, it has surprisingly been found that graft polymers which are prepared on the basis of the agglomerated rubbers according to the invention with a defined non-uniformity of the agglomerated fraction (s), in particular based on the agglomerated diene rubbers of the invention, are distinguished by excellent impact strengths. These graft polymers are therefore outstandingly suitable as impact modifiers for thermoplastic molding compositions. Furthermore, thermoplastic molding compositions, in particular ASA, based on graft polymers which are based on the agglomerated rubbers according to the invention with a defined non-uniformity of the agglomerated fraction (s), in particular on the agglomerated acrylate rubbers according to the invention, are distinguished by excellent dyeability.

• (p₁) 30 bis 99 Gew.-%, bevorzugt 30 bis 90 Gew.-%, besonders bevorzugt 40 bis 90 Gew.-%, ganz besonders bevorzugt 40 bis 85 Gew.-%, bezogen auf P, eines teilchenförmigen Kautschuks K hergestellt gemäß dem erfindungsgemäßen Verfahren, als Pfropfgrundlage;
• (p₂) 1 bis 70 Gew.-%, bevorzugt 10 bis 70 Gew.-%, besonders bevorzugt 10 bis 60 Gew.-%, ganz besonders bevorzugt 15 bis 60 Gew.-%, bezogen auf P, einer auf die Pfropfgrundlage gepfropften Pfropfauflage.

In principle, the particulate rubbers K can be grafted with a wide variety of unsaturated compounds. Corresponding compounds and methods are known to the person skilled in the art. Graft polymers P are preferably composed of

• (p ₁ ) 30 to 99 wt .-%, preferably 30 to 90 wt .-%, particularly preferably 40 to 90 wt .-%, most preferably 40 to 85 wt .-%, based on P, of a particulate rubber K prepared according to the method of the invention, as a graft base;
• (p ₂ ) 1 to 70 wt .-%, preferably 10 to 70 wt .-%, particularly preferably 10 to 60 wt .-%, most preferably 15 to 60 wt .-%, based on P, one on the graft base grafted graft pad.

• (p₁) 30 bis 99 Gew.-%, bevorzugt 30 bis 90 Gew.-%, besonders bevorzugt 40 bis 90 Gew.-%, ganz besonders bevorzugt 40 bis 85 Gew.-%, bezogen auf P, eines teilchenförmigen Kautschuks K hergestellt gemäß dem erfindungsgemäßen Verfahren, als Propfgrundlage;
• (p₂) 1 bis 70 Gew.-%, bevorzugt 10 bis 70 Gew.-%, besonders bevorzugt 10 bis 60 Gew.-%, ganz besonders bevorzugt 15 bis 60 Gew.-%, bezogen auf P, einer auf die Propfgrundlage aufgepfropften Propfauflage mit einer T_g von mehr als 50 °C, bevorzugt aufgebaut aus (α) (p₂₁) 50 bis 100 Gew.-%, bezogen auf (p₂), mindestens eines vinylaromatischen Monomeren, (p₂₂) 0 bis 50 Gew.-%, bezogen auf (p₂), mindestens eines polaren, copolymerisierbaren Comonomeren, bevorzugt ausgewählt aus der Gruppe bestehend aus Acrylnitril, Methacrylnitril, Ester der (Meth)acrylsäure mit 1 bis 4 Kohlenstoffatomen im Alkylrest, Maleinsäureanhydrid und dessen Imiden, (Meth)acrylamid und Vinylalkylethern mit 1 bis 8 Kohlenstoffatomen im Alkylrest; (p₂₃) 0 bis 40 Gew.-%, bezogen auf (p₂), eines oder mehrerer weiterer monoethylenisch ungesättigter Monomere, wobei sich die Komponenten (p₂₁), (p₂₂) und (p₂₃) zu 100 Gew.-% ergänzen, oder (β) (p₂₄) 50 bis 100 Gew.-%, bezogen auf (p₂), Methylmethacrylat, (p₂₅) 0 bis 50 Gew.-%, bezogen auf (p₂), mindestens eines weiteren copolymerisierbaren Monomeren, bevorzugt Styrol, (Meth)acrylnitril oder Ester der Acrylsäure,

wobei sich die Komponenten (p₂₄) und (p₂₅) zu 100 Gew.-% ergänzen.Preferably, a rubbery graft copolymer P is composed of

• (p ₁ ) 30 to 99 wt .-%, preferably 30 to 90 wt .-%, particularly preferably 40 to 90 wt .-%, most preferably 40 to 85 wt .-%, based on P, of a particulate rubber K prepared according to the method of the invention, as graft base;
• (p ₂ ) 1 to 70 wt .-%, preferably 10 to 70 wt .-%, particularly preferably 10 to 60 wt .-%, most preferably 15 to 60 wt .-%, based on P, one on the graft base grafted graft with a T _g of more than 50 ° C, preferably composed of (α) (p ₂₁ ) 50 to 100 wt .-%, based on (p ₂ ), at least one vinyl aromatic monomer, (p ₂₂ ) 0 to 50 % By weight, based on (p ₂ ), of at least one polar, copolymerizable comonomer, preferably selected from the group consisting of acrylonitrile, methacrylonitrile, esters of (meth) acrylic acid having 1 to 4 carbon atoms in the alkyl radical, maleic anhydride and its imides, ( Meth) acrylamide and vinyl alkyl ethers having 1 to 8 carbon atoms in the alkyl radical; (p ₂₃ ) 0 to 40 wt .-%, based on (p ₂ ), of one or more further monoethylenically unsaturated monomers, wherein the components (p ₂₁ ), (p ₂₂ ) and (p ₂₃ ) to 100 wt. %, or (β) (p ₂₄ ) 50 to 100 wt .-%, based on (p ₂ ), methyl methacrylate, (p ₂₅ ) 0 to 50 wt .-%, based on (p ₂ ), at least one other copolymerizable monomers, preferably styrene, (meth) acrylonitrile or esters of acrylic acid,

wherein the components (p ₂₄ ) and (p ₂₅ ) add up to 100 wt .-%.

• (p₂₁) 50 bis 100 Gew.-%, bevorzugt 60 bis 100 Gew.-%, besonders bevorzugt 65 bis 100 Gew.-% einer Styrolverbindung der allgemeinen Formel
  
  in der R und R unabhängig voneinander Wasserstoff oder C₁-C₈-Alkyl bedeuten,
• (p₂₂) 0 bis 50 Gew.-%, bevorzugt 0 bis 40 Gew.-%, besonders bevorzugt 0 bis 35 Gew.-%, bezogen auf (p₂) Acrylnitril, Methacrylnitril oder Methylmethacrylat oder deren Mischungen,
• (p₂₃) 0 bis 40 Gew.-%, bevorzugt 0 bis 30 Gew.-%, besonders bevorzugt 0 bis 20 Gew.-%, bezogen auf (p₂), eines oder mehrerer weiterer monoethylenisch ungesättigter Monomere,

wobei sich die Komponenten (p₂₁), (p₂₂) und (p₂₃) zu 100 Gew.-% ergänzen.The graft (p ₂ ) is preferably composed of

• (p ₂₁ ) 50 to 100 wt .-%, preferably 60 to 100 wt .-%, particularly preferably 65 to 100 wt .-% of a styrene compound of the general formula
  
  in which R and R independently of one another are hydrogen or C ₁ -C ₈ -alkyl,
• (p ₂₂ ) 0 to 50 wt .-%, preferably 0 to 40 wt .-%, particularly preferably 0 to 35 wt .-%, based on (p ₂ ) acrylonitrile, methacrylonitrile or methyl methacrylate or mixtures thereof,
• (p ₂₃ ) 0 to 40% by weight, preferably 0 to 30% by weight, particularly preferably 0 to 20% by weight, based on (p ₂ ), of one or more further monoethylenically unsaturated monomers,

wherein the components (p ₂₁ ), (p ₂₂ ) and (p ₂₃ ) supplement to 100 wt .-%.

• (p₂₄) 50 bis 100 Gew.-%, bevorzugt 60 bis 100 Gew.-%, besonders bevorzugt 70 bis 100 Gew.-%, bezogen auf (p₂) Methylmethacrylat, und
• (p₂₅) 0 bis 50 Gew.-%, bevorzugt 0 bis 40 Gew.-%, besonders bevorzugt 0 bis 30 Gew.-%, bezogen auf (p₂) eines oder mehrerer weiterer ungesättigter Monomere,

wobei sich die Komponenten (p₂₄) und (p₂₅) zu 100 Gew.-% ergänzen.Furthermore, a graft (p ₂ ) is suitably constructed

• (p ₂₄ ) 50 to 100 wt .-%, preferably 60 to 100 wt .-%, particularly preferably 70 to 100 wt .-%, based on (p ₂ ) methyl methacrylate, and
• (p ₂₅ ) 0 to 50 wt .-%, preferably 0 to 40 wt .-%, particularly preferably 0 to 30 wt .-%, based on (p ₂ ) of one or more other unsaturated monomers,

wherein the components (p ₂₄ ) and (p ₂₅ ) add up to 100 wt .-%.

The graft (p ₂ ) can be prepared in one or more process steps. Here, the monomers (p ₂₁ ), (p ₂₂ ) and (p ₂₃ ) or (p ₂₄ ) and (p ₂₅ ) may be added to the particulate rubber K singly or in admixture with each other. The monomer ratio of the mixture may be constant in time or a gradient. Combinations of these procedures are possible. For example, first styrene alone and then a mixture of styrene and acrylonitrile on the graft base (p ₁ ) used particulate rubber K polymerize.

Furthermore, the graft (p ₂ ) at the expense of the monomers (p ₂₁ ) and (p ₂₂ ) or (p ₂₄ ) one or more other monoethylenically unsaturated monomers (p ₂₃ ) or (p ₂₅ ) included. Suitable further monoethylenically unsaturated monomers (p ₂₃ ) or (p ₂₅ ) are, for example, C ₁ - to C ₄ -alkyl esters of methacrylic acid or of acrylic acid, methyl methacrylate already being mentioned as component (p ₂₂ ) or (p ₂₄ ), the glycidyl esters, glycidyl acrylate and glycidyl methacrylate; N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexylmaleimide; Acrylic acid, methacrylic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their anhydrides such as maleic anhydride; nitrogen-functional monomers such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole, vinylaniline, acrylamide and methacrylamide; aromatic and araliphatic esters of acrylic acid and methacrylic acid such as phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate; unsaturated ethers such as vinyl methyl ether and mixtures of these monomers.

Preferred graft supports (p ₂ ) are, for example, composed of styrene and / or α-methylstyrene and one or more of the monomers mentioned under (p ₂₂ ) and (p ₂₃ ). Preferred are methyl methacrylate, N-phenylmaleimide, maleic anhydride and acrylonitrile, more preferably methyl methacrylate and acrylonitrile.

Preferred grafting conditions (p ₂ ) are composed of:
p ₂ -1: styrene,
p ₂ -2: styrene and acrylonitrile,
p ₂ -3: α-methylstyrene and acrylonitrile,
p ₂ -4: styrene and methyl methacrylate,
p ₂ -5: methyl methacrylate.

Particularly preferably, the proportion of styrene or α-methylstyrene, or the proportion of the sum of styrene and α-methylstyrene, at least 40 wt .-%, based on (p ₂ ).

One Another object of the present application is the use a particulate rubber K prepared according to the method of the invention as Pfropfggrundlage for the preparation of a graft copolymer P. By using the according to the inventive method produced particulate K rubbers can Graft copolymers P with opposite improved graft copolymers known in the art Properties are obtained.

The graft copolymers P can be used for the preparation of thermoplastic molding compositions T. For this purpose, the graft polymers P are mixed with one or more further polymers (matrix polymer) and optionally further components. The graft (p ₂ ) acts as a compatibilizer between the graft (p ₁ ), ie the particulate rubber K, and the matrix polymer, in which the graft polymers P are embedded. Due to the effect of the graft (p ₂ ) as a compatibilizer, a uniform grafting onto the graft base is important in order to achieve a good compatibility between the graft polymer P and the matrix polymers. The monomers (p ₂ ) preferably correspond to the monomers from which the matrix polymers are synthesized. If the matrix is composed entirely or predominantly of a styrene-acrylonitrile copolymer (SAN), then the grafting layer is also generally wholly or predominantly composed of styrene and / or α-methylstyrene and acrylonitrile.

In general, the graft (p ₂ ) is emulsified in the presence of the agglomerated particle milled rubber K polymerized. Usually, polymerized at temperatures of 20 to 100 ° C, preferably 50 to 80 ° C, wherein the grafting can be carried out in a batch process, in the feed process or continuously.

When Polymerization initiator for the graft pad can the same water-soluble Compounds are used in the polymerization of the graft be used. Furthermore, oil-soluble or used in the Monomer soluble Initiators, for example dialkyl peroxides such as dilauryl peroxide, dibenzyl peroxide, Peresters such as tert-butyl pivalvalent and tert-butylperoxineodecarnoate, and diperoxiketals, peroxycarbonates and azo compounds such as azobisisobutyronitrile (AIBN) and azobisisovaleronitrile (ADVN) can be used. Furthermore hydroperoxides, preferably cumene hydroperoxide, are used as polymerization initiators into consideration.

details to carry out the grafting reaction in emulsion are those skilled in the art and for example in DE-A 24 27 960 and EP-A 0 062 901.

The The gross composition of the graft polymers P remains from those mentioned Embodiments of the method untouched.

Furthermore, the graft polymers P can have a plurality of "soft" and "hard" stages, for example a structure according to (p ₁ ) - (p ₂ ) - (p ₁ ) - (p ₂ ), especially in the case of larger particles.

As far as non-grafted polymers of the monomers (p ₂ ) are formed in the grafting, these amounts, which are generally below 10 wt .-%, based on (p ₂ ), the mass of the graft polymer P assigned.

The graft polymers P are preferably mixed for the preparation of thermoplastic molding compositions T with at least one matrix polymer and optionally other components. Suitable matrix polymers (t ₁ ) are, for example, amorphous polymers. Examples of suitable matrix polymers (t ₁ ) are SAN (styrene-acrylonitrile), AMSAN (α-methylstyrene-acrylonitrile), styrene maleimide, SMSAN (styrene-maleic acid (anhydride)) acrylonitrile polymers or SMSA (styrene-maleic anhydride).

• (t₁₁) 60 bis 100 Gew.-%, bevorzugt 60 bis 99 Gew.-%, besonders bevorzugt 65 bis 85 Gew.-%, Einheiten eines vinylaromatischen Monomeren, bevorzugt Styrol, substituiertes Styrol oder (Meth)acrylsäureester oder Gemische davon, insbesondere Styrol und/oder α-Methylstyrol,
• (t₁₂) 0 bis 40 Gew.-%, bevorzugt 1 bis 40 Gew.-%, besonders bevorzugt 15 bis 35 Gew.-%, Einheiten eines ethylenisch ungesättigten Monomeren, bevorzugt Acrylnitril, Methacrylnitril oder Methylmethacrylat (MMA), besonders bevorzugt Acrylnitril,

wobei die Summe aus (t₁₁) und (t₁₂) 100 Gew.-% ergibt.The component (t ₁ ) is preferably a copolymer

• (t ₁₁ ) from 60 to 100% by weight, preferably from 60 to 99% by weight, particularly preferably from 65 to 85% by weight, of units of a vinylaromatic monomer, preferably styrene, substituted styrene or (meth) acrylic acid esters or mixtures thereof, in particular styrene and / or α-methylstyrene,
• (t ₁₂ ) 0 to 40 wt .-%, preferably 1 to 40 wt .-%, particularly preferably 15 to 35 wt .-%, units of an ethylenically unsaturated monomer, preferably acrylonitrile, methacrylonitrile or methyl methacrylate (MMA), more preferably acrylonitrile .

wherein the sum of (t ₁₁ ) and (t ₁₂ ) gives 100 wt .-%.

According to one embodiment of the present invention, a copolymer of styrene and / or α-methylstyrene with acrylonitrile is used as component (t ₁ ). The acrylonitrile content in these copolymers is 0 to 40 wt .-%, preferably 15 to 35 wt .-%, based on the total weight of component (t ₁ ).

The thermoplastic molding composition T may further as matrix polymers in addition to the component (t ₁₎ or in place of the component (t _1), for example, at least one polymeric from the group of partly crystalline polyamides, partially aromatic copolyamides, polyesters, polyoxyalkylenes, polycarbonates, polyarylene sulphides, Contain polyether ketones and polyvinyl chlorides. It is also possible to use mixtures of two or more of the stated polymers. It is also possible to use mixtures of different polymers of the abovementioned polymer groups, for example mixtures of different polyamides, different polyesters or different polycarbonates.

Suitable polymers (t ₂ ) which can be used as matrix polymers in addition to or instead of the polymers (t ₁ ) are thus partially crystalline, preferably linear, polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide 6,12 and partially crystalline copolyamides. In addition, suitable components (t ₂ ) are semicrystalline polyamides whose acid component consists wholly or partly of adipic acid and / or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid , and their diamine component wholly or partially in particular from m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-dimethylhexamethylenediamine and / or isophoronediamine. Suitable compositions of these partially crystalline polyamides are known in the art.

Other suitable polymers (t ₃ ) which can be used in place of or in addition to the components (t ₁ ) and / or (t ₂ ) are polyesters such as polymethyl methacrylate. Furthermore, instead of or in addition to components (t ₁ ) and / or (t ₂ ) and / or (t ₃ ), aromatic-aliphatic polyesters can be used as component (t ₄ ). Examples are polyalkylene terephthalates, for example based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethylcyclohexane, preferably polybutylene terephthalate (PBT), polypropylene terephthalate (PPT) and polyethylene terephthalate (PET) , and polyalkylene naphthalates such as polyethylene naphthalate.

Further polymers (t ₅ ) which are suitable as matrix polymers and can be used in addition to or instead of the components (t ₁ ), (t ₂ ), (t ₃ ) and / or (t ₄ ) are polyoxyalkylenes, for example polyoxymethylene.

Other suitable matrix polymers which can be used in addition to or instead of the components (t ₁ ), (t ₂ ), (t ₃ ), (t ₄ ) and / or (t ₅ ) are polycarbonates (t ₆ ). Suitable polycarbonates are known to the person skilled in the art or obtainable by processes known to the person skilled in the art. Preference is given to using polycarbonates based on diphenyl carbonate and bisphenols. Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, which is usually referred to as bisphenol A, as in the following.

Instead of of bisphenol A can also other aromatic dihydroxy compounds are used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane, 4,4-Dihydroxydiphenyl or Dihydroxydiphenylcycloalkane, preferred Dihydroxydiphenylcyclohexane or dihydroxycyclopentane, especially preferably 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and Mixtures of the aforementioned dihydroxy compounds.

Particularly preferred polycarbonates (t ₆ ) are those based on bisphenol A or bisphenol A together with up to 80 mol% of the abovementioned aromatic dihydroxy compounds.

It can furthermore, copolycarbonates are used; of special interest are copolycarbonates based on bisphenol A and di (3,5-dimethyldihydroxyphenyl) sulfone, characterized by a high heat resistance distinguished.

Furthermore, as components (t ₁ ) to (t ₆ ) or in addition to the components (t ₁ ) to (t ₆ ), polyarylene sulfides, in particular polyphenylene sulfide, are suitable as components (t ₁ ).

Furthermore can the molding materials T as further component additives. In a preferred embodiment contain the thermoplastic molding compositions T 0 to 60 wt .-%, preferably 0 to 40 wt .-%, particularly preferably 0 to 30 wt .-% fiber or particulate fillers or mixtures thereof (t,), in each case based on the total amount the molding material T.

reinforcing agents such as carbon fibers and glass fibers, if used are used, generally in amounts of 5 to 50 wt .-%, based on the total mass of the molding material T.

suitable Glass fibers can be made of E, A or C glass and are preferred with a sizing and a bonding agent. Their diameter is generally between 6 and 20 microns. It can both Endowed fibers (Rowings) as well as chopped glass fibers (Stable) with a length of 1 to 10 μm, preferably 3 to 6 microns be used.

Furthermore, fillers or reinforcing agents such as glass beads, mineral fibers, whiskers, alumina fibers, mica, quartz powder, CaCO ₃ and wollastonite may be added.

In addition, metal flakes, For example, aluminum flakes, metal powder, metal fiber, metal coated fillers, for example, nickel-coated glass fibers, as well as other additives, shield the electromagnetic waves, the molding compounds T admixed become. Furthermore, can the molding compounds with additional Carbon fibers, soot, in particular conductivity black, or nickel-coated C fibers are mixed.

The molding compositions T can also contain further additives (t ₈ ). Examples which may be mentioned are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve the thermal stability, to increase the light stability, to indicate the resistance to hydrolysis and chemical resistance, means against the heat decomposition and in particular lubricants or lubricants used for the production Of moldings or moldings or films are useful. The metering in of these further additives can be carried out at any stage in the production process of the molding compositions T, but preferably at an early stage, in order to take advantage of the stabilization effects (or other special effects) of the particular additive at an early stage.

Suitable stabilizers are, for example, hindered phenols, but also vitamin E or analogously constructed compounds such as butylated condensation products of p-cresol and dicyclopentadiene. Also HALS stabilizers (hindered amine light stabilizers), benzophenones, resorcinols, salicylates, benzotriazoles. Other suitable compounds are, for example, thiocarboxylic acid esters. Preference is given to C ₆ - to C ₂₀ -fatty acid esters of thiopropionic acid, particularly preferably stearyl esters and lauryl esters. Very particular preference is given to dilauryl thiodipropionate (dilauryl thiodipropionate), thistipropionic distearyl ester (distearyl thiodipropionate) or mixtures thereof. Further additives are, for example, HALS absorbers, such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacad or UV absorbers such as 2-H-benzotriazol-2-yl) (4-methylphenol). Such additives are usually used in amounts of up to 2 wt .-% (based on the total mixture T).

suitable Lubricants and mold release agents are cearic acids, cearyl alcohol, stearic acid esters, amide waxes (Bisstearylamid), polyolefin waxes or generally higher fatty acids whose Derivatives and corresponding fatty acid mixtures with 12 to 30 carbon atoms. The quantities of these additives are in the range of 0.05 to 5 wt .-%, based on the total molding composition T.

Also Silicone oils, oligomeric isobutylene or the like Substances are considered as additives. The usual quantities, if used, be from 0.001 to 5 wt .-%, based on the molding compositions T. pigments, Dyes, colorants such as ultramarine blue, phthalocyanines, titanium dioxide, Cadmium sulfides, derivatives of perylenetetracarboxylic acid are also useful.

processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used, if used used in amounts of 0.01 to 5 wt .-%, based on the total molding composition T.

• (t₀) ein erfindungsgemäßes kautschukartiges Propfcopolymerisat und
• (t₁) ein geeignetes Matrixpolymer, bevorzugt ausgewählt aus SAN (Styrol-Acrylnitril)-, AMSAN (α-Methylstyrol-Acrylnitril)-, Styrolmaleinimid-, SMSAN (Stynol-Maleinsäure(anhydrid))-acrylnitril-Polymerisate und SMSA (Styrol-Maleinsäureanhydrid); und/oder
• (t₂) teilkristalline, bevorzugt lineare, Polyamide wie Polyamid-6, Polyamid-6,6, Polyamid-4,6, Polyamid-6,12 oder teilkristalline Copolyamide; und/oder
• (t₃) Polyester wie Polymethylmethacrylat; und/oder
• (t₄) aromatisch-aliphatische Polyester, bevorzugt ausgewählt aus Polybutylenterephthalat, Polypropylenterephthalat, Polynaphthalenterephthalat und Polyethylenterephthalat; und/oder
• (t₅) Polyoxyalkylene, zum Beispiel Polyoxymethylen; und/oder
• (t₆) Polycarbonate; und/oder
• (t₇) Polyarylensulfide, insbesondere Polyphenylensulfid; und
• (t₈) gegebenenfalls faser- oder teilchenförmige Füllstoffe oder deren Mischungen; und
• (t₉) gegebenenfalls weitere Zusatzstoffe.

Another object of the present application are thus thermoplastic molding compositions containing T

• (t ₀ ) a rubbery graft copolymer according to the invention and
• (t ₁ ) a suitable matrix polymer, preferably selected from SAN (styrene-acrylonitrile), AMSAN (α-methylstyrene-acrylonitrile), styrene maleimide, SMSAN (styrene-maleic acid (anhydride)) acrylonitrile polymers and SMSA (styrene-acrylonitrile) maleic anhydride); and or
• (t ₂ ) partially crystalline, preferably linear, polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 or partially crystalline copolyamides; and or
• (t ₃ ) polyesters such as polymethylmethacrylate; and or
• (t ₄ ) aromatic-aliphatic polyesters, preferably selected from polybutylene terephthalate, polypropylene terephthalate, polynaphthalene terephthalate and polyethylene terephthalate; and or
• (t ₅ ) polyoxyalkylenes, for example polyoxymethylene; and or
• (t ₆ ) polycarbonates; and or
• (t ₇ ) polyarylene sulfides, especially polyphenylene sulfide; and
• (t ₈ ) optionally fibrous or particulate fillers or mixtures thereof; and
• (t ₉ ) optionally further additives.

Preferred embodiments and amounts of the components (t ₀ ) to (t ₉ ) are already mentioned above.

The preparation of the thermoplastic molding compositions T takes place by mixing the components mentioned. A further subject of the present application is therefore a process for the preparation of the thermoplastic molding compositions T according to the invention, wherein the components (t ₀ ) and (t ₁ ) and / or (t ₂ ) and / or (t ₃ ) and / or (t ₄ ) and / or (t ₅ ) and / or (t ₆ ) and / or (t ₇ ) and optionally (t ₈ ) and optionally (t ₉ ) are mixed together.

The The dispersion of the graft polymer P obtained can be either directly mixed with the other components of the thermoplastic molding composition T. be, or it can be worked up beforehand. The latter approach is preferred.

The Workup of the dispersion of the graft polymer P takes place in in a known manner. Üblicherwise will be first the graft polymer P precipitated from the dispersion, for example by precipitation acting salt solutions (such as calcium chloride, magnesium sulfate, alum) or acids (such as Acetic acid, hydrochloric acid or sulfuric acid) or by freezing (freeze coagulation) - The aqueous phase can be in the usual Such as by sieving, filtering, decanting or Zen centrifuging, be separated. You get by this prior separation of the dispersion water moist water Graft polymers P having a residual water content of up to 60% by weight, based on P, wherein the residual water, for example, both externally on the graft polymer attach as well as can be included in it.

The If necessary, graft polymer can be prepared in a known manner be further dried, for example by hot air or by means of a power dryer. It is also possible to spray the dispersion by spray drying work up. The graft polymers P are with the other Components of the thermoplastic molding composition T in a mixing device mixed. As mixing devices, those are used which are the Are known in the art. You can, for example, through the components co-extruding, kneading or rolling mixed, wherein if necessary, the components have previously been removed from the polymer during the polymerization obtained solution or from the aqueous Dispersion have been isolated.

in the Case of mixing one or more components in the form of a aqueous Dispersion or an aqueous or non-aqueous Solution, is the water or the solvent over a Degassing unit from the mixing device, preferably an extruder, away.

When Mixing device for the implementation the method according to the invention are, for example, discontinuous, heated internal kneaders with or without stamp, continuously working kneaders such as Example continuous internal kneader, screw kneader with axial oscillating snails, Banbury kneaders, Extru's continue as well Roll mills, Mills with heated rolls and calenders, to name a few.

Prefers is used as a mixing device, an extruder. For melt extrusion For example, single or twin-screw extruders are particularly suitable. A twin-screw extruder is preferred.

The Mixing of the graft polymers P with the other ingredients The molding compounds T can after all manner known to all Methods are done. Preferably, the mixing of the components takes place by co-extruding, kneading or rolling the components, for example, at temperatures in the range of 180 to 400 ° C, wherein the components, if necessary, previously in the polymerization contained solution or aqueous Dispersion have been isolated.

The in water Dispersion obtained products of the graft polymerization (graft polymers P) can for example, only partially dehydrated and as moist Particles (crumbs) be mixed with the matrix polymers, then during the Mixing the whole Drying of the graft polymers takes place. Suitable methods were mentioned above.

The Molding compounds can to shaped bodies, as plates or semi-finished, processed films, fibers or foams become.

One Another object of the present application is therefore the use the thermoplastic molding compositions T for the production of moldings, films, Fibers or foams.

These shaped bodies, films, fibers or foams can be prepared by methods known to the person skilled in the art the thermoplastic processing of the molding compositions T are produced. In particular, the production by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding, take place.

The Dispersions containing the particulate Contain rubbers K, or the dispersions after grafting The rubbers K contain the graft polymers P, can also be used as such. You can, for example, as a binder, for example for Adhesives, in particular pressure-sensitive adhesives, paints, lacquers or Paper coatings are used. They can also be used as additives in construction chemicals, especially as an additive to cement or as Binders are used for the consolidation of fiber tiles. For the Uses mentioned may be dispersions according to the invention containing the particulate Rubbers K or graft polymers P with additives such as leveling agents, Thickeners, antioxidants, stabilizers, pigments or fillers or mixtures thereof.

With the method according to the invention Is it possible, the non-uniformity of agglomerated fractions in a particulate rubber to control.

• a1) mindestens eines hydrophoben Monomeren in einem ersten Schritt und
• a2) eines Monomerengemisches umfassend hydrophobe und hydrophile Monomere in einem weiteren Schritt

in Gegenwart eines Emulgators erhältlich ist, wobei man

• i) den Agglolatex A mit einer definierten Uneinheitlichkeit U_A durch Einsatz von einem Alkalisalz einer Säure, eines Sulfats oder eines Sulfonates mit einem aliphatischen Rest von 10 bis 20 Kohlenstoffatomen als Emulgator herstellt, und
• ii) mit einem in Emulsion vorliegenden teilchenförmigen Substratkautschuk S umsetzt.

A further subject of the present application is therefore a method for controlling the non-uniformity U _{F of} at least one agglomerated fraction F of a particulate agglomerated Agglomeration by means of Agglolatex A rubber K, the Agglolatex A itself being particulate and by emulsion polymerization

• a1) at least one hydrophobic monomer in a first step and
• a2) a monomer mixture comprising hydrophobic and hydrophilic monomers in a further step

in the presence of an emulsifier, wherein

• i) the Agglolatex A with a defined nonuniformity U _A by using an alkali metal salt of an acid, a sulfate or a sulfonate having an aliphatic radical of 10 to 20 carbon atoms as emulsifier, and
• ii) with a particulate substrate rubber S present in emulsion.

preferred hydrophobic and hydrophilic monomers as well as preferred emulsifiers for the preparation of Agglolatex A and suitable reaction conditions for the preparation of Agglolatex A and preferred Agglolatices A. already mentioned above. Suitable and preferably used particulate Substrate rubbers S are also already mentioned above.

With Help of the method according to the invention Is it possible, Graft polymers P produce a uniform distribution of the grafted Monomers on the particulate Having rubber K. Due to the uniform distribution becomes a get uniform graft shell, their compatibility in matrix polymers Graft polymers of the prior art is improved. Thereby can thermoplastic molding compositions prepared with improved properties become.

The explain the following examples the invention additionally.

Examples

1. butadiene rubber S ₁

The preparation of the butadiene rubbers S ₁₁ to S ₁₆ is carried out by emulsion polymerization by the feed process. The comonomer used is 7% by weight of styrene.

The preparation of the butadiene rubber S _{12 is} exemplified below. The butadiene rubbers S ₁₁ , S ₁₃ to S ₁₆ are prepared in an analogous manner.

The emulsion polymerization is carried out in a 150 l reactor at a temperature of 67 ° C. 43120 g of the monomer mixture (butadiene and styrene) are polymerized at 67 ° C. in the presence of 431.2 g of tert-dodecylmercaptan (TDM), 311 g of potassium stearate, 82 g of potassium persulfate, 147 g of sodium bicarbonate and 58,400 g of water, a polybutadiene Latex is obtained. The monomers are added to the reactor in the order listed below:
First, the addition of styrene in an amount of 7 wt .-%, based on the total amount of monomer, within 20 minutes. Following the styrene addition, the addition of a first portion of the butadiene in an amount of 7 wt .-%, based on the total amount of monomer, within 25 minutes. The remaining portion of the butadiene, which corresponds to 86% by weight, based on the total amount of monomer, is then added within 8.5 hours. TDM is added at the beginning of the reaction at once. The conversion is ≥95%, the swelling index of the obtained product is 21%, the gel content is 83%, the D50 value (determined by HDF) is 93 nm, and the inconsistency is 0.35.

• 1) Quellungsindex
• 2) Gelgehalt
• 3) Ermittelt mittels HDF
• 4) Uneinheitlichkeit, (D90-D10)/D50

The butadiene rubbers S ₁₁ to S ₁₆ have the following properties: TABLE 1

• 1) swelling index
• 2) Gel content
• 3) Determined by HDF
• 4) Nonuniformity, (D90-D10) / D50

The D10, D50 and D90 values are determined by hydrodynamic fractionation (HDF) determined.

Of the Gel content and swelling index are determined by adding a sample of the dried rubber in toluene and after a Day of the unresolved Rubber is separated from the toluene by centrifugation. Of the swollen rubber is weighed, dried and weighed once more.

The swelling index is defined as follows:

The gel content is defined as follows:
Gel content = proportion of the rubber which is not soluble in toluene

2. Polybutylacrylatdispersionen S ₂

Three polyacrylate dispersions (S ₂₁ , S ₂₂ and S ₂₃ ) are prepared by emulsion polymerization by the feed process. For this purpose, the following starting materials are presented: 1289.06 g completely desalinated water 29.38 g 40% strength by weight solution of emulsifier K30 in water (= 11.75 g solid); [Emulsifier K30 has the following formula: C ₁₂ -C ₁₈ -SO ₃ ^- K +] 4.39 g sodium bicarbonate 3.47 g Potassium persulfate.

The water and emulsifier are heated to 65 ° C and sodium bicarbonate and potassium persulfate are added at 65 ° C. After 3 minutes, the feed 1 is started, which is added in 3 hours. Feed 1 has the following composition: 1132.47 g butyl acrylate 23.11 g DCPA (Dihydrocyclopentadienylacrylat).

To When the reaction has started, the temperature is reduced to 60.degree. After the end of feed is polymerized at 60 ° C for 1 hour. The stirrer speed is while the preparation of the polybutyl acrylate dispersion 140 rpm.

It a polybutyl acrylate dispersion is obtained which has a solids content of 47% by weight.

By using the emulsifier K30, the polybutyl acrylate dispersion S _{21 is} obtained. In an analogous manner, the Poylbutylacrylat dispersions S ₂₂ and S ₂₃ are obtained, wherein for the preparation of the polyacrylate dispersion S ₂₂ instead of the emulsifier K30 as an emulsifier, the Na salt of a C ₁₀ fatty acid is used and for the preparation of the polybutyl acrylate dispersion S _23rd instead of the emulsifier K30, the Na salt of a C ₁₆ fatty acid. The emulsifier is used in each case in an amount of about 1 wt .-%, based on the amount of the template.

• 1) Ermittelt mittels HDF
• 2) Uneinheitlichkeit, (D90-D10)/D50

The polybutyl acrylate dispersions have the following properties: TABLE 2

• 1) Determined by HDF
• 2) nonuniformity, (D90-D10) / D50

The D10, D50 and D90 values are determined by hydrodynamic fractionation (HDF) determined.

3. Production of Agglolatex A

Agglolatex A ₁ (comparative example):

The following initial charge is placed in a 10 l four-necked flask with paddle stirrer, metering pumps and reflux condenser and N ₂ purge: 771.14 g completely desalinated water 39.24 g 40 wt .-% solution of the emulsifier K30 in water 166.37 g ethyl acrylate 3.14 g Potassium persulfate.

The components of the template are heated to 80 ° C and stirred for 15 minutes (stirrer speed 160-180 rpm). Subsequently, the feeds 1, 2 and 3 are added dropwise in parallel within 2.5 hours at 80 to 81 ° C. Feeds 1, 2 and 3 have the following compositions: Feed 1: 1340.38 g of ethyl acrylate Feed 2: 62.78 g of methacrylamide 39.24 g of 40% strength by weight solution of the emulsifier K30 in water 1324.57 g of demineralized water. Feed 3: 3.14 g of potassium persulfate 250.00 g of demineralized water.

To Inlet end is stirred for 2 hours at 80 ° C.

• 1) C₁₂-C₁₈-SO₃ ^–K⁺

Analogous to the above-mentioned preparation of Agglolatex A ₁ Agglolatices A ₂ to A ₁₅ are prepared. The only difference to the preparation of Agglolatex A ₁ is the use of different emulsifiers in the template and in feed 2 or different amounts of emulsifier in the template. In the following Table 3 is in each case the type of emulsifier and the amount of emulsifier used in the template or in the feed 2 in wt .-%, each based on the total amount of monomers for the agglomerates A ₂ to A ₁₅ (inventive Examples): Table 3

• 1) C ₁₂ -C ₁₈ -SO ₃ ^- K ⁺

• 1) Uneinheitlichkeit U
• 2) Feststoffgehalt FG in Gew.-%

The Agglolatices A ₂ to A ₁₄ have the following properties listed in Table 4 Table 4

• 1) inconsistency U
• 2) Solids content FG in% by weight

4. Agglomeration of the Polybutadiene Dispersion S ₁

The agglomeration is carried out in a 10 l four-necked flask equipped with stirrer and thermometer. The respective polybutadiene dispersion S ₁ is diluted with water to a solids content of 40 wt .-% and heated to 68 ° C. The agglomerate (diluted to 10% solids by weight) is added continuously over 30 minutes. About 15 minutes after completion of the addition of Agglolatex, water and potassium stearate are added.

The Properties of the obtained particulate rubbers K are in shown in the following Tables 5 to 9.

It can be seen from Table 5 that the non-uniformity of the agglomerated fraction U _{F of} the agglomerated rubber can be controlled by the choice of the nonuniformity U _{A of} the agglomeratex. It is un essentially, whether the agglomerated rubber K has a bimodal particle size distribution, wherein the maximum particle size of the fraction of non-agglomerated particles (M1) is smaller than the minimum particle size of the fraction F of agglomerated particles (M2) or a broad particle size distribution (gradual transition) maximum particle size of fraction of non-agglomerated particles is equal to the minimum particle size of fraction F of agglomerated particles (M2).

It is clear from Table 6 that when the same polybutadiene is used as the substrate rubber, the D50 value of the agglomerated fraction of the agglomerated rubber K (M2) is proportional to the D50 value of Agglolatex. The ratio between the D50 value of the agglomerated fraction F of the particulate rubber K and the D50 value of the agglomerate A is approximately between 4 and 5.

From Table 7, it can be seen that the D50 value of the agglomerated fraction F of the pond-shaped rubber K when using the same Agglolatex to the D50 value of the used as a substrate rubber poly butadiene is proportional. The ratio of the D50 value of the agglomerated fraction of the particulate rubber K to the D50 value of the polybutadiene used as the substrate rubber is in the range of 5.5 to 6.5.

It is apparent from Table 8 that trimodal particle size distributions of the particulate rubber K are obtained with a mixture of agglomerates having different particle sizes a fraction of non-agglomerated particles and two fractions, F1 and F2, of agglomerated particles. The addition mode of Agglolatices 1 and 2 has no influence on the D50 value of the agglomerated fractions and on the yield of the agglomerated fractions. However, it can be seen from Table 8, an influence of the addition amount of Agglolatex on the yield and the D50 value of the agglomerated fractions.

From the first two examples in Table 9 it can be seen that the yield of agglomerated particles is increased by the addition of an electrolyte. At the same time, the D50 value of the agglomerated frak decreases tion with addition of an electrolyte significantly.

Out The third and fourth examples in Table 9 show that the type of emulsifier used to prepare the Agglolatex has an influence on the yield of agglomerated particles.

5th agglomeration the polybutyl acrylate dispersions

• 5.1 100 ml of the corresponding polybutyl acrylate dispersion are placed in a 250 ml beaker and 50 rpm by means of a glass stirrer touched. The corresponding Agglolatex (2.0 wt .-% solids, based on the amount of polybutyl acrylate in solid form) is at once added to the polybutyl acrylate dispersion. After 5 minutes will be stirring finished, and the agglomerated dispersion is placed in a glass bottle filled. The dispersions are further used as prepared, i. With a solids content of about 46% regarding the butyl acrylate and about 39% to 40% regarding the Agglolatex. The properties the obtained particulate Rubbers K are shown in Table 10.

• 5.2 Die gemäß Beispiel 2 erhaltene Polybutylacrylat-Dispersion S₂₁ wird unter Rühren (50 Upm) schnell mit 87,72 g (3 Gew.-%) des Agglolatex A₉ (Beispiel 3) versetzt. Es wird 15 Minuten bei 50 Upm nachgerührt. Anschließend werden – vor der Pfropfung der erhaltenen Polybutylacrylat-Dispersion – 28,9 g des Emulgators K30 (40 gew.-%ig) in einem Guss zugegeben. In Tabelle 11 sind die Daten agglomerierter Kautschuke auf Basis der Polybutylacrylat-Dispersion S₂₁, die mit verschiedenen Mengen des Agglolatex A₉ bzw. mit dem Agglolatex A₁ agglomeriert wurde, angegeben.

After agglomeration, rubbers with bimodal particle size distribution can be obtained (see K ₂₁ , K ₂₂ , K ₂₃ , K ₂₄ , K ₂₅ , K ₂₆ , K ₂₇ ). From Table 10 it can be seen that the inconsistency of the agglomerated Fraction O _{F of} the agglomerated rubber is controlled by the choice of the nonuniformity U _A of Agglolatex. When using the Agglolatex A ₁ , which is prepared in the presence of the emulsifier K30, the nonuniformity U _{F of} the agglomerated fraction of the agglomerated rubber is significantly greater than when using the Agglolatex A ₂ , which in the presence of an alkali metal salt of an acid with a defined chain length (C10 ) is prepared as an emulsifier. Furthermore, the difference between the maximum particle size of the fraction of non-agglomerated particles and the minimum particle size of the fraction of agglomerated particles is particularly large when agglomeration is carried out using an agglomerate x (A ₂ ) having a small nonuniformity.

• 5.2 The polybutyl acrylate dispersion S ₂₁ obtained according to Example 2 is mixed rapidly with 87.72 g (3% by weight) of Agglolatex A ₉ (Example 3) with stirring (50 rpm). It is stirred for 15 minutes at 50 rpm. Subsequently, before the grafting of the polybutyl acrylate dispersion obtained, 28.9 g of the emulsifier K30 (40% strength by weight) are added in one pour. Table 11 shows the data for agglomerated rubbers based on the polybutyl acrylate dispersion S ₂₁ which has been agglomerated with various amounts of agglomerate A ₉ and agglolatex A ₁ , respectively.

6. agglomeration and Grafting of the agglomerated polybutadiene rubber dispersions

6.9 Agglomeration

For agglomeration, 5265 g of the polybutadiene rubber dispersion S _{12 are} diluted to a total solids content of 40% by weight and agglomerated at 68 ° C. by addition of an Agglolatex (see Table 12) (partial agglomeration). The agglomerate is added in the form of a dispersion in an amount of 526.5 g (solids content: 10% by weight).

The Agglolatex used is composed of 96 wt .-% ethyl acrylate and 4 wt .-% methacrylamide. The agglomerated rubbers K ₁₇ , K ₁₈ , K ₁₉ , K ₁₁₀ and K ₁₁₁ , which have the properties listed in Table 12, are obtained.

6.2 grafting

in the After agglomeration, add 20 g of emulsifier (K-stearate) and 3 g of initiator (K-persulfate) to the agglomerated polybutadiene rubber dispersion given. It is added so much water that the total solids content the dispersion after completion of the polymerization a theoretical Value of 40 wt .-% has. Subsequently, 74.7 g of acrylonitrile and 298.8 g of styrene was added. Following that will be 224.1 g Acrylonitrile and 896.4 g of styrene over added a period of 190 minutes, with the temperature after half the time to 77 ° C elevated becomes. After complete Adding the monomers again 3 g of initiator (K-persulfate) is added and the polymerization is continued for 60 minutes.

The The graft polymer dispersion obtained has a bimodal particle size distribution on.

0.1% by weight of silicone oil, 0.2% by weight of stabilizer, in each case based on the total solids content, are added to the dispersion obtained. The mixture is cooled and coagulated at about 60 ° C in an aqueous 0.5% by weight MgSO ₄ solution, followed by an aging step for 10 minutes at 100 ° C. The mixture is then cooled, centrifuged and washed with water. A graft polymer having a moisture content of about 30% by weight is obtained.

After the grafting step, the graft rubbers P ₁₇ , P ₁₈ , P ₁₉ , P ₁₁₀ and P ₁₁₁ are obtained.

7. Grafting of the agglomerated Polybutyl acrylate dispersions

The dispersion of the agglomerated polybutyl acrylate rubber K ₂₁₀ (Example 5.2) is mixed with 1817.24 g of fully desalted water heated to 60 ° C. For grafting the Rührgeschwindigleit is raised to 160 rpm. At 60 ° C, potassium persulfate (4.66 g) is added. Subsequently, the feeds 2 and 3 are added over a period of 2.5 hours at 60 ° C: Feed 2: 518.0 g styrene 172.7 g acrylonitrile Feed 3: 28.9 g 40 wt .-% solution of the emulsifier K30 in water 300 g completely desalinated water

After the end of feed is polymerized for 60 minutes, the stirrer speed is reduced to 100 rpm. A dispersion of the graft polymer P _{210 is} obtained.

In an analogous manner, by grafting the agglomerated rubbers K ₂₈ , K ₂₉ , K ₂₁₁ dispersions of the graft polymers P ₂₈ , P ₂₉ and P ₂₁₁ are obtained.

8. Thermoplastic molding compounds containing the example according to 6 prepared graft polymers

The residual water-containing graft rubbers P ₁₇ , P ₁₈ , P ₁₉ , P ₁₁₀ and P ₁₁₁ produced according to Example 6 are metered into a Werner and Pfleiderer ZSK30 extruder, whose two screw conveyors are provided in the front part with pressure-building stowage elements. A considerable part of the residual water is pressed out mechanically in this way and leaves the extruder in liquid form through drainage openings. Poly (styrene-co-acrylonitrile) (PSAN) having an acrylonitrile content of 24% by weight and a viscosity number of 64 is fed to the extruder downstream of the stagnation zones and intimately mixed with the dewatered component P. The remaining residual water is removed via degassing in the back of the extruder as a vapor. The extruder is operated at 250 ° C and 250 rpm, with a throughput of 10 kg / h. The molding compound is extruded and the molten polymer mixture is subjected to a rapid cooling, in which it is introduced into a water bath of 25 ° C. The solidified molding material is granulated. The thermoplastic molding materials T ₁₇ , T ₁₈ , T ₁₉ , T ₁₁₀ and T ₁₁₁ are obtained.

The viscosity is in accordance with DIN 53726 on a 0.5 wt .-% solution of the polymer in dimethylformamide.

Table 12 shows some properties of the thermoplastic molding materials T ₁₇ , T ₁₈ , T ₁₉ , T ₁₁₀ and T ₁₁₁ :

9. Thermoplastic molding compounds containing the example according to 7 prepared graft polymers

1 part by weight of the dispersion of the graft polymer P ₂₁₀ is coagulated with 2 parts by weight of 0.8 wt.% Aqueous MgSO ₄ solution at 23 ° C. Subsequently, the coagulated dispersion is sintered at 95 ° C and centrifuged. The coagulated rubber (water content about 40% by weight) is then mixed with PSAN (poly (styrene-co-acrylonitrile)) (acrylonitrile content: 33% by weight) having a viscosity number of 80 in a melt extruder at 260 ° C. The water is removed by means of fans along the extruder. The polymer melt is extruded as a strand, cooled and processed into pellets. The resulting thermoplastic molding materials T ₂₁₀ (93/34/5) contain 29 parts by weight of the graft polymer P ₂₁₀ and 71 parts by weight of PSAN.

The viscosity is in accordance with DIN 53726 on a 0.5% by weight solution of the polymer in dimethylformamide.

In an analogous manner, thermoplastic molding compositions T ₂₈ , T ₂₉ and T ₂₁₁ containing in each case 29 parts by weight of one of the graft polymers P ₂₈ , P ₂₉ and P ₂₁₁ and 71 parts by weight of PSAN are obtained.

10. Dyeability the thermoplastic molding compositions according to Example 9

• 1 hervorragende Anfärbbarkeit
• 2 gute Anfärbbarkeit
• 3 mäßige Anfärbbarkeit
• 4 unzureichende Anfärbbarkeit

The thermoplastic molding materials T ₂₈ , T ₂₉ , T ₂₁₀ and T ₂₁₁ are each extruded a second time with the addition of 0.5 parts by weight of Helliogen blue type K7090 from BASF AG. The dyeability of samples obtained by injection molding of 5 cm × 5 cm × 2 mm plates is evaluated by visual comparison of color depth. The following scale is used for the assessment:

• 1 excellent dyeability
• 2 good dyeability
• 3 moderate dyeability
• 4 insufficient dyeability

The results are shown in Table 13: Table 13

The result shows that the thermoplastic molding compositions whose agglomerated fraction of the rubber K used as a base has a narrow particle size distribution (T ₂₈ , T ₂₉ , T ₂₁₀ ) have a significantly better dyeability than thermoplastic molding compositions whose agglomerated fraction of the rubber used as the base K has a broad particle size distribution (T ₂₁₁ ).

Claims (26)

A process for the preparation of a particulate rubber K comprising at least one fraction F of agglomerated particles, wherein the at least one fraction F has a defined nonuniformity U _F , by agglomeration of a particulate substrate rubber S present in an emulsion by means of at least one particulate agglomerate A, the agglomerate A being a defined nonuniformity U _A of ≤ 0.65. A method according to claim 1, characterized in that the ratio of the nonuniformity U _{F of} the at least one fraction F to the nonuniformity U _{A of} the at least one particulate Agglolatex A is 0.75 to 1.50. A method according to claim 1 or 2, characterized in that the nonuniformity U _{A of} the at least one particulate Agglolatex ≤ 0.5, more preferably ≤ 0.45. Method according to one of claims 1 to 3, characterized in that the Agglolatex A a d ₅₀ value of 60 to 180 nm, preferably 65 to 160 nm, particularly preferably 65 to 150 nm. Method according to one of claims 1 to 4, characterized that the particulate Agglolatex A is a dispersion of an acrylic ester polymer from 90 to 99.9 wt .-% of at least one alkyl ester as hydrophobic Monomer and 0.1 to 10% by weight of at least one hydrophilic monomer, the sum total of hydrophobic and hydrophilic monomers 100 wt .-% results. Method according to one of claims 1 to 4, characterized that the particulate Agglolatex A is a dispersion of an acrylic ester polymer from 45 to 99 wt .-% of at least one alkyl ester as hydrophobic Monomer and 0.1 to 25% by weight of at least one hydrophilic monomer, 0 to 40 wt .-% of other monomers, wherein the total of hydrophobic and hydrophilic monomers gives 100% by weight. Method according to claim 5 or 6, characterized the acrylic esters are acrylic esters of alcohols having 1 to 4 carbon atoms with ethyl acrylate being preferred, and at least one hydrophilic monomer selected is selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, Methacrylamide, N-methylolmethacrylamide and N-vinylpyrrolidone, wherein Methacrylamide, acrylic acid and methacrylic acid are preferred are. Process according to any one of Claims 5 to 7, characterized in that an agglomerate A containing a particulate copolymer constituted by (a ₁₁ ) contains from 1 to 80% by weight relative to the total of the rubbery copolymer, ethyl acrylate as the core, and (a ₁₂ ) 20 to 99 wt .-%, based on the total amount of the particulate copolymer, of a core grafted on the core composed of (a ₁₂₁ ) 75 to 99 wt .-%, preferably 92 to 97 wt .-%, particularly preferably 93 to 97 wt .-%, based on the total amount of the shell-forming monomers, ethyl acrylate and (a ₁₂₂ ) 1 to 25 wt .-%, preferably 3 to 8 wt .-%, particularly preferably 3 to 7 wt .-%, based to the total amount of the shell-forming monomers, methacrylamide, acrylic acid and / or methacrylic acid; is used. Method according to one of claims 1 to 8, characterized that the particulate Agglolatex A by emulsion polymerization (i) at least one hydrophobic monomers in a first step and (ii) one Monomeric mixture comprising hydrophobic and hydrophilic monomers in a second step wherein steps (i) and (ii) in Presence of an emulsifier done. Method according to one of claims 1 to 9, characterized that the particulate Agglolatex A to the substrate rubber present in an emulsion S is given. Method according to one of claims 1 to 10, characterized in that a particulate rubber having a bimodal particle size distribution comprising unagglomerated rubber particles and a fraction F agglomerated rubber particles with a defined non-uniformity U _F by agglomeration by means of a particulate Agglolatex A with defined nonuniformity U _A of ≤ 0.65 is produced. Method according to one of claims 1 to 10, characterized in that a particulate rubber having a trimodal particle size distribution comprising non-agglomerated rubber particles and a fraction F1 agglomerated rubber particles with defined non-uniformity U _F1 and another fraction F2 agglomerated rubber particles with defined non-uniformity U _F2 by agglomeration two particulate Agglolatices A1 with defined non-uniformity U _A1 and A2 with defined non-uniformity U _A2 , wherein the Ag glolatices A1 and A2 have different average particle sizes TG _A1 and TG _A2 is prepared. Method according to one of claims 1 to 9, characterized that an electrolyte is selected from Lithium hydroxide, sodium hydroxide and potassium hydroxide, preferably before Agglomeration of the particulate substrate rubber present in an emulsion S, is added. Method according to one of claims 1 to 13, characterized in that the substrate rubber S has a d ₅₀ value in the range of 50 to 200 nm, preferably 60 to 150 nm, particularly preferably 70 to 120 nm having. Method according to one of claims 1 to 14, characterized in that the substrate rubber S has a glass transition temperature (T _g ) of less than -10 ° C and is composed of (s ₁ ) an at least partially crosslinked Acrylesterpolymerisats formed from (s ₁₁ ) 50 bis 99.99 wt .-%, based on (s ₁ ), of at least one alkyl acrylate having 1 to 10 carbon atoms in the alkyl radical, (s ₁₂ ) 0.01 to 5 wt .-%, based on (s ₁ ), at least one polyfunctional , crosslinking monomers, and (s ₁₃ ) 0 to 49.9 wt .-%, based on (s ₁ ), at least one further copolymerizable with (s ₁₁ ) monomers, preferably selected from the group consisting of vinyl alkyl ethers having 1 to 8 Carbon atoms in the alkyl radical, butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, acrylic acid, methacrylic acid, itaconic acid and maleic anhydride and (s ₁₄ ) 0 to 5 wt .-% groups, of the optionally used in the preparation of the substrate rubber S th controllers, initiators and / or emulsifier come; and / or (s ₂ ) a diene polymer composed of (s ₂₁ ) 60 to 100% by weight, based on (s ₂ ), of at least one diene and (s ₂₂ ) 0 to 40% by weight, based on ( s ₂ ), further polymerizable monomers, preferably selected from the group consisting of alkyl acrylates having 1 to 10 carbon atoms in the alkyl radical, vinyl alkyl ethers having 1 to 8 carbon atoms in the alkyl radical, butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile and methyl methacrylate, acrylic acid, methacrylic acid, itaconic acid and Maleic anhydride, and (s ₂₃ ) from 0 to 5% by weight of groups derived from any regulators, initiators and / or emulsifier systems used in the preparation of the substrate rubber S. A method according to claim 15, characterized in that the substrate rubber S is a diene polymer (s ₂ ), preferably a Butadienpolymerisat is. particulate Rubber K preparable by a process according to one of claims 1 to 16th Agglolatex A having a defined non-uniformity U _A preparable by emulsion polymerization a1) of one or more hydrophobic monomers in a first step and a2) a monomer mixture comprising hydrophobic and hydrophilic monomers in a further step in the presence of an alkali salt of an acid, a sulfate or sulfonate with an aliphatic Balance of 10 to 20 carbon atoms as emulsifier. Use of an agglomerate A according to claim 18 for agglomerating a particulate substrate rubber S present in emulsion to produce a particulate rubber K comprising at least one fraction F of agglomerated particles, wherein the at least one fraction F has a defined nonuniformity U _F , preferably a nonuniformity O _F of <1 , having. Rubbery graft copolymer P composed of (p ₁ ) 30 to 99% by weight, preferably 30 to 90% by weight, based on P, of a particulate rubber K according to Claim 15 or prepared by a process according to one of Claims 1 to 16, as grafting basis; (p ₂ ) 1 to 70% by weight, preferably 10 to 70% by weight, based on P, of a graft support grafted onto the graft base with a T _g of more than 50 ° C., preferably composed of (α) (p ₂₁ ) 50 to 100% by weight, based on (p ₂ ), of at least one vinylaromatic monomer, (p ₂₂ ) 0 to 50% by weight, based on (p ₂ ), of at least one polar, copolymerizable comonomer, preferably selected from the group consisting of acrylonitrile, methacrylonitrile, esters of (meth) acrylic acid having 1 to 4 carbon atoms in the alkyl radical, maleic anhydride and its imides, (meth) acrylamide and vinyl alkyl ethers having 1 to 8 carbon atoms in the alkyl radical; (p ₂₃ ) 0 to 40 wt .-%, based on (p ₂ ), of one or more further monoethylenically unsaturated monomers, wherein the components (p ₂₁ ), (p ₂₂ ) and (p ₂₃ ) to 100 wt. %, or (β) (p ₂₄ ) 50 to 100 wt .-%, based on (p ₂ ), (p ₂₅ ) 0 to 50 wt .-%, based on (p ₂ ), of at least one further copolymerizable monomer , before added to styrene, (meth) acrylonitrile or esters of acrylic acid, wherein the components (p ₂₄ ) and (p ₂₅ ) to 100 wt .-% complement. Use of a particulate rubber according to claim 17 as grafting base for the preparation of a rubbery graft copolymer. Thermoplastic molding composition T comprising (t ₀ ) a rubbery graft copolymer according to claim 20, and (t ₁ ) a suitable matrix polymer, preferably selected from polymers prepared from SAN (styrene-acrylonitrile), AMSAN (α-methylstyrene-acrylonitrile), styrene maleimide, SMSAN (Styrene-maleic acid (anhydride)) - acrylonitrile and SMSA (styrene-maleic anhydride); and / or (t ₂ ) partially crystalline, preferably linear, polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 or partially crystalline copolyamides; and / or (t ₃ ) polyesters such as polymethylmethacrylate; and / or (t ₄ ) aromatic-aliphatic polyesters, preferably selected from polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polyethylene terephthalate; and / or (t ₅ ) polyoxyalkylenes, for example polyoxymethylene; and / or (t ₆ ) polycarbonates; and / or (t ₇ ) polyarylene sulfides, in particular polyphenylene sulfide; and (t ₈ ) optionally fibrous or particulate fillers or mixtures thereof; and (t ₉ ) optionally further additives. A process for preparing thermoplastic molding compositions according to claim 22, characterized in that the components (t ₀ ) and (t ₁ ) and / or (t ₂ ) and / or (t ₃ ) and / or (t ₄ ) and / or (t ₅ ) and / or (t ₆ ) and / or (t ₇ ) and optionally (t ₈ ) and optionally (t ₉ ) are mixed together. Use of the thermoplastic molding compositions after Claim 22 for the production of films, moldings, fibers and foams. moldings available using the thermoplastic molding compositions according to claim 22nd Process for controlling the nonuniformity U _{F of} at least one agglomerated fraction of a particulate agglomerated Agglomeration by means of Agglolatex A rubber K, the Agglolatex A itself being particulate and by emulsion polymerization a1) at least one hydrophobic monomer in a first step and a2) a monomer mixture comprising hydrophobic and hydrophilic monomers are obtainable in a further step in the presence of an emulsifier, characterized in that (i) the agglomerate A with a defined nonuniformity U _A by use of an alkali salt of an acid, a sulfate or a sulfonate having an aliphatic radical of 10 to 20 carbon atoms as emulsifier and (ii) reacting with a present in emulsion particulate substrate rubber S.