EP3161041A1 - Procédé d'isolation de copolymères greffés abs - Google Patents

Procédé d'isolation de copolymères greffés abs

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Publication number
EP3161041A1
EP3161041A1 EP15730750.5A EP15730750A EP3161041A1 EP 3161041 A1 EP3161041 A1 EP 3161041A1 EP 15730750 A EP15730750 A EP 15730750A EP 3161041 A1 EP3161041 A1 EP 3161041A1
Authority
EP
European Patent Office
Prior art keywords
weight
copolymer
graft
styrene
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15730750.5A
Other languages
German (de)
English (en)
Inventor
Roland Walker
Sabine Oepen
Gisbert Michels
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos Styrolution Group GmbH
Original Assignee
Ineos Styrolution Group GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ineos Styrolution Group GmbH filed Critical Ineos Styrolution Group GmbH
Publication of EP3161041A1 publication Critical patent/EP3161041A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
    • C08C1/04—Purifying; Deproteinising
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation

Definitions

  • the invention relates to a process for the preparation or isolation of ABS graft copolymers.
  • Natural rubbers are known to be capable of being coagulated by salt solutions. For this, the Rev. Gen. Cautchouc Indochine, Paris (1956, 33, 615-22 and 644-50) for an overview.
  • WO 00/049053 describes ABS graft copolymers which are precipitated with a 0.5% strength by weight MgSO 4 solution and for easier drying of the coagulated graft copolymers with aqueous solutions of salts, alcohols, acids or sugars in a concentration of 5 to 40 wt .-% are treated.
  • US 5,514,772 describes a process for the preparation of powdery polymers comprising two coagulation steps.
  • a surface-active sulfuric or sulfonic acid ester in combination with an acid in the second step an acid and / or a salt for coagulation are used.
  • Preference is given to the sole use of sulfuric acid.
  • the precipitants such as chlorides or sulfates usually used in the large-scale coagulation of graft copolymers from their emulsion or dispersion have the disadvantage that residual amounts either have to be removed with difficulty or remain in the product. This increases the cost of the manufacturing process or it must accept quality losses in the processed finished product.
  • the quality losses are usually attributable to the fact that when the graft copolymers are incorporated into a matrix, the precipitant residues interact with this matrix, resulting in discoloration, in particular yellow discoloration (high yellowness index), during the subsequent processing to the finished product.
  • surface defects in the finished product may, for example, be due to interactions between the precipitant residues and the materials used in the manufacture of the finished products.
  • the precipitant residues can also undergo side reactions, forming clusters and crystallites, which in turn affect the quality of the finished products.
  • the temperature resistance and / or the weathering stability may be impaired.
  • the residues of the precipitants can reduce the transparency, which is noticeable by increasing the so-called haze (turbidity value).
  • alkali metal and / or alkaline earth metal formates are used as precipitants for the precipitation of ABS graft copolymers.
  • Specimens of the graft copolymers were prepared with a SAN matrix. An improvement in yellowness, transparency and turbidity of the samples could be achieved.
  • the precipitation with alkali and / or alkaline earth metal formates has u. a. the disadvantage that such precipitants are too expensive for large-scale use.
  • An object of the present invention is to provide an alternative process for the isolation of ABS graft copolymers which is industrially applicable and overcomes the aforementioned disadvantages of the known processes, so that ABS graft copolymers are obtained in good yield.
  • the ABS molding compositions and moldings obtained have a low yellowness value and high gloss.
  • the invention particularly relates to a process for the preparation of ABS graft copolymers, which comprises a step for isolating the graft copolymer B present in an aqueous dispersion with a precipitating agent, wherein the precipitating agent is an aqueous solution a1) of the components
  • A1) and A2); A1) and A3); A2) and A3); or A1), A2) and A3) is used, wherein: A1) 0.10 to 0.65 wt .-% MgS0 4 , based on the total amount of water, and
  • the amount A1) is greater than the amount A2); or A1) 0.1 to 0.65 wt .-% MgS0 4 , based on the total amount of water, and A3) 0.01 to 0.40 wt .-%, based on the total amount of water, of a monodisperse water-soluble aluminum salt of Sulfuric acid, preferably Al 2 (S0 4 ) 3 ,
  • A3) from 0.01 to 0.40% by weight, based on the total amount of water, of a monodisperse, water-soluble aluminum salt of sulfuric acid, preferably Al 2 (SO 4 ) 3 ; or
  • A1) 0.10 to 0.40 wt .-% MgS0 4 , based on the total amount of water, A2) 0.01 to 0.10 wt .-% sulfuric acid, based on the total amount of water, and
  • A3) from 0.01 to 0.20% by weight, based on the total amount of water, of a monodisperse, water-soluble aluminum salt of sulfuric acid, preferably Al 2 (SO 4 ) 3 ,
  • the amount A1) is greater than the amount A3) and the amount A3) greater than the amount A2);
  • graft copolymer B has a bimodal particle size distribution and is composed of:
  • B1 from 40 to 85% by weight, based on the solids content of the graft copolymer B, of a graft base (B1) obtainable by (a) polymerization of:
  • (B21) 70 to 90 wt .-%, based on the graft shell (B2), styrene and / or ⁇ -methyl styrene, in particular styrene, and
  • the above concentration data (in% by weight) of the components A1), A2) and A3) relate to the total amount of water in the reactor (or reaction vessel). Under the total amount of water, the amount of water is the entire aqueous
  • Phase i. the aqueous dispersion of the graft copolymer and the aqueous solution a1) of the precipitating agent to understand.
  • Isoprene, butadiene and / or chloroprene can be used as the diene component (B12), for example, preference is given to using isoprene and / or butadiene, more preferably butadiene.
  • component (B1 1) it is possible to use styrene or styrene derivatives such as C 1 -C 8 -alkyl-substituted styrenes such as ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene and p-butylstyrene, preferably ⁇ -methylstyrene and / or styrene; In particular, only styrene is used.
  • the diene component (B12) is generally in an amount of 75.5 to 89.5 wt .-%, in particular 76 to 89 wt .-%, preferably 78 to 88 wt .-%, very particularly preferably 79 to 86 wt .-%, and the vinyl aromatic component (B1 1) in an amount of 10.5 to 24.5, in particular 1 1 to 24 wt .-%, preferably 12 to 22 wt .-%, completely particularly preferably used 14 to 21 wt .-%.
  • a graft base B1 of butadiene and styrene in the abovementioned composition is preferred.
  • the preparation of the graft base B1 is known to the person skilled in the art or can be carried out by methods known to the person skilled in the art. Heterogeneous, particle-forming polymerization processes are preferred for the preparation of the graft base B1. This dispersion polymerization can be carried out, for example, in a manner known per se by the method of emulsion, inverse emulsion, miniemulsion, microemulsion or micro-suspension polymerization in the feed process, continuously or batchwise.
  • the graft base (B1) can also be prepared in the presence of a finely divided latex (so-called "seed latex procedure" of the polymerization). Suitable seed latices consist for example of polystyrenes.
  • the components (B12) and (B1.sub.1) are preferably polymerized in processes known to those skilled in the art at temperatures of generally from 20 to 100.degree. C., preferably from 50 to 90.degree.
  • the monomer addition is carried out such that initially only vinylaromatic (B1 1), in particular styrene, in an amount of 3 to 10% by weight, preferably 5 to 8 wt .-%, with respect to the total monomer Amount (B1 1) and (B12), added and polymerized.
  • the addition of (B1 1) is preferably carried out within 5 to 30 minutes. Thereafter, usually over a period of 1 to 18 hours, preferably 2 to 16 hours, more preferably 4 to 12 hours, the addition and polymerization of a mixture of diene (B12) and residual vinyl aromatic (B1 1) at temperatures of 30 to 80 ° C. , preferably 50 to 80 ° C.
  • the feed of the abovementioned monomer mixture to the initially charged reaction mixture can take place all at once, in several portions, or preferably continuously during the polymerization.
  • the usual emulsifiers such as alkali metal salts of alkyl or Arylsulfonsauren, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or resin soaps can be used.
  • 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 graft base (B1). 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 also 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 graft (B1), depends on the desired molecular weight.
  • the customary buffer substances which adjust pH values of preferably 6 to 10, 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 ⁇ -methylstyrene can be used become.
  • the exact polymerization conditions, in particular the type, dosage and amount of the emulsifier are chosen within the ranges given above so that the graft base (B1) particle sizes (weight average d 50 ) in the range of 80 to 800 nm, preferably 80 to 600 nm, particularly preferably 85 to 400 nm.
  • the reaction conditions are chosen so that the polymer particles have a bimodal particle size distribution, in particular a particle size distribution with two maxima whose spacing can vary.
  • the particle sizes and their distribution can be determined by conventional methods.
  • the first maximum is more pronounced (peak comparatively narrow) than the second and is generally from 25 to 200 nm, preferably from 60 to 170 nm and particularly preferably from 70 to 150 nm.
  • the second maximum is comparatively broader and lies generally at 150 to 800 nm, preferably 180 to 700 nm, particularly preferably at 200 to 600 nm.
  • the bimodal particle size distribution can be achieved by (partial) agglomeration of the polymer particles of the graft base B1.
  • the monomers B1 1 and B12 which form the core are first polymerized to a conversion of at least 90%, preferably more than 95%, based on the monomers B1 1 and B12. This turnover is usually achieved in 4 to 20 hours.
  • the obtained rubber latex has a mean particle size d50 of at most 200 nm and a narrow particle size distribution (almost monodisperse system).
  • an agglomerating component (C) is used, which is preferably a copolymer of one or more hydrophobic C 1 to C 2 alkyl, preferably C 1 to C 4 alkyl acrylates or C 1 to C 2 alkyl , preferably Ci to C 4 - alkyl methacrylates, more preferably ethyl acrylate, and 0.1 to 20 wt.%, Preferably 0.1 to 10 wt .-%, one or more polar monomers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, N Methylolmethacrylamide and N-vinylpyrrolidone, especially methacrylamide.
  • polar monomers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, N Methylolmethacrylamide and N-vinylpyrrolidone, especially methacrylamide.
  • the proportion of hydrophobic monomers is generally from 80 to 99.9, preferably 90 to 99.9 wt .-%
  • the proportion of the polar monomers is generally 0.1 to 20 wt.%, Preferably 0.1 to 10 wt. -%.
  • Particularly preferred is a copolymer of 92 to 98 wt .-% ethyl acrylate and 2 to 8 wt .-% methacrylamide.
  • a copolymer (C) described above which has a core composed of at least one of said hydrophobic monomers, preferably of ethyl acrylate, which core is grafted with a copolymer of the aforementioned polar monomers.
  • the copolymer (C) used as an aqueous dispersion, as a so-called agglomeration latex.
  • the agglomeration of the graft base (B1) is usually done by adding a dispersion of the copolymer (C) described above.
  • concentration of the Polymer (C) in the dispersion used for agglomeration should generally be between 3 to 60% by weight, preferably between 5 to 40% by weight.
  • 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, of the dispersion of the copolymer C per 100 parts of the graft base B1, each calculated on solids, are generally used.
  • the agglomeration is generally carried out at a temperature of 20 to 120 ° C, preferably from 30 to 100 ° C, particularly preferably from 30 to 75 ° C.
  • the addition of C can take place all at once or in portions, continuously or with a feed profile over a certain period of time.
  • the agglomeration time i. the time from the beginning of the addition of C to the start of the subsequent graft copolymerization is preferably from one minute to several hours, for example up to 2 hours, more preferably from 10 to 60 minutes.
  • the pH during agglomeration is generally from 6 to 13, preferably 8 to 13.
  • the latex of the graft base B1 is only partially agglomerated, resulting in a bimodal particle size distribution. More than 60%, preferably 70 to 85%, of the particles (distribution by number) are usually in the non-agglomerated state after agglomeration.
  • the resulting partially agglomerated latex of the graft base B1 is relatively stable, and can therefore be well, that is, without coagulation occurs, store and transport.
  • graft base B1 In order to achieve a bimodal particle size distribution of the graft base B1, it is also possible, but less preferred, separately to produce two different graft bases B1 and B1 ', which differ in their average particle size, and mix these grafting bases B1 and BT in the desired mixing ratio.
  • the graft copolymer B may be composed of the partially agglomerated graft base B1 and one or more graft shells B2.
  • the term graft copolymer B is to be understood as meaning that a graft copolymer B alone as well as a mixture of two or more different graft copolymers B should be included. According to one of the preferred embodiments, a graft copolymer B is used alone.
  • the agglomerated graft base B1 is grafted with the monomers B21 and B22.
  • the graft copolymer B generally contains from 40 to 85% by weight, based on the solids content of the graft copolymer B, of a graft base (B1) and from 15 to 60% by weight, based on the solids content of the graft copolymer B, of a graft shell (B2).
  • B1 and B2 gives 100 wt .-%.
  • the graft shell (B2) can be obtained by reacting (B21) 70 to 90% by weight, preferably 75 to 85% by weight, of styrene and / or ⁇ -methylstyrene, in particular styrene, and 10 to 30% by weight. %, preferably 15 to 25 wt .-%, acrylonitrile, methacrylonitrile and / or methyl methacrylate, in particular acrylonitrile, in the presence of the agglomerated graft base (B1). The sum of B21 and B22 gives 100% by weight.
  • Preferred graft shells B2 are composed of: B2-1 copolymers of styrene and acrylonitrile, B2-2 copolymers of ⁇ -methylstyrene and acrylonitrile. Particularly preferred are B2-1 copolymers of styrene and acrylonitrile. Particularly preferred grafted shells B2 are obtained by reacting 75 to 85% by weight of styrene and from 15 to 25% by weight of acrylonitrile.
  • the graft shell (B2) is preferably produced after the agglomeration of the graft base (B1) by an emulsion polymerization process.
  • the graft copolymerization for producing the graft shell (B2) can be carried out in the same system as the emulsion polymerization for the preparation of the graft base (B1), it being possible, if necessary, to add further emulsifiers and auxiliaries. NEN.
  • the monomer mixture to be grafted can be added to the reaction mixture all at once, distributed over several stages-for example, to build up a plurality of graft coatings-or continuously during the polymerization.
  • the monomers B21 and B22 especially styrene and acrylonitrile may be added simultaneously.
  • the graft shell (B2) is polymerized in the presence of the agglomerated graft base (B1) obtained by the process described above from a monomer mixture consisting of the components B21 and B22, in particular styrene and acrylonitrile.
  • the monomers can be added individually or in mixtures with each other. For example, one can first graft B21 alone and then a mixture of B21 and B22. It is advantageous to carry out this graft copolymerization again in aqueous emulsion under the usual conditions described above for the grafting base.
  • graft copolymers B composed of:
  • B1 40 to 85% by weight of a graft base (B1) obtainable by (a) polymerisation of:
  • a graft shell B2 15 to 60% by weight of a graft shell B2 obtainable by reacting the agglomerated graft base B1 with a mixture of:
  • graft copolymers B synthesized from: B1: from 40 to 85% by weight of a graft base (B1) obtainable by (a) polymerization of:
  • a graft shell B2 15 to 60% by weight of a graft shell B2 obtainable by reacting the agglomerated graft base B1 with a mixture of:
  • B1 40 to 85% by weight of a graft base (B1) obtainable by (a) polymerisation of:
  • a graft shell B2 15 to 60% by weight of a graft shell B2 obtainable by reacting the agglomerated graft base B1 with a mixture of:
  • the graft copolymer B is isolated from an aqueous dispersion.
  • the aqueous phase of the dispersion is to be understood here as the continuous phase in which the graft copolymer B is present as a discontinuous phase.
  • the aqueous phase of the dispersion is based on water or else a solvent mixture which contains a large proportion, ie at least 20% by weight, of water.
  • the aqueous phase may contain, in addition to water, for example, solvents such as acetone or alcohol, of which ethanol is preferred.
  • the aqueous phase contains for the most part water, especially only water.
  • compounds derived from the production process such as those not removed, can of course be used in the aqueous phase Be contained emulsifiers, monomer residues or stabilizers.
  • Graft copolymer B should also be understood here as meaning a mixture of different graft copolymers B used according to the invention.
  • the solution, suspension or emulsion of one or more further graft copolymers B or the one or more further graft copolymers B are added per se.
  • the mixture of these graft copolymers B can then be isolated. More preferably, the graft copolymer B is isolated from its reaction mixture.
  • the precipitant used is preferably an aqueous solution a1) of components A1) and A2) in the following composition:
  • the precipitant used is preferably an aqueous solution a1) of components A1) and A3) in the following composition:
  • A3 from 0.02 to 0.40% by weight of a monodisperse, water-soluble aluminum salt of sulfuric acid, preferably Al 2 (SO 4 ) 3 ;
  • A1 0.20 to 0.50 wt .-% MgS0 4 , and A3) 0.05 to 0.30 wt .-% of a monodisperse water-soluble aluminum salt of sulfuric acid, preferably
  • A3 from 0.05 to 0.20% by weight of a monodisperse, water-soluble aluminum salt of sulfuric acid
  • the precipitant used is preferably an aqueous solution a1) of components A2) and A3) in the following composition:
  • A2) from 0.02 to 0.10% by weight of sulfuric acid, and A3) from 0.02 to 0.40% by weight of a monodisperse, water-soluble aluminum salt of sulfuric acid, preferably Al 2 (SO 4 ) 3 ;
  • Aluminum salt of sulfuric acid preferably Al 2 (S0 4 ) 3 ; and most preferably A2) 0.04 to 0.06 wt .-% sulfuric acid, and
  • A3 from 0.05 to 0.20% by weight of a monodisperse, water-soluble aluminum salt of sulfuric acid, preferably Al 2 (SO 4 ) 3 .
  • the precipitant used is preferably an aqueous solution a1) of components A1), A2) and A3) in the following composition:
  • Aluminum salt of sulfuric acid preferably Al 2 (S0 4 ) 3 ; and particularly preferably A1) from 0.10 to 0.30% by weight of MgS0 4 ,
  • Aluminum salt of sulfuric acid preferably Al 2 (S0 4 ) 3 .
  • an aqueous solution a1) of components A1) and A2) is used particularly preferably as precipitant as described above.
  • magnesium sulfate (MgS0 4 ) is used as MgS0 4 ⁇ 7 hydrate or anhydrous magnesium sulfate.
  • the sulfuric acid can be used as concentrated sulfuric acid.
  • the term "monodisperse water-soluble aluminum salts of sulfuric acid” means in the context of this invention those aluminum salts which give a "true solution” with water, examples of such aluminum salts being Al 2 (SO 4 ) 3 ,
  • KAI (S0 4 ) 2 KAI (S0 4 ) 2 ,, NaAl (S0 4 ) 2 or NH 4 Al (S0 4 ) 2 , more preferably Al 2 (S0 4 ) 3 .
  • the abovementioned aluminum salts are industrially preferably used as anhydrous aluminum salts, in the laboratory as the corresponding hydrates.
  • the components of the precipitating agent used according to the invention are used as aqueous solution.
  • the aqueous solution contains the components used according to the invention dissolved in an aqueous solvent, e.g. in water or a water / ethanol mixture, especially in water.
  • the components are particularly preferably used dissolved in water.
  • the addition of the precipitating agent can take place all at once, in portions or in the feed process with or without profile. Preferably, the addition is carried out batchwise or on an industrial scale continuously.
  • the pH of the aqueous phase in which the graft copolymer is present can vary within wide limits.
  • the pH of the aqueous phase after precipitation is particularly preferably in the range from 4 to 11, for example in the range from 5 to 10.
  • the pH of the aqueous phase after the precipitation is in the range of 7, if used according to the invention
  • Precipitant contains no component A2), otherwise in the presence of component A2), the pH is in the range of 5.
  • the aqueous solution a1) is initially charged with the components of the precipitating agent and the aqueous solution in aq. grafted graft copolymer present to the presented solution of the precipitating agent.
  • the amount of precipitant needed for the precipitation can vary within wide limits and depends, inter alia, on the concentration of the graft copolymer in the aqueous phase and the excipients used, such as emulsifiers. In general, the amount of graft copolymer (solid), based on the total aqueous phase, 10 to 30 wt .-%, preferably from 15 to 25 wt .-%, in particular from 18 to 22 wt .-%. Under the entire aqueous phase, the aqueous phase is out
  • the precipitation can be carried out at normal pressure. However, it can also be done at a pressure below or above e.g. in the range of 1 to 10 bar. Advantageous for the method according to the invention is a pressure in the range of 1 to 5, in particular of 4 bar.
  • the temperature at which the precipitation is carried out can vary within wide limits. For the graft copolymers used according to the invention, temperatures in the range from 20 to 140.degree. C., preferably from 70 to 100.degree. C., particularly preferably from 80 to 95.degree. C., have proved favorable.
  • the aqueous phase is sheared, for example by stirring.
  • the shear rates strongly depend on the present system.
  • the shear rate can also be varied during the course of the precipitation.
  • the precipitation can be carried out in a wide variety of reactors. Suitable reactors include stirred tanks, stirred tank cascades, tube reactors with static mixers, or tube reactors with dynamic mixers.
  • the precipitation may be carried out in a batch or in a continuous process or in a semi-batch process. In a batchwise procedure, for example, in stirred tanks can be used.
  • the dispersion of the graft copolymer can be introduced into a flow-through tube with or without mixing elements.
  • the solution of the precipitant may e.g. be sprayed.
  • the process according to the invention may comprise further steps or measures for the work-up which are known to the person skilled in the art in principle.
  • the graft copolymer is sintered after being isolated according to the invention.
  • the sintering process can be very short, for example, take a few seconds or in the minute range. However, it may also be necessary to sinter the graft copolymer over a longer period of time. So the sintering process can take up to several hours. Often, the graft copolymers are sintered for a period of one minute to two hours.
  • the temperature of the sintering process is usually in the range of about 70 to 200 ° C, preferably at 90 to 125 ° C. During the sintering process the temperature can be constant. However, it may also be advantageous to change the temperature during the sintering step.
  • the pressure during the sintering process is preferably in the range of 1 to 5 bar.
  • the precipitated and optionally sintered graft copolymer may be e.g. by sieving, squeezing, filtering, decanting, sedimentation, preferably centrifuging, or be separated by partial thermal drying of the aqueous phase.
  • the separation can also be carried out by means of squeezing in an extruder with a suitable construction known per se for the person skilled in the art.
  • the graft copolymer can also be separated from the aqueous phase by a combination of said steps.
  • thermoplastic molding compositions which comprise at least one thermoplastic copolymer A, at least one graft copolymer B and, if appropriate, further components K in the following composition:
  • thermoplastic copolymer A 40 to 80% by weight of at least one thermoplastic copolymer A obtainable from:
  • A1 20 to 31 wt .-%, based on the copolymer A, acrylonitrile
  • A2 69 to 80 wt .-%, based on the copolymer A, styrene or a-methyl styrene or a mixture of styrene and a-methyl styrene,
  • K 0 to 5% by weight of further components K, where the sum of A, B and K is 100% by weight.
  • thermoplastic molding compositions according to the invention containing (or consisting of):
  • thermoplastic copolymer A 50 to 75% by weight of at least one thermoplastic copolymer A obtainable (or obtained) from:
  • A1 20 to 31 wt .-%, based on the copolymer A, acrylonitrile
  • A2 69 to 80 wt .-%, based on the copolymer A, styrene or a-methyl styrene or a mixture of styrene and a-methyl styrene,
  • K 0 to 5 wt .-% further components K, wherein the sum of A, B and K 100 wt .-% results.
  • thermoplastic molding compositions comprising (or consisting of):
  • thermoplastic copolymer A from 55 to 75% by weight of at least one thermoplastic copolymer A obtainable from:
  • A1 20 to 31 wt .-%, based on the copolymer A, acrylonitrile
  • A2 69 to 80 wt .-%, based on the copolymer A, styrene or a-methyl styrene or a mixture of styrene and a-methyl styrene
  • B 25 to 45 wt .-% of at least one, according to the invention
  • K 0 to 5 wt .-% further components K, wherein the sum of A, B and K 100 wt .-% results.
  • the copolymer A is preferably prepared from the components acrylonitrile and styrene and / or ⁇ -methylstyrene by bulk polymerization or in the presence of one or more solvents. Preference is given to copolymers A having molecular weights M w of 50,000 to 300,000 g / mol, wherein the molecular weights, for example by light scattering in tetrahydrofuran (GPC with UV detection). The copolymer A forms the matrix of the thermoplastic molding composition.
  • the copolymer A may in particular contain or consist of:
  • the copolymer A can also be obtained by copolymerization of acrylonitrile, styrene and ⁇ -methylstyrene. In principle, however, it is also possible to use polymer matrices which contain further monomer building blocks.
  • the viscosity (Vz) of the copolymeric matrix A is (measured according to DIN 53726 at 25 ° C. in a 0.5% by weight solution in DMF), e.g. from 50 to 120 ml / g.
  • the copolymer matrix A can be prepared by a method, as described for example in Kunststoff-Handbuch, Vieweg-Daumiller, Volume V, (polystyrene), Carl Hanser Verlag, Kunststoff 1969, pages 122 f., Lines 12th ff. Is described.
  • the preferred copolymer matrix component A is a polystyrene-acrylonitrile, poly- ⁇ -methylstyrene-acrylonitrile or mixtures thereof.
  • the component A is isolated after the preparation by methods known to those skilled in the art and preferably processed into granules.
  • the copolymers A used according to the invention in the molding composition can also be used e.g. be mixed with other thermoplastic polymers (TP).
  • TP thermoplastic polymers
  • partially crystalline polyamides, partly aromatic copolyamides, polyesters, polyoxyalkylene, polyarylene sulfides, polyether ketones, polyvinyl chlorides and / or polycarbonates are suitable.
  • the suitable polycarbonates or polyester carbonates may be linear or branched. Branched products are preferably prepared by incorporation from 0.05 to 2.0 Mol%, based on the sum of the diphenols used, of three or more than trifunctional compounds, for example those having three or more than three phenolic OH groups.
  • the polycarbonates or polyester carbonates may contain aromatically bonded halogen, preferably bromine and / or chlorine. Preferably, however, they are halogen-free. They have average molecular weights (M w , weight average, determined, for example, by ultracentrifugation or scattered light measurement) of from 10,000 to 200,000, preferably from 20,000 to 80,000.
  • Suitable thermoplastic polyesters are preferably polyalkylene terephthalates, i. Reaction products of aromatic dicarboxylic acids or their reactive derivatives (for example dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.
  • Preferred polyalkylene terephthalates can be prepared from terephthalic acids (or their reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods (see Kunststoff-Handbuch, Volume VI II p.
  • polyalkylene terephthalates are 80 to 100, preferably 90 to 100 mol% of the dicarboxylic acid residues, terephthalic acid residues and 80 to 100, preferably 90 to 100 mol% of the diol residues, ethylene glycol and / or butanediol 1, 4 residues ,
  • the polyalkylene terephthalates may contain 0 to 20 mol% of radicals of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 12 C atoms (see, for example, DE 2 407 647 DE 2 407 776 and DE 2715 932).
  • the polyalkylene terephthalates can be branched by incorporation of relatively small amounts of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, as described in DE 1
  • branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. It is advisable to use not more than 1 mol% of the branching agent, based on the acid component. Preference is given to polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example their dialkyl esters) and ethylene glycol and / or butanediol-1, 4, and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters prepared from at least two of the abovementioned alcohol components: particularly preferred copolyesters are poly (ethylene glycol-butanediol-1,4) terephthalates.
  • Suitable polyamides are known homopolyamides, copolyamides and mixtures of these polyamides. They may be partially crystalline and / or amorphous polyamides.
  • Polycrystalline polyamides which are suitable are polyamide-6, polyamide-6,6, mixtures and corresponding copolymers of these components.
  • partially crystalline polyamides the acid component of which wholly or partly consists of terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, whose diamine component is wholly or partly composed of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4-trimethylhexamethylenediamine and / or 2,2,4-trimethylhexamethylenediamine and / or isophoronediamine and whose composition is known.
  • polyamides which are wholly or partly made of lactams having 7-12 carbon atoms in the ring, optionally with the concomitant use of one or more of the abovementioned starting components.
  • amorphous polyamides known products can be used which are obtained by polycondensation of diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, m- and / or p-xylylenediamine, bis- (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 3,3'-di-methyl-4,4'-diaminodicyclohexylmethane, 3-aminomethyl, 3,5,5-trimethylcyclohexylamine, 2,5- and / or 2,6-bis (aminomethyl) norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid, hepta
  • Copolymers obtained by polycondensation of several monomers are also suitable, and copolymers which are prepared with addition of aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoundecanoic acid or ⁇ -aminolauric acid or their lactams.
  • aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoundecanoic acid or ⁇ -aminolauric acid or their lactams.
  • Particularly suitable amorphous polyamides are polyamides prepared from isophthalic acid, hexamethylenediamine and further diamines such as 4,4'-diaminodicyclohexylmethane, isophoronediamine, 2,2,4- and / or 2,4,4-tri-methylhexamethylenediamine, 2,5- and or 2,6-bis (aminomethyl) norbornene; or from isophthalic acid, 4,4'-diaminodicyclohexylmethane and ⁇ -caprolactam; or isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam; or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine.
  • thermoplastic molding compositions of the invention based on the amount of copolymer A plus graft copolymer B, 0 to 90 wt .-%, preferably 0 to 50 wt .-%, particularly preferably 0 to 20 wt .-% of the above-mentioned polymers (TP) ,
  • thermoplastic molding composition If at least one of the aforementioned polymers (TP) is present in the thermoplastic molding composition, its minimum content is usually 0.1% by weight. Preference is given to thermoplastic molding compositions consisting of copolymer A and graft copolymer B and optionally other components K.
  • thermoplastic molding composition may contain one or more components selected from the group consisting of dispersants (DM), fillers (F) and additives (D).
  • component (K) is present, it is often used in amounts of 0.01 to 5% by weight, preferably in amounts of 0.05 to 5% by weight, particularly preferably 0.1 to 5% by weight. used.
  • thermoplastic molding compositions according to the invention often have the following composition:
  • thermoplastic copolymer A 40 to 79.99% by weight of at least one thermoplastic copolymer A obtainable from:
  • A1 20 to 31 wt .-%, based on the copolymer A, acrylonitrile, and
  • A2 from 69 to 80% by weight, based on the copolymer A, of styrene or of
  • thermoplastic molding compositions according to the invention are preferably containing (or consisting of): A: 50 to 74.95% by weight of at least one thermoplastic copolymer A obtainable from:
  • A1 20 to 31 wt .-%, based on the copolymer A, acrylonitrile
  • A2 69 to 80 wt .-%, based on the copolymer A, styrene or a-methyl styrene or a mixture of styrene and a-methyl styrene,
  • K 0.05 to 5 wt .-% further components K, wherein the sum of A, B and K is 100 wt .-%.
  • thermoplastic molding compositions according to the invention are particularly preferably containing (or consisting of):
  • thermoplastic copolymer A from 55 to 74.9% by weight of at least one thermoplastic copolymer A
  • A1 20 to 31 wt .-%, based on the copolymer A, acrylonitrile
  • A2 69 to 80 wt .-%, based on the copolymer A, styrene or a-methyl styrene or a mixture of styrene and a-methyl styrene
  • B 25 to 44.9 wt .-% of at least one, according to the invention
  • K 0.1 to 5 wt .-% further components K, wherein the sum of A, B and K is 100 wt .-%.
  • the thermoplastic molding compositions may also contain 0 to 5, often 0.1 to 5 wt .-% of fibrous or particulate fillers (F) or mixtures thereof, each based on the amount of components A plus B plus K.
  • fibrous or particulate fillers F
  • glass fibers which may be equipped with a size and a bonding agent, glass beads, mineral fibers, alumina fibers, mica, quartz powder or wollastonite may be added as fillers or reinforcing agents.
  • metal flakes, metal powders, metal fibers, metal-coated fillers for example nickel-coated glass fibers and other additives which shield electromagnetic waves, can be admixed with the molding compositions according to the invention.
  • carbon fibers carbon black, in particular conductive carbon black or nickel-coated C fibers can be added.
  • the molding compositions can be added as auxiliary and processing additives various additives (D) in amounts of 0 to 5, often 0.1 to 5 wt .-%. Suitable additives (D) are all those substances which are usually used for processing or finishing the polymers.
  • the dosing of these other additives can be done at any stage of the manufacturing process, but preferably at an early stage, to take advantage of the stabilizing effects (or other specific effects) of the additive at an early stage.
  • other customary auxiliaries and additives e.g. on "Plastics Additives Handbook", Ed. Gumbleter and Muller, 4th edition, Hanser Publ., Kunststoff, 1996, referenced.
  • Suitable pigments are titanium dioxide, phthalocyanines, ultramarine blue, iron oxides or carbon black, as well as the entire class of organic pigments.
  • Suitable colorants are e.g. all dyes which can be used for the transparent, semitransparent or non-transparent coloring of polymers, in particular those which are suitable for coloring styrene copolymers.
  • Suitable flame retardants may be, for example, the halogen-containing or phosphorus-containing compounds known to those skilled in the art, magnesium hydroxide, as well as other conventional compounds, or mixtures thereof.
  • Suitable antioxidants include sterically hindered mononuclear or polynuclear phenolic antioxidants, which may be substituted in various ways and may also be bridged via substituents. These include not only monomeric but also oligomeric compounds which can be composed of several phenolic basic bodies. Also suitable are hydroquinones and hydroquinone-analogous, substituted compounds, as well as antioxidants based on tocopherols and their derivatives. Also mixtures of different antioxidants can be used.
  • co-stabilizers can be used, in particular phosphorus or sulfur-containing co-stabilizers.
  • P- or S-containing co-stabilizers are known to the person skilled in the art.
  • Suitable light stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones.
  • Suitable matting agents are both inorganic substances such as talc, glass spheres or metal carbonates (such as MgCC> 3, CaCC> 3), as well as polymer particles - in particular spherical particles with diameters d 50 over 1 mm - based on, for example, methyl methacrylate, styrene compounds , Acrylonitrile or mixtures thereof.
  • polymers which comprise copolymerized acidic and / or basic monomers are also possible to use.
  • Suitable anti-drip agent are, for example, polytetrafluoroethylene (Teflon) polymers and ultra-high molecular weight polystyrene (molecular weight M w over 2,000,000).
  • fibrous or pulverulent fillers are carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, chopped glass, glass beads and wollastonite, particularly preferably glass fibers.
  • glass fibers When glass fibers are used, they can be provided with a size and an adhesion promoter for better compatibility with the blend components.
  • the incorporation of the glass fibers can take place both in the form of short glass fibers and in the form of endless strands (rovings).
  • Suitable particulate fillers are e.g. Carbon black, amorphous silica, magnesium carbonate, powdered quartz, mica, mica, bentonite, talc, feldspar or in particular calcium silicates such as wollastonite and kaolin.
  • Suitable antistatics include, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or alkylene amines, polyethylene glycol esters, copolymers of ethylene oxide glycol and propylene oxide glycol (especially diblock or triblock copolymers of ethylene oxide and propylene oxide blocks) and glycerol mono- and distearates , as well as their mixtures.
  • Suitable stabilizers are, for example, hindered phenols, but also vitamin E or analogously constructed compounds, as well as butylated condensation products of p-cresol and dicyclopentadiene.
  • Hindered amine light stabilizers benzophenones, resorcinols, salicylates, benzotriazoles are also suitable.
  • Other suitable compounds are, for example, thiocarboxylic acid esters.
  • HALS absorbers such as bis (2, 2,6,6-tetramethyl-4-piperidyl) sebazate
  • UV absorbers such as 2H-benzotriazol-2-yl- (4-methylphenol).
  • HALS absorbers such as bis (2, 2,6,6-tetramethyl-4-piperidyl) sebazate
  • UV absorbers such as 2H-benzotriazol-2-yl- (4-methylphenol).
  • Such additives are usually used in amounts of 0.01 to 2 wt .-% (based on the total mixture).
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters, amide waxes (bisstearylamide), polyolefin waxes or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms.
  • amide waxes bisstearylamide
  • polyolefin waxes or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms.
  • Ethylene-bis-stearamide eg Irgawax, manufacturer Ciba, Switzerland
  • the amounts of these additives are in the range of 0.05 to 5 wt .-%.
  • Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives.
  • the usual amounts, if used, are from 0.001 to 3% by weight based on the amount of components A plus B plus K.
  • pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid are usable.
  • Processing aids and stabilizers such as UV stabilizers, heat stabilizers (eg butylated reaction products of p-cresol and dicyclopentadiene, Wingstay L, manufacturer: Omnova, or thiouripropionic acid dilauryl ester, Irganox PS 800, manufacturer: BASF), lubricants and antistatics (eg ethylene oxide -Propylene oxide copolymers such as Pluronic (manufacturer: BASF), if used, are usually used in amounts of 0.01 to 5 wt .-%, based on the total molding composition.
  • UV stabilizers eg butylated reaction products of p-cresol and dicyclopentadiene, Wingstay L, manufacturer: Omnova
  • thiouripropionic acid dilauryl ester Irganox PS 800, manufacturer: BASF
  • lubricants and antistatics eg ethylene oxide -Propylene oxide copolymers such as Pluronic (manufact
  • the individual additives are generally used in the usual quantities.
  • the preparation of the molding compositions from the components A and B (and optionally further polymers (TP), and components K such as fillers (F) and conventional additives (D)) can be carried out by all known methods.
  • the mixing of the components by melt mixing, for example, common extrusion, kneading or rolling of the components. This is carried out at temperatures in the range of 160 to 400 ° C, preferably from 180 to 280 ° C.
  • component (B) is previously partially or completely isolated from the aqueous dispersion obtained in the respective production steps.
  • the graft copolymers B can be mixed with the matrix polymers as moist or dry crumbs / powders (for example with a residual moisture content of 1 to 40%, in particular 20 to 40%), the complete drying of the graft copolymers then taking place during the mixing.
  • the drying of the particles can also be carried out according to DE-A 19907136.
  • the graft copolymers prepared by the process according to the invention are in particular essentially free of gel and can be dried easily and quickly.
  • the molding compositions obtainable from the graft copolymers can be processed into shaped articles by means of the known methods of thermoplastic processing; in particular, the molded articles can be produced by thermoforming, extrusion, injection molding, calendering, hollow-body blowing, pressing, press-sintering, deep drawing or sintering, preferably by injection molding.
  • the aforementioned moldings can be used in principle in all technical fields. Their field of application can range, for example, from the medical or sanitary sector via vehicle construction to consumer goods in the leisure sector or in the home. Shaped bodies produced using the graft copolymers prepared according to the invention are distinguished by good mechanical properties. In particular, they have surfaces which contain little to no surface defects and have a high surface gloss. Furthermore, they hardly tend to yellowish, are good temperature-resistant and weather-resistant. In addition, transparent moldings which have been produced using the graft copolymers prepared according to the invention have only a slight turbidity tendency. The invention is further illustrated by the following examples and claims: First, the investigation methods used to characterize the polymers are briefly summarized: a) Charpy notched impact strength [kJ / m 2 ]:
  • the notched impact strength is determined on test specimens (80 ⁇ 10 ⁇ 4 mm, produced by injection molding at a melt temperature of 240 ° C. and a mold temperature of 70 ° C.), at 23 ° C. according to ISO 179-1A b) flowability (MVR [ml / 10 min]):
  • a disk centrifuge DC 24000 from CPS Instruments Inc. was used to measure the weight-average particle size d w of the rubber dispersions of the graft base B1. The measurement was carried out in 17.1 ml of an aqueous sugar solution with a sucrose density gradient of 8 to 20 wt .-% in order to achieve a stable flotation behavior of the particles. A polybutadiene latex with a narrow distribution and a mean particle size of 405 nm was used for the calibration.
  • the measurements were taken at a speed of the disc of 24000 rpm by injecting 0.1 ml of a dilute rubber dispersion (aqueous 24 wt .-% sucrose solution containing about 0.2 to 2 wt .-% rubber particles) in the Disc centrifuge, containing the aqueous sugar solution with a sucrose density gradient of 8 to 20 wt .-% performed.
  • a dilute rubber dispersion aqueous 24 wt .-% sucrose solution containing about 0.2 to 2 wt .-% rubber particles
  • the determination of the Yl value was carried out on plates with the dimensions 60 ⁇ 40 ⁇ 2 mm, produced by injection molding at a melt temperature of 240 ° C and a mold temperature of 70 ° C according to ASTM method E313-96 (light / observer combination C / 2 ").
  • the preparation of the graft base B1-V (not used according to the invention) is carried out by emulsion polymerization by the feed process.
  • the comonomer used is 7% by weight of styrene.
  • 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), 31 g of potassium stearate, 82 g of potassium persulfate, 147 g of sodium bicarbonate and 58,400 g of water a latex of the graft base having a solids content of 42.1% by weight is obtained.
  • TDM tert-dodecylmercaptan
  • the monomers are added to the reactor in the order listed below: First, the addition of styrene in an amount of 7% by weight, based on the total amount of monomer, takes place 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 wt .-%, 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 turnover is> 95%.
  • the preparation of the graft base B1 -2 (used according to the invention) is carried out by emulsion polymerization according to the feed process. The comonomer used is 14% by weight of styrene.
  • 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), 31 g of potassium stearate, 82 g of potassium persulfate, 147 g of sodium bicarbonate and 58,400 g of water a latex of the graft base having a solids content of 42.1% by weight is obtained.
  • TDM tert-dodecylmercaptan
  • the monomers are added to the reactor in the order listed below:
  • styrene in an amount of 7 wt .-%, based on the total amount of monomer, within 20 minutes.
  • a mixture of 0.527% by weight of styrene and 6.473% by weight of butadiene, based on the total amount of monomer is added within 25 minutes.
  • the total styrene content is the total amount of styrene, based on the total amount of monomer; the core styrene content refers to the first polymerized styrene, it is 7 wt .-%, based on the total amount of monomer in all experiments.
  • the preparation of the copolymer C-1 takes place by means of emulsion polymerization.
  • the particle size distribution of the agglomerated graft base B1 is measured. Only a fraction of the particles in the latex of the graft base B1 are agglomerated into larger particles.
  • the agglomeration yield is the proportion of agglomerated particles in% by weight based on the total amount of the particles.
  • the agglomeration yield is determined from the cumulative distribution curve of the particle size measurement.
  • the temperature is raised to 80 ° C.
  • the polymerization is continued for 80 minutes at 80 ° C and the resulting latex of the graft copolymer B is cooled to ambient temperature.
  • a dispersion of a stabilizer (based on solids of the dispersion having a solids content of 60% by weight) are added to the obtained graft latex.
  • the dispersion of the graft copolymer is precipitated by means of an aqueous solution of a precipitating agent in a steam-heated precipitation vessel with stirrer at 4 bar and at a temperature of 88 ° C.
  • the aqueous solution of the precipitant is placed in the steam-heated precipitation vessel, and after reaching a temperature of 88 ° C, the dispersion of the graft copolymer is added slowly with stirring.
  • the respective reactor mixture had the following composition:
  • the precipitation suspension is transferred to a steam-heated sintering vessel with stirrer.
  • the sintering takes place at 4 bar and 1 16 ° C for 60 minutes.
  • the sintered graft copolymer is spun in a centrifuge, washed twice with 550 parts by weight of demineralized water.
  • the polymer thus processed, with a residual moisture content of 15 to 30%, is further processed by means of extrusion.
  • SAN polymer Luran VLN, random copolymer of styrene and acrylonitrile with an acrylonitrile content of 24 wt .-% with a Mw of 120000 g / mol of a viscosity number of 67 ml / g (concentration 5 g / l in dimethylformamide at 20 ° C. measured) and a melt flow rate MVR of 64 [ml / 10 min], measured at 220 ° C and 10 kg load according to ISO 1 133. additives
  • Stabilizer masterbatch with thermal and light stabilizers e.g. Tinuvin 770, Cyasorb 3853, Chimasorb 944 in SAN polymer (Luran VLN)
  • the abovementioned SAN polymer A and the graft copolymer B are mixed in the proportions indicated in the respective table (based on the total molding composition) with the addition of 1% by weight of the abovementioned stabilizer masterbatch in a twin-screw extruder with a shaft diameter of 25 mm.
  • the temperature was set at 200 to 250 ° C, and processing was performed at 700 rpm of the twin screw extruder.
  • the batch size for all examples was 4 kg.
  • tests for the determination of the flowability (MVR), the Charpy notched impact strength, the Yellowness Index (YI), and the surface gloss were carried out. The above test methods were used. Tables 3 and 4 summarize the test results of the investigated ABS molding compositions.
  • Graft copolymer B-2 35.2 37.0 39.2 33.0 34.6 36.8 31, 0 33.9 35.6 (wt%)
  • the MgS0 4 / Al 2 (S0 4 ) 3 precipitant used according to the invention is very efficient, since lower amounts of salt are required to achieve the same high yields of the graft copolymer B.
  • the investigated ABS molding compositions which comprise the graft copolymer obtained by the process according to the invention have a constant notched impact strength with an improved yellowness value compared to a pure Al 2 (SO 4 ) 3 solution of the same salt concentration (Table 3).
  • Table 4 shows investigations for corresponding molding compositions of a SAN polymer A and a graft copolymer B, wherein the graft copolymer B used according to the invention as the graft copolymer B-2 (with the graft base B1 -2) or as a comparison, the graft copolymer BV (with graft base B1-V) has been.
  • Table 4 shows that the use of the claimed MgS0 4 / H 2 S0 4 - precipitant to graft copolymers and derived ABS molding compositions leads which have a significantly improved yellowness index and surface gloss, VO out set as impressive the comparison shows that the graft copolymer is a graft copolymer having a styrene-rich grafting base as claimed in the process of the invention.

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Abstract

L'invention concerne un procédé de production d'un copolymère greffé ABS, comprenant une étape consistant à isoler le copolymère greffé B, présent dans une dispersion aqueuse, à l'aide d'un agent de précipitation qui est une solution aqueuse d'un mélange de MgSO4, d'Al2(SO4) et/ou de H2SO4. Les matières moulables ABS obtenues ont un indice de jaunissement amélioré et une brillance de surface élevée.
EP15730750.5A 2014-06-25 2015-06-17 Procédé d'isolation de copolymères greffés abs Withdrawn EP3161041A1 (fr)

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