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WO1999025749A1 - Procede de production de polymeres greffes - Google Patents

Procede de production de polymeres greffes Download PDF

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Publication number
WO1999025749A1
WO1999025749A1 PCT/EP1998/007097 EP9807097W WO9925749A1 WO 1999025749 A1 WO1999025749 A1 WO 1999025749A1 EP 9807097 W EP9807097 W EP 9807097W WO 9925749 A1 WO9925749 A1 WO 9925749A1
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WIPO (PCT)
Prior art keywords
alkyl
weight
polymerization
graft
oxyl
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PCT/EP1998/007097
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German (de)
English (en)
Inventor
Peter Barghoorn
Norbert Güntherberg
Heinz Friedrich Sutoris
Michael Fischer
John Lynch
Franz Benedix
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BASF SE
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BASF SE
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Priority to EP98961146A priority Critical patent/EP1034201A1/fr
Priority to KR1020007005426A priority patent/KR20010032225A/ko
Publication of WO1999025749A1 publication Critical patent/WO1999025749A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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

Definitions

  • the invention relates to a process for the preparation of graft polymers A from, based on A),
  • R 1 and R 2 represent hydrogen or Ci-Cs-alkyl
  • the invention also relates to the graft polymers prepared by the process and the use of the radical N-oxyl compounds to prevent deposits on reactor surfaces during the graft polymerization in the aqueous phase.
  • DE-OS 196 09 312 describes a process for preventing the premature polymerization of certain monomers containing vinyl groups, for example during distillation, purification, storage and during transport, by adding N-oxyl compounds of secondary amines.
  • N-oxyl compounds has also been described for the stabilization of styrene and other vinylaromatic compounds during distillation (US Pat. No. 5,254,760).
  • traces of such nitroxyl compounds already follow the polymerization process that follows to disturb; they cause a delayed polymerization and uncontrolled chain termination, which leads to polymers with poor reproducibility and short chain length.
  • sterically hindered N-oxyl radicals are used together with a co-initiator as initiators in living radical polymerization.
  • N-oxyl radical / co-initiator ratio is limited to 0.5 to 2.5 and in WO 96/24620 to 1.2 to 1.6. Since the reaction rate is comparatively slow with the chosen initiator ratios, polymerization must be carried out at higher temperatures, usually above 100.degree.
  • the object was to provide a method which does not have the disadvantages described.
  • a process should be found which enables the production of graft polymers in particular in the aqueous phase, the formation of polymer deposits on the reactor walls being reduced or completely prevented, without appreciably impairing the polymerization process, for example with regard to its speed.
  • this object is achieved by first completing the polymerization of the basic stage a1) and then at least one radical N-oxyl compound of a secondary one before and / or during the polymerization of the grafting stage a2) A ins, which carries no hydrogen atoms on the ⁇ -C atoms.
  • graft polymers 5 prepared by the process and the use of the radical N-oxyl compounds to prevent deposits on reactor surfaces during the graft polymerization in the aqueous phase were found.
  • the graft polymers A) contain, based on A), 10 al) 30 to 95, preferably 40 to 90 and particularly preferably 40 to
  • al3 * 0 to 40, preferably 0 to 30 and particularly preferably 0 to 20% by weight of one or more further 35 monoethylenically unsaturated monomers,
  • a2) 5 to 70, preferably 10 to 60 and particularly preferably 15 to 60% by weight of a graft stage, based on a2),
  • R 1 and R 2 are hydrogen or -CC 8 alkyl
  • a22 0 to 40, preferably 0 to 38 and particularly preferably 0 to 35% by weight of acrylonitrile or methacrylonitrile or mixtures thereof,
  • a23 0 to 40, preferably 0 to 30 and particularly preferably 0 to 20% by weight of one or more further monoethylenically unsaturated monomers.
  • dienes with conjugated double bonds are butadiene, isoprene, norbornene and their halogen-substituted derivatives, such as chloroprene.
  • the other monoethylenically unsaturated monomers a 12) which may be present in the graft core a1) at the expense of the monomers a1) are, for example:
  • vinyl aromatic monomers such as styrene, styrene derivatives of the general formula
  • R 1 and R 2 represent hydrogen or Ci to CQ alkyl
  • Ci to C 4 alkyl esters of methacrylic acid such as methyl methacrylate, and also the glycidyl esters, glycidyl acrylate and methacrylate;
  • N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexyl maleimide
  • Acrylic acid, methacrylic acid, furthermore dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their anhydrides such as maleic anhydride
  • dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their anhydrides such as maleic anhydride
  • Nitrogen-functional monomers such as dirnethylaminoethyl 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
  • Preferred monomers al2) are styrene, acrylonitrile, methyl methacrylate, glycidyl acrylate and methacrylate, acrylamide and methacrylamide.
  • Suitable as (C ⁇ -C ⁇ o-alkyl) esters of acrylic acid, component all *), are especially ethyl acrylate, 2-ethylhexyl acrylate and n-butyl acrylate. Preferred are 2-ethylhexyl acrylate and n-butyl acrylate, and n-butyl acrylate is very particularly preferred . Mixtures of different alkyl acrylates which differ in their alkyl radical can also be used.
  • Crosslinking monomers al2 *) are bifunctional or polyfunctional comonomers with at least two olefinic double bonds, for example butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl and divinyl ethers of bifunctional alcohols such as ethylene glycol and butane 1,4-diols, diesters of acrylic acid and methacrylic acid with the bifunctional alcohols mentioned, 1,4-divinylbenzene and triallyl cyanurate.
  • bifunctional or polyfunctional comonomers with at least two olefinic double bonds for example butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl and divinyl ethers of bifunctional alcohols such as ethylene glycol and butane 1,4-diols, diesters of acrylic acid and methacrylic acid with the bifunctional
  • acrylic acid ester of tricyclodecenyl alcohol see DE-OS 12 60 135, which is known under the name dihydrodicyclopentadienyl acrylate, and the allyl esters of acrylic acid and methacrylic acid.
  • Crosslinking monomers al2 * can be present in the molding compositions depending on the type of molding compositions to be produced, in particular depending on the desired properties of the molding compositions Not. If crosslinking monomers a1 *) are contained in the molding compositions, the amounts are 0.01 to 10, preferably 0.2 to 10 and particularly preferably 1 to 5% by weight, based on a1).
  • the monomers which have already been mentioned for the monomers al2) can also be used as further monoethylenically unsaturated monomers a1 *).
  • Preferred monomers al3 *) are styrene, acrylonitrile, methyl methacrylate, glycidyl acrylate and methacrylate, acrylamide and methacrylamide.
  • the graft core a1) can also be composed of a mixture of the monomers all) and a12), and all *) to a3 *).
  • the graft core contains the monomers all) and al2), then after mixing with a thermoplastic polymer composed of styrene and acrylonitrile (SAN), molding compounds of the ABS type (acrylonitrile - butadiene - styrene) are formed. If the graft core contains the monomers all *) to al3 *), so-called ASA molding compounds (acrylonitrile - styrene alkyl acrylate) are formed after mixing with a thermoplastic polymer made from styrene and acrylonitrile (SAN).
  • SAN thermoplastic polymer composed of styrene and acrylonitrile
  • the graft polymer A) is accordingly ABS or ASA graft polymers, or mixtures thereof.
  • the styrene compound of the general formula (I) (component a21)) is preferably styrene, ⁇ -methyl styrene, and also ring-alkylated with Ci-C ⁇ alkyl styrenes such as p-methyl styrene or tert. - butyl styrene, a. Styrene is particularly preferred. Mixtures of the styrenes mentioned, in particular styrene and ⁇ -methylstyrene, can also be used.
  • Component a2) may also contain one or more further monoethylenically unsaturated monomers a23) at the expense of monomers a21) and a22). With regard to the monomers a23), reference is made to the comments on component al3).
  • Preferred graft a2) are for example polystyrene and copolymers of styrene and / or ⁇ -methyl styrene and one or meh ⁇ reren of the other monomers mentioned under a22) and a23).
  • ⁇ are the more sustainable methyl methacrylate, N-phenylmaleimide, maleic anhydride and acrylonitrile, particularly preferably methyl methacrylate and acrylonitrile.
  • Examples of preferred grafting steps a2) are:
  • the proportion of styrene or ⁇ -methylstyrene, or the proportion of the sum of styrene and ⁇ -methylstyrene, is particularly preferably at least 40% by weight, based on a2).
  • the process according to the invention relates to graft polymerizations in the aqueous phase.
  • solutions, emulsions and suspensions of the corresponding monomers or polymers in water as well as in solvent mixtures which to a large extent, i.e. contain at least 20% by weight of water.
  • the graft polymerization is generally carried out in a manner known per se by the method of emulsion, mini-emulsion,
  • the polymerization is carried out according to the emulsion procedure, in which the monomers are polymerized in aqueous emulsion at 20 to 100 ° C., preferably at 50 to 80 ° C., it being possible for all of the components of the batch to be combined (batch process), or the monomer alone or an emulsion of monomer, water and emulsifiers can be added gradually to the other components (semi-batch process).
  • the reaction can also be carried out continuously. The semi-batch process is preferred.
  • Suitable emulsifiers are, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms, sulfosuccinates, ether sulfonates or resin soaps.
  • Preference ⁇ example take the alkali metal salts of alkylsulfonates or fatty acids having 10 to 18 carbon atoms. Their amount is usually 0.5 to 5% by weight, based on the core monomers a1).
  • Sufficient water is preferably used to prepare the dispersion so that the finished dispersion has a solids content of 20 to 50% by weight.
  • All free radical formers which decompose at the selected reaction temperature are suitable for starting the polymerization reaction, that is to say both those which decompose thermally on their own and those which do so in the presence of a redox system.
  • Free radical formers for example peroxides such as preferably peroxosulfates (for example sodium or potassium persulfate) and azo compounds such as azodiisobutyronitrile, are preferably used as polymerization initiators.
  • redox systems in particular those based on hydroperoxides such as cumene hydroperoxide, can also be used.
  • the polymerization initiators are used in an amount of 0.1 to 2% by weight, based on the graft base monomers a1).
  • the radical formers and also the emulsifiers are added to the reaction batch, for example, discontinuously as a total amount at the start of the reaction, or divided into several portions, batchwise at the start and at one or more later times, or continuously during a certain time interval.
  • the continuous addition can also take place along a gradient, e.g. can be ascending or descending, linear or exponential, or also stepwise (stair function).
  • Molecular weight regulators such as e.g. Ethylhexylthiog - lycolate, n- or t-dodecyl mercaptan or other mercaptans, terpinols and dimeric ⁇ -methylstyrene or other compounds suitable for regulating the molecular weight are also used.
  • the molecular weight regulators are added to the reaction batch discontinuously or continuously, as was described above for the radical formers and emulsifiers.
  • buffer substances such as Na 2 HP0 / NaH P0 4, Natriumpyrrophosphat, sodium hydrogen carbonate or buffers based on citric acid / citrate, concomitantly. Regulators and buffer substances are used in the usual quantities, so that further details are not necessary.
  • the graft base a1) can also be prepared by polymerizing the monomers a1) in the presence of a finely divided latex (so-called "seed latex mode of operation" of the polymerization).
  • This latex is presented and can consist of rubber-elastic polymer-forming monomers, or also of other monomers, as already mentioned.
  • seed latices consist, for example, of polybutadiene or polystyrene.
  • the graft base a1) can be produced using the so-called feed process.
  • a certain proportion of the monomers a1) is introduced and the polymerization is started, after which the remainder of the monomers (“inflow fraction”) a1) are added as an inflow during the polymerization.
  • the feed parameters (shape of the gradient, amount, duration, etc.) depend on the other polymerization conditions. The statements made regarding the addition of the radical start or emulsifier also apply here analogously.
  • the proportion of the monomers a1) is preferably 5 to 50% by weight, particularly preferably 8 to 40% by weight, based on a1).
  • the feed fraction of a1) is preferably allowed to run in within 1-18 hours, in particular 2-16 hours, very particularly 4 to 12 hours.
  • Graft polymers with several "soft” and “hard” shells e.g. of the structure al) -a2) -al) -a2), or a2) -al) -a2), especially in the case of larger particles.
  • the exact polymerization conditions, in particular the type, amount and dosage of the emulsifier and the other polymerization auxiliaries are preferably chosen so that the latex of the graft polymer A obtained, an average particle size, defined by the total particle size distribution, usually from 30 to 1000, preferably 50 to 800 and particularly preferably 50 to 400 nm.
  • a bimodal particle size distribution is desired, this can be achieved by a (partial) agglomeration of the polymer particles. This can be done, for example, as follows:
  • the monomers a1) which build up the core are polymerized up to a conversion of usually at least 90%, preferably greater than 95%, based on the monomers used.
  • the rubber latex obtained preferably has a medium one
  • Particle size dso of maximum 200 nm and a narrow particle size distribution (almost monodisperse system).
  • the rubber latex is then agglomerated, for example by adding a dispersion of an acrylic ester polymer.
  • a dispersion of an acrylic ester polymer Preferably ⁇ the dispersions of Copolymeris2011en from (Ci -C alkyl) esters of acrylic acid, preferably ethyl acrylate, with from 0.1 to 10 wt -.% monomers forming polar polymers, such as, for example, acrylic acid, methacrylic acid, acrylamide or methacrylamide, N-methylolmethacrylamide or N-vinylpyrrolidone. A copolymer of 96% ethyl acrylate and 4% methacrylamide is particularly preferred.
  • the concentration of the acrylic ester polymers in the dispersion used for agglomeration should generally be between 3 and 40% by weight.
  • 0.2 to 20, preferably 1 to 5 parts by weight of the agglomerating dispersion to 100 parts of the rubber latex, calculated in each case on solids, are used.
  • the agglomeration is carried out by adding the agglomeration dispersion to the rubber.
  • the rubber latex can also be coated with other agglomerating agents such as e.g.
  • Acetic anhydride to be agglomerated is also possible.
  • the methods mentioned are known to the person skilled in the art.
  • the rubber particles Under the conditions mentioned, only a part of the rubber particles is agglomerated, so that a bimodal distribution is produced. After agglomeration there are generally more than 50, preferably between 75 and 95% of the particles (number distribution) in the non-agglomerated state.
  • the partially agglomerated rubber latex obtained is relatively stable, so that it can be easily stored and transported without coagulation occurring.
  • the basic al After the polymerization is completed the basic al), according to the invention before and / or a radical N-oxyl -ver ⁇ bond added to the basic level during polymerization of the graft a2).
  • the N-oxyl compound and further details are described below.
  • the N-oxyl compound may prior to agglomeration, during, or be added after the agglomeration. Addition before agglomeration is preferred.
  • the graft stage a2) can be prepared under the same conditions in emulsion as the preparation of the basic stage al), it being possible to produce the graft stage a2) in one or more process steps.
  • the monomers a21), a22) and a23) can be added individually or in a mixture with one another. The monomer ratio of the mixture can be constant over time or a gradient. Combinations of these procedures are also possible.
  • the graft stage a2) acts as a compatibilizer between the basic rubber stage a1) and the matrix polymer in which the graft polymers A are embedded.
  • the monomers a2) therefore preferably correspond to those of the matrix. If the matrix consists entirely or predominantly of a styrene-acrylonitrile copolymer (SAN), as is the case with the ABS or ASA molding compositions mentioned, the graft shell usually also consists entirely or predominantly of styrene and / or ⁇ -methylstyrene and acrylonitrile. However, other monomers a2) can also be used, for example methyl methacrylate.
  • SAN styrene-acrylonitrile copolymer
  • other monomers a2) can also be used, for example methyl methacrylate.
  • the method according to the invention can also be carried out as a miniemulsion polymerization.
  • the miniemulsion polymerization differs from the normal, just described Emul ⁇ sionspolymerisation mainly characterized in that the particle size is nm usually 50 to 500, and the particles are typically stabilized by a combination of ionic emulsifiers and co-emulsifiers to the convergence.
  • the stability of a mini emulsion is usually lower than that of a conventional emulsion.
  • Long-chain alkanes such as hexadecane or long-chain alcohols such as hexadecanol are usually used as co-emulsifiers.
  • mini-emulsion polymerization the mixture of monomers, water, emulsifiers and co-emulsifiers is exposed to high shear forces, as a result of which the components are mixed intimately. It is then polymerized.
  • the high shear forces can be generated, for example, by ultrasound or a microfluidizer device, or also by the homogenizers mentioned below in the description of the microsuspension polymerization.
  • the person skilled in the art can find details on mini-emulsion polymerization, for example, in P. Covell, M. El-Aasser, Emulsion Polymerization and Emulsion Polymers, published by John Wiley, New York, 1997, pp. 699-722.
  • shearing e.g. continuous, batch, etc.
  • shearing Possible ways of shearing (e.g. continuous, batch, etc.) are described below in microsuspension polymerization.
  • the process according to the invention can also be carried out as suspension polymerization.
  • Suspension polymerization differs from emulsion polymerization essentially in that the initiators dissolve not or only slightly in the aqueous phase, but in the monomer, and in that a protective colloid is used instead of an emulsifier.
  • the monomer is dispersed into droplets by stirring in the aqueous phase, the protective colloid preventing the droplets from converging.
  • the particles formed in the suspension polymerization are generally considerably larger than particles produced in emulsion.
  • the method can also be a micro-suspension polymerization ⁇ performed.
  • Microsuspension polymerization differs from normal suspension polymerization essentially in that the suspension of the monomers in water is stirred much more intensively (exposure to considerably higher shear forces). The process is described in more detail below.
  • the monomers M (or the monomer mixture M) which correspond to the desired polymer A) are dispersed in water using at least one protective colloid SK, so that a dispersion of the monomer droplets in water with a volume-average droplet diameter knife dso of usually 700 nm to 100 ⁇ m. After that the droplets are polymerized using a radical polymerization initiator RI.
  • the amount of water in which the monomers M and the protective colloids SK are dispersed is usually from 25 to
  • the protective colloids SK which are suitable for stabilizing the dispersion are water-soluble polymers which coat the monomer droplets and the polymer particles formed therefrom and in this way protect them against coagulation.
  • Suitable protective colloids SK are cellulose derivatives such as carboxymethylcellulose and hydroxymethylcellulose, poly-N-vinylpyrrolidone, polyvinyl alcohol and polyethylene oxide, anionic polymers such as polyacrylic acid and their copolymers and cationic polymers such as poly-N-vinylimidazole.
  • the amount of these protective colloids is preferably 0.1 to 10% by weight, based on the total mass of the emulsion.
  • One or more polyvinyl alcohols are preferably used as the protective colloid, in particular those with a degree of hydrolysis below 96 mol%, particularly preferably 60 to 94 and very particularly preferably 65 to 92 mol%.
  • the preferred polyvinyl alcohols have a viscosity of 2 to 100 mPa / s, in particular 4 to 60 mPa / s, measured as a 4% strength by weight solution in water at 20 ° C. according to DIN 53015.
  • colloidal silica in a concentration of generally 0.2 to 5% by weight, based on the amount of the dispersion, can also be used. More about this method, which works particularly well with a water-soluble polymer of adipic acid and diethanolamine as a protective colloid, can be found in US Pat. No. 3,615,972.
  • a water-soluble inhibitor In order to suppress the simultaneous emulsion polymerization process in microsuspension polymerization, in which much smaller and therefore undesirable particles are formed, a water-soluble inhibitor can be used, which inhibits the Emulsion polymerization suppressed.
  • Effective compounds of this type are, for example, chromium (+6) compounds such as potassium dichromate.
  • An emulsion is prepared from the monomers M, water and the protective colloids SK by allowing high shear forces to act. Homogenizers known to those skilled in the art are used for this.
  • Examples include:
  • these devices operate at speeds from 1000 to 25,000 min -1, preferably from 2000 to 15,000 min '1.
  • the dispersion is usually prepared at room temperature, but depending on the type of monomers and protective colloids, higher or lower temperatures can also be useful.
  • the dispersion can be prepared either batchwise (batch mode) or continuously.
  • monomers, water and protective colloids are placed in a container and mixed to form a microsuspension (dispersion) using the homogenizer.
  • the homogenizer can also be arranged parallel to the container and the components are circulated through the homogenizer.
  • the duration of homogenization can be between 0.1 sec and several hours, depending on, for example, the desired diameter of the monomer droplets and the size distribution to be set, the mixing behavior of the monomers with water, the quantitative ratios of monomer, water and protective colloid, and the protective colloid used.
  • the monomers, water and protective colloids can be fed to the homogenizer and the dispersion prepared in this way can be fed directly into the reactor in which the polymerization is carried out.
  • monomers, water and protective colloids are circulated through the homogenizer and only part of the circulated mixture is branched off and fed to the polymerization reactor.
  • This circular procedure is particularly recommended if the dispersion of the monomers after only one throughput through the homogenizer is still insufficient, for example if the droplet size is too large and / or the size distribution is too wide.
  • the dispersion can also be prepared batchwise and in a first step
  • the components are dispersed as a batch as described, and the resulting dispersion is then subjected to a second continuous dispersion. This creates the finished dispersion, which is fed continuously to the reactor.
  • microsuspenion polymerization is initiated with a radical polymerization initiator RI.
  • RI radical polymerization initiator
  • Such compounds are known to the person skilled in the art. Compounds with a half-life of one hour are preferred if the temperature is 60 to
  • initiators RI organic peroxides, azo compounds and / or compounds with CC single bonds are used as initiators RI.
  • radical polymerization initiators are monomers which spontaneously polymerize at elevated temperature.
  • 2,2'-Azobis (2-methylbutyronitrile) and 2,2'-azobis (isobutyronitrile) are preferred as azo compounds.
  • 3,4-Dimethyl-3,4-diphenylhexane and 2,3-dimethyl-2,3-diphenyl-butane are preferably used as compounds with labile C-C bonds.
  • the initiating monomers which polymerize spontaneously at elevated temperature are preferably styrene and its derivatives, such as vinyltoluene, particularly preferably styrene.
  • the amount of initiator RI is usually 0.05 to 4, preferably 0.1 to 2 and particularly preferably 0.3 to 1, by weight, based on the amount of the monomers M. These amounts of course do not apply in the event that the Monomer is also an initiator, such as styrene.
  • the initiator can be added as such, but preferably as a solution, dispersion (liquid in liquid) or suspension (solid in liquid), so that small amounts of initiator in particular can be metered more precisely.
  • Suitable solvents or liquid phases for the initiator are organic solvents such as benzene, toluene, ethylbenzene and cyclohexane, especially cyclohexane, or the monomers themselves.
  • organic solvents such as benzene, toluene, ethylbenzene and cyclohexane, especially cyclohexane, or the monomers themselves.
  • the monomers themselves are used as solvents or liquid phases for the initiator, the initiator becomes dissolved or emulsified / suspended in the total amount of the monomers or preferably in a smaller proportion of the monomers, and this proportion is then added to the remaining components.
  • the initiator (s) RI can be added before or after the preparation of the dispersion, or only immediately before the start of the polymerization, or can be metered in continuously in the course of the polymerization. In particular in the case of monomers which tend to undergo uncontrolled polymerization or which polymerize at the temperature of the dispersion preparation, it is advisable to add the initiator RI only after the emulsification, and in some cases only immediately before the polymerization.
  • the initiator in the case of polymerizations with a long polymerization time in particular, it may be advantageous to add the initiator as a continuous feed or in portions during the polymerization.
  • the duration of the initiator feed can be different or the same as the duration of the polymerization.
  • Further additives such as buffer substances and molecular weight regulators can be added continuously or discontinuously at the beginning and / or during the preparation of the dispersion and / or during the polymerization.
  • the polymerization is carried out in the customary manner, for example by heating the reactor contents, as a result of which the polymerization reaction is started. If necessary, the initiator RI can only then be added, that is to say to the heated dispersion.
  • the polymerization temperature depends, among other things. on the monomers and initiators used and on the desired degree of crosslinking of the resulting polymers A). Polymerization is generally carried out at from 30 to 120 ° C., it also being possible to set different temperatures or a temperature gradient in succession.
  • the polymerization reaction is usually carried out with slow or moderate stirring, in which (in contrast to the preceding emulsification by high shear forces) the droplets are no longer broken down.
  • the particle size in microsuspension polymerization can therefore essentially be controlled by appropriately selecting and controlling the conditions during the preparation of the dispersion (for example, choice of homogenizer, duration of homogenization, quantitative ratios of monomers: water: protective colloids, mode of dispersion) (simple , multiple, as a batch or continuously, circular mode), speed of the homogenizer etc.).
  • the grafting stage a2) is polymerized by the same method as the basic stage a1). So if the basic stage polymerized in emulsion, for example, the graft stage is usually also polymerized in emulsion.
  • the procedure is usually from 20 to 100 ° C., preferably 50 to 80 ° C.
  • water-soluble compounds which are used in the polymerization of the basic stage can be used as the polymerization initiator for the graft stage.
  • ollosliche or. initiators soluble in the monomer for example dialkyl peroxides such as dilauryl peroxide and dibenzyl peroxide, peresters such as tert. Butyl perpivalate and tert. -Butylperoxyneodecanoate, di-peroxyketals, peroxycarbonates and azo compounds such as azodiisobutyronitrile (AIBN) and azodiisovaleronitrile (ADVN) can also be used.
  • AIBN azodiisobutyronitrile
  • ADVN azodiisovaleronitrile
  • the gross composition of the graft polymers A remains unaffected by the above-mentioned embodiments of the process.
  • Graft polymers with several "soft” and “hard” stages e.g. of the structure al) -a2) -al) -a2) or a2) -al) -a2), especially in the case of larger particles.
  • non-grafted polymers are formed from the monomers a2) during the grafting, these amounts, which are generally below 10% by weight of a2), are assigned to the mass of component A.
  • the process according to the invention uses at least one radical N-oxyl compound of a secondary amine which has no hydrogen atoms on the ⁇ -C atoms. These compounds can exist as free compounds or in the form of their salts.
  • Suitable N-oxyls of amines are, for example, the following structures
  • R is the same or different alkyl, cycloalkyl, aralkyl or aryl radicals, which can also be connected in pairs to form a ring system
  • Y is a group which is required to complete a 5- or 6-membered ring.
  • R represents a C ⁇ -C o-, especially Ci-C ß- alkyl radical, a C 5 - or C 6 -cycloalkyl radical, a benzyl radical or a phenyl radical.
  • Y is, for example, an alkylene group - (CH 2 ) 2 - or - (CH 2 ) 3 -.
  • N-oxyl compounds such as the following structures are also suitable.
  • aromatic rings can each carry 1 to 3 inert substituents, such as C 1 -C 4 alkyl, C 1 -C 4 alkoxy or cyano.
  • Sterically hindered amine derivatives of cyclic amines are preferably used, for example of piperidine or pyrrolidine compounds which may contain a further heteroatom such as nitrogen, oxygen or sulfur in the ring, this hetero- atom is not adjacent to the hindered amine nitrogen.
  • the steric hindrance is given by substituents in both neighboring positions to the amine nitrogen, hydrocarbon radicals which replace all 4 hydrogen atoms of the ⁇ -CH 2 groups being considered as substituents.
  • phenyl, C 3 -C 6 cycloalkyl, benzyl and in particular C ⁇ -C 6 alkyl radicals may be mentioned as substituents, it being possible for the alkyl radicals bonded to the same ⁇ -C atom to be linked to one another to form a 5- or 6-ring.
  • the radicals listed below under R 5 , R 6 are particularly preferred.
  • Derivatives of 2,2,6,6-tetraalkylpiperidine are preferably used as N-oxyls of sterically hindered amines.
  • Preferred N-oxyl compounds in the substance mixtures according to the invention are those of the general formula (VI)
  • R 1 and R 2 independently of one another in each case C1-C4-alkyl, phenyl or together with the carbon atom to which they are attached, a 5- or 6-membered saturated hydrocarbon ring,
  • R3 is hydrogen, hydroxy, amino, S0 3 H, S0 3 M, P0 3 H 2 , P0 3 HM, P0 3 M 2 , organosilicon radicals or an m-valent organic or organosilicon radical bonded via oxygen or nitrogen or together with R 4 Oxygen or a ring structure defined under R 4 , where M stands for an alkali metal.
  • R 4 is hydrogen, -CC 2 -alkyl, C1 . -C 1 2 alkoxy or together with R 3 oxygen or together with R 3 and the C atom to which they are attached, the following ring structures
  • R5 hydrogen f, -CC 2 alkyl or - (CH 2 ) z -C00R 6 ,
  • R6 the same or different Ci-Cis-alkyl
  • z and p are each independently 1 to 12 and
  • R 1 and R 2 can be -C 4 alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl, or they can together be a tetra- or form pentamethylene group.
  • R 1 and R 2 are preferably methyl groups.
  • R 4 are for example hydrogen, the above -CC 4 alkyl groups and pentyl, sec-pentyl, tert. -Pentyl, neo-oentyl, 2, 3-dimethyl-but-2-yl, hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, 2-ethylhexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 2-methylnonyl, isononyl , 2-Methyloctyl, Decyl, Isodecyl, 2-Methylnonyl, Undecyl, Isoundecyl, Dodecyl and Isododecyl, (the designations isooctyl, isononyl and isodecyl are trivial designations and come from the carbonyl compounds obtained after oxo synthesis; see also Ulimann'
  • p is preferably 6 to 12, particularly preferably 9.
  • R 5 may include, for example, the C 1 -C 2 -alkyl groups given above.
  • R 5 preferably represents hydrogen, C 1 -C 4 -alkyl or (CH 2 ) Z -C00 (-C-C 6 -alkyl), particularly preferably the radicals -CH 2 -CH 2 -C00 (CH 2 ) n- CH 3 and -CH 2 -CH 2 -COO (CH 2 ) ⁇ 3 -CH 3 .
  • R 6 can be, for example, one of the above -CC 2 alkyl groups or tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Dodecyl and hexadecyl are preferred.
  • Preferred monovalent radicals R 3 are hydrogen, the C 1 -C 4 -alkyl groups already mentioned above and organosilicon radicals of the formula ⁇
  • groups T can be identical or different from one another and are C 1 -C 12 -alkyl or phenyl.
  • Li, Na and K are preferably used as alkali metals M in the groups -S0 3 M, -P0 3 HM and -P0 3 M.
  • Preferred monovalent, oxygen-linked groups R 3 are hydroxy and C 4 alkoxy groups such as methoxy, ethoxy, propoxy and t-butoxy, but also the siloxane residues derived from the above organosilicon residues.
  • Preferred m-valent radicals R 3 are, for example, the following radicals
  • R 8 is hydrogen or Ci-Cis-Al yl
  • R 11 is hydrogen or an organic radical, as is usually produced in the radical polymerization of the starting compounds,
  • n is an even number m
  • R 4 is preferably hydrogen.
  • the variable m can mean 1 to 100.
  • M is 1, 2, 3, 4 or a number from 10 to 50, mixtures being used in particular in the case of the oligomeric or polymeric radicals R 3 .
  • the same radicals as R 7 are suitable as those mentioned for R 9 5.
  • R 7 is preferably C 1 -C 4 alkyl.
  • R 8 in addition to hydrogen, the same radicals come into consideration as have been mentioned for R 6 .
  • R 8 is preferably hydrogen.
  • R 9 in particular includes vinyl, isopropenyl, methyl, ethyl, propyl, i-propyl, t-butyl or Ci 5 -C ⁇ 7 alkyl radicals.
  • R i for example, the above-mentioned Cg-Cig-alkyl radicals and nonadecyl, eicosyl, uneicosyl and doeicosyl come into consideration. Mixtures of different radicals R 10 , which differ in the length of the carbon chain, are preferred.
  • the radicals R 11 are hydrogen or organic radicals, such as those formed during the radical polymerization of the starting compounds, that is to say, for example, a radical which arises from the polymerization initiator or from an intermediate radical which has occurred or another radical of this type, as is known to the person skilled in the art.
  • radicals R 11 can, for example, be styrene in the case of the starting compound
  • R ' stands for any primary radical which starts the polymerization of the styrene - or in the general case of the compounds (A).
  • Nitroxyl compounds of the formula (II ') can also be used
  • R i2 and R 13 independently of one another are each C 1 -C 4 -alkyl, phenyl or, together with the carbon atom to which they are attached, a 5- or 6-membered saturated hydrocarbon ring,
  • R 14 is an m '-valent radical bonded via carbon, oxygen or nitrogen,
  • R 15 is hydrogen, -CC 2 -alkyl, C 1 -C 12 -alkoxy or together with R 14 a m '-valent radical bonded via carbon or nitrogen through a chemical double bond to the carbon atom bearing these groups or together with R i4 and the C atom bearing these groups has a saturated isocyclic or heterocyclic 3- to 7-membered ring,
  • radicals R 12 and R i3 corresponds to that of the radicals R 1 and R 7 already mentioned above and should also be used here. Again methyl groups are preferably used as substituents R 12 and R i3 .
  • R i4 in question are C 1 -C 4 alkyl, and unsubstituted and having from one to three C ⁇ -C 4 alkyl substituted phenyl, with examples of C ⁇ -C 4 alkyl radicals have already been given above.
  • the attachment of these residues to the piperidine ring can be via oxygen, an NH or an
  • N (C ⁇ -C 4 alkyl) group take place. In the case of connection via a C atom, this should already be counted as belonging to the radical R 14 .
  • Possible residues R i4 are, for example (the lines here indicate the free valences):
  • N P Rl6 "NP-OR i6 , - N p _ N ( R 16) 2
  • R i4 and R 15 radicals can also together form a group which is then bonded to the carbon atom carrying the groups (the carbon atom in position 4 of the piperidine ring) via a chemical double bond via carbon or nitrogen.
  • Such m '-value groups can be, for example (the dashes indicate the free valences):
  • radicals R i4 and R i5 can form a 3- to 7-membered isocyclic or heterocyclic ring with the C atoms bearing these groups.
  • the groups R i6 here mean hydrogen, -CC 2 -alkyl and unsubstituted or substituted by one to four C 1 -C 4 -alkyl groups phenyl. Examples of corresponding C 1 -C 12 alkyl groups and C 1 -C 4 alkyl groups which can occur as substituents on the phenyl ring have already been mentioned above.
  • the variable k 'can have a value of 0.1 or 2.
  • N-oxyls are also oligomeric or polymeric compounds which have a polysiloxane as the main polymer chain and are substituted in the side chain with N-oxyl groups which are derived from 2, 2, 6, 6-tetraalkylpiperidine.
  • the 2, 2, 6, 6-tetramethyl-piperidine-N-oxyl radical is used as the preferred N-oxyl grouping.
  • Examples of such N-oxyls, which can also be used according to the invention, can be found in WO 69/17002. This document also contains examples of synthetic sen of the amino compounds on which the N-oxylene is based.
  • N-oxyl compounds are also the following: l-oxyl-2, 2,6, 6-tetramethylpiperidine, l-0xyl-2, 2,6, 6-tetramethylpiperidin-4-ol, l-0xyl- 2, 2,6, 6-tetramethylpiperidin-4-one, l-0xyl-2, 2,6, 6-tetramethylpiperidin-4-yl acetate, l-oxyl-2, 2,6, 6-tetramethylpiperidin-4- yl-2-ethylhexanoate, l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl-stearate, l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl-benzoate, l-oxyl- 2, 2,6, 6-tetramethylpiperidin-4-yl- (4-tert-butyl) benzoate,
  • Tris (2,2,6,6-tetramethyl-1-oxyl-piperidin-4-yl) phosphite Tris (2,2,6,6-tetramethyl-1-oxyl-piperidin-4-yl) phosphite.
  • the radical N-oxyl compounds can be obtained from the corresponding amino or piperidine compounds by oxidation e.g. with hydrogen peroxide. Details of this oxidation are e.g. called in DE-OS 195 101 84.
  • the secondary amines, which do not have hydrogen atoms on the ⁇ -C atoms, such as piperidine compounds, and their preparation are generally known. Since the oxidation reactions do not always proceed completely, the amino or piperidine compounds serving as starting compounds and partially oxidized intermediates such as hydroxylamines can also be present in the N-oxyl-containing mixtures.
  • the N-oxyl compound is added after the polymerization of the basic step a1) before and / or during the polymerization of the grafting step a2). If the polymer base stage (a1) is subjected to partial or complete agglomeration before the polymerization of graft stage a2) (see the explanations for emulsion polymerization), the N-oxyl compound can be added before, during or after the agglomeration, preferably before the agglomeration .
  • N-oxyl compounds can be applied in various ways.
  • N-oxyl compound it has proven advantageous to add the N-oxyl compound to the polymerization mixture from the end of the polymerized basic stage a1) and the grafting stage monomers a21) to a23).
  • the N-oxyl compound can also be contained in the graft monomers a21) to a23) in order to protect them from premature polymerization.
  • the concentration of the N-oxyl compound should be present in the polymerization mixture in such a way that it has little effect on the rate of polymerization.
  • the sensitivity of the polymerization with regard to the amount of the N-oxyl compound depends on various parameters, in particular on the type of monomer, on the structure of the N-oxyl compound, on the temperature and on other radical formers and radical scavengers which may be present in the reaction mixture.
  • the optimal concentration can be determined in a few preliminary tests with given process parameters.
  • the surface of the grafting stage reactor is accordingly wetted. If the base and graft stages are polymerized in the same reactor, the reactor is generally emptied, its surface is wetted and then fill it again with the previously drained mixture.
  • the wetting can be achieved simply and effectively by spraying the reactor wall and other parts in the reactor, such as the stirrer and heating or cooling elements, with a solution of the N-oxyl compound.
  • the N-oxyl compounds are often only slightly water-soluble, but mostly dissolve in organic solvents such as methanol, ethanol, propanol, acetone, ethyl acetate, dirnethylformamide, etc.
  • a particularly suitable solvent for many N-oxyl compounds is methanol.
  • concentration of the N-oxyl compound in the spray solution is not critical; it is advantageously set between 0.01 and 1% by weight, based on the total mass of the spray solution.
  • the reactor surface can also be wetted by filling it with a solution similar to the spray solution and then draining it off.
  • the wetting of the reactor surface has the advantage over the addition of the N-oxyl compound to the polymerization mixture that the influence on the rate of polymerization is extremely small and that the area above the liquid level, in particular the area just above the liquid level, in which deposits often occur are protected from fouling.
  • the aqueous dispersion of the graft polymers A) obtained is worked up onto the particulate graft polymers A) by completely or partially removing the aqueous medium.
  • the particulate polymer A) dispersed in the aqueous medium is first precipitated, if necessary, for example by adding a coagulating precipitant such as CaCl 2 , MgS0 4 , acetic acid, sulfuric acid, etc. Centrifugation or other solid-liquid separation processes separated.
  • the moist polymer A) obtained can either be processed further directly, or the residual moisture can be removed by thermal drying, for example by means of warm air in a current dryer.
  • the aqueous dispersion can also be worked up by the spray drying method. It is also possible to further process the aqueous polymer dispersion as such.
  • the dispersion can be mixed with other polymers in a mixing device with simultaneous removal of the aqueous phase.
  • the graft polymers A obtainable by the process according to the invention can be used as a constituent of thermoplastic molding compositions.
  • thermoplastic polymers with a glass transition temperature Tg> 25 ° C. are suitable as the thermoplastic matrix polymer which is contained in the molding compositions. Some such polymers are mentioned below as examples.
  • the matrix polymer contains 50 to 100, preferably 60 to 95 and particularly preferably 60 to 90% by weight of a styrene compound of the general formula as already described above for a21), or a (C 1 -C 8 -alkyl) ester acrylic acid or methacrylic acid or mixtures of the styrene compound and (Ci-Cs-alkyl) ester of acrylic acid or methacrylic acid, furthermore 0 to 40, preferably 5 to 38% by weight of acrylonitrile or methacrylonitrile or mixtures thereof, and 0 to 40, preferably 0 up to 30% by weight of one or more further monoethylenically unsaturated monomers as have already been mentioned for al2), al3 *) and a23).
  • the matrix polymer preferably has a glass transition temperature T g of 50 ° C. or above.
  • the matrix is therefore a hard polymer. The following applies to the matrix polymer:
  • the styrene compound of the general formula described is preferably styrene, .alpha.-methylstyrene and, moreover, styrenes which are core-alkylated with C.sub.1-C.sub.1-alkyl, such as p-methylstyrene or tert-butylstyrene. Styrene and ⁇ -methylstyrene are particularly preferred.
  • ci- to Cg-alkyl esters of acrylic acid and / or methacrylic acid come into consideration, especially those which are derived from methanol, ethanol, n- and iso-propanol, sec.-, tert.- and iso -Butanol, pentanol, hexanol, heptanol, octanol, 2 -ethylhexanol and n-butanol.
  • Methyl methacrylate is particularly preferred.
  • Preferred matrix polymers are, for example:
  • M / 1 polymethyl methacrylate (PMMA) - in this case A) can be obtained by polymerizing 100% by weight of methyl methacrylate (component ml)),
  • M / 2 polymers, obtainable by copolymerization from 40 to
  • styrene and / or ⁇ -methylstyrene with 10 to 60, preferably 20 to 40% by weight of acrylonitrile, and optionally 0 to 30, preferably 0 to 20% by weight of further monoethylenically unsaturated Monomers.
  • the matrix polymer preferably contains styrene and acrylonitrile
  • the known commercially available SAN copolymers are produced. They usually have a viscosity number VZ (determined according to
  • the matrix polymers can be prepared in a manner known per se, e.g. obtained by substance, solution, suspension, precipitation or emulsion polymerization. Details of these methods are e.g. in the plastics handbook, ed. Vieweg and Daumiller, Carl -Hanser - Verlag Kunststoff, vol. 1 (1973), pp. 37 to 42 and vol. 5 (1969), pp. 118 to 130, as well as in Ullmann's Encyclopedia of Technical Chemistry, 4th edition, Verlag Chemie Weinheim, Vol. 19, pp. 107 to 158 "Polymerizationstechnik" described.
  • the matrix is polyvinyl chloride PVC.
  • Suitable polyvinyl chlorides are known per se.
  • vinyl chloride Either only vinyl chloride or mixtures of vinyl chloride and other monomers (comonomers) with at least 40% by weight of vinyl chloride, based on the total mass of the monomers, can be used as the monomer for PVC.
  • Comonomers of vinyl chloride include, in particular, vinyl esters, for example vinyl acetate, vinyl propionate and others, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether and others, vinylidene chloride, C ⁇ -Ci 8- alkyl esters of acrylic acid such as butyl acrylate and 2-ethylhexyl acrylate, dialkyl maleates such as dibutyl maleate Ethene, propene, isobutene and longer-chain C 6 -Ci 5 -01efine, dienes such as butadiene and vinyl-aromatic compounds such as styrene into consideration.
  • the vinyl chloride is polymerized in a manner known per se, for example as an emulsion, suspension or bulk polymerization, preferably as a suspension polymerization.
  • the polymerization temperature depends on the desired molecular weight or K value of the PVC product and is between 20 and 100 ° C, preferably between 35 ' and 80 ° C, for most products between 45 and 70 ° C.
  • the polymerization is generally stopped at a conversion of 60 to 95%, preferably 70 to 90%.
  • the matrix is a polycarbonate or a polyester.
  • Suitable polycarbonates are known per se. They are e.g. obtainable according to the processes of DE-B-1 300 266 by interfacial polycondensation or according to the process of DE-A-14 95 730 by reacting biphenyl carbonate with bisphenols. Before - added bisphenol is 2, 2-di (4-hydroxyphenyl) propane, generally - as in the following - referred to as bisphenol A.
  • aromatic dihydroxy compounds can also be used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxy naphthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4 '-Dihydroxy- diphenyl sulfite, 4,4' -Dihydroxydiphenylmethan, 1, 1-di- (4-hydroxyphenyDethan or 4, 4-Dihydroxydipheny1 and mixtures of the aforementioned dihydroxy compounds.
  • 2,2-di (4-hydroxyphenyl) pentane 2,6-dihydroxy naphthalene
  • 4,4'-dihydroxydiphenyl sulfone 4,4'-dihydroxydiphenyl ether
  • 4,4 '-Dihydroxy- diphenyl sulfite 4,4' -Dihydroxydiphenylmethan
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 30 mol% of the aromatic dihydroxy compounds mentioned above.
  • the relative viscosity of these polycarbonates is generally in the range from 1.1 to 1.5, in particular 1.28 to 1.4 (measured at 25 ° C. in a 0.5% strength by weight solution in dichloromethane).
  • polyesters are also known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from an aromatic dicarboxylic acid.
  • the aromatic ring can also be substituted, for example by halogen such as chlorine and bromine or by -CC 4 alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or tert-butyl - groups.
  • the polyesters can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives thereof with aliphatic dihydroxy compounds.
  • the preferred dicarboxylic acids are naphthalenedicarboxylic acid
  • Terephthalic acid and isophthalic acid or mixtures thereof Up to 10 mol .-% of aromatic dicarboxylic acids can to be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
  • diols with 2 to 6 carbon atoms in particular 1, 2-ethanediol, 1,4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol and neopentyl glycol or their mixtures preferred.
  • polyesters are polyalkylene terephthalates which are derived from alkane diols having 2 to 6 carbon atoms. Of these, polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate are particularly preferred.
  • the viscosity number of the polyesters is generally in the range from
  • thermoplastic molding compositions can contain conventional additives, such as e.g. Lubricants or mold release agents, pigments, dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdery fillers or reinforcing agents or antistatic agents, as well as other additives or mixtures thereof.
  • additives such as e.g. Lubricants or mold release agents, pigments, dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdery fillers or reinforcing agents or antistatic agents, as well as other additives or mixtures thereof.
  • Suitable lubricants and mold release agents are e.g. Stearic acids, stearyl alcohol, stearic acid esters or amides as well as silicone oils, montan waxes and those based on polyethylene and polypropylene.
  • pigments are, for example, titanium dioxide, phthalocyanines, ultramarine blue, iron oxides or carbon black, as well as the class of organic pigments.
  • Dyes are to be understood as all dyes which can be used for the transparent, semi-transparent or non-transparent coloring of polymers, in particular those which are suitable for coloring styrene copolymers. Dyes of this type are known to the person skilled in the art.
  • flame retardants e.g. the halogen-containing or phosphorus-containing compounds known to the person skilled in the art, magnesium hydroxide and other customary compounds, or mixtures thereof, are used.
  • antioxidants are, for example, sterically hindered phenols, hydroquinones, various substituted representatives of this group and mixtures thereof. They are commercially available as Topanol ® or Irganox.
  • Suitable light stabilizers are, for example, various substituted resorcinols, salicylates, benzotriazoles, benzophenones, HALS (Hindered Amine Light Stabilizers), as they are, for example commercially available as Tinuvin ®.
  • fibrous or powdered fillers are carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, cut glass, glass balls and wollastonite, particularly preferably glass fibers.
  • glass fibers these can be equipped with a size and an adhesion promoter for better compatibility with the blend components.
  • Glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings).
  • Suitable particulate fillers are carbon black, amorphous silica ⁇ acid, magnesium carbonate (chalk), powdered quartz, mica, bentonites, talc, feldspar or in particular calcium silicates, such as wollastonite, and kaolin.
  • Suitable antistatic agents are, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or alkylene amines, polyethylene glycol esters, glycerol mono- and distearates, copolymers of ethylene oxide and propylene oxide, polypropylene glycol, N, N-bis (2-hydroxyalkyl) -Nn- octyl-N-methyl-ammonium-p-toluenesulfonate, and mixtures thereof.
  • amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or alkylene amines, polyethylene glycol esters, glycerol mono- and distearates, copolymers of ethylene oxide and propylene oxide, polypropylene glycol, N, N-bis (2-hydroxyalkyl) -Nn- octyl-N-methyl-ammonium-p-toluenesulfonate, and mixtures thereof.
  • thermoplastic molding compositions are prepared by mixing the matrix polymers and the graft polymers A and, if appropriate, the additives, in a suitable mixing device and processing them into a molding composition at suitable temperatures.
  • the molding compositions can be produced by mixing processes known per se, for example by melting in an extruder, Banbury mixer, kneader, roller mill or calender. However, the components can also be used "cold” and the powdery or granular mixture is only melted and homogenized during processing. Mixing usually takes place at temperatures of 130 to 350 ° C.
  • the molding compositions can advantageously be produced in an extruder in which the residual moisture is removed through drainage openings as liquid water and / or through degassing openings as steam.
  • Moldings of all types, including films, can be produced from the particulate polymers A) and in particular from the molding compositions.
  • the process according to the invention enables the preparation of graft polymers in the aqueous phase by all customary polymerization processes with a significantly reduced formation of wall coverings or completely without wall cover formation on the reactor surfaces.
  • the polymerization process is not impaired, especially not slowed down.
  • molding compositions made from matrix polymer and the graft polymers A) produced according to the invention have better mechanical properties, in particular a higher notched impact strength.
  • the weight average particle size dso of compo nent ⁇ B is, the weight average particle size as determined using an analytical ultracentrifuge by the method of W. Scholtan and H. Lange, Kolloid-Z. and Z. Polymer 250 (1972) pages 782 to 796.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
  • the weight-average particle diameter dso indicates the particle diameter in which 50% by weight of all particles have a larger and 50% by weight a smaller particle diameter.
  • Butadiene was polymerized in an aqueous emulsion.
  • the procedure was as described in DE-OS 31 49 046, page 15, lines 5 to 34.
  • the polybutadiene latex obtained had one Solids content of 40% by weight and an average particle size d 50 of 80 nm.
  • the coating on the reactor surface, on the stirrer and on the thermometer was then removed mechanically and weighed out.
  • a copolymer of 65% by weight of styrene and 35% by weight of acrylonitrile was produced by the process of continuous solution polymerization, as described in the plastics manual, ed. R. Vieweg and G. Daumiller, Vol. V "Polystyrene", Carl Hanser Verlag Kunststoff 1969, pages 122 to 124, is described.
  • the viscosity number VZ (determined according to DIN 53 726 at 25 ° C., 0.5% by weight in dimethylformamide) was 80 ml / g. e) Production and testing of moldings
  • the latex of the graft polymer A) drained off under c) was coagulated by adding a magnesium sulfate solution and the precipitated graft polymer was separated off, washed with water and dried with warm air.
  • ABS granules obtained were injected into standard small bars (see DIN 53 453) at a melt temperature of 220 ° C. and a mold temperature of 60 ° C.
  • the notched impact strength a ⁇ was determined on the standard small bars in the impact bending test according to ISO 179-211 eA (S).

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Abstract

L'invention concerne un procédé de production de polymères greffés (A) composés, par rapport à (A), de a1) 30 à 95 % en poids d'une base élastique en caoutchouc constituée, par rapport à a1), de a11) 50 à 100 % en poids d'un diène ayant des liaisons doubles conjuguées; a12) 0 à 50 % en poids d'au moins un autre monomère monoéthyléniquement insaturé, ou constituée, par rapport à a1), de a11*) 50 à 100 % en poids d'un ester (alkyle C1-C10) de l'acide acrylique; a12*) 0 à 10 % en poids d'un monomère réticulant et polyfonctionnel; a13*) 0 à 40 % en poids d'au moins un autre monomère monoéthyléniquement insaturé; a2) 5 à 70 % en poids d'une greffe composée, par rapport à a2), de a21) 50 à 100 % en poids d'un composé styrène de la formule générale (1) où R<1> et R<2> représentent de l'hydrogène ou alkyle C1-C8; a22) 0 à 40 % en poids d'acrylonitrile ou de méthacrylonitrile ou de leur mélange et a23) 0 à 40 % en poids d'au moins un autre monomère monoéthyléniquement insaturé, en phase aqueuse. L'invention est caractérisée en ce que l'on commence par réaliser la polymérisation de la base a1). Ensuite seulement, on ajoute au moins un composé N-oxyl radical d'une amine secondaire qui ne porte aucun atome d'hydrogène sur les atomes de carbone alpha , avant et/ou pendant la polymérisation de la greffe a2).
PCT/EP1998/007097 1997-11-19 1998-11-06 Procede de production de polymeres greffes Ceased WO1999025749A1 (fr)

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WO2000014134A1 (fr) * 1998-09-03 2000-03-16 Ciba Specialty Chemicals Holding Inc. Greffe de monomeres non satures en ethylene sur des polymeres
WO2000014135A1 (fr) * 1998-09-03 2000-03-16 Ciba Specialty Chemicals Holding Inc. Greffe de monomeres non satures en ethylene sur des polymeres
CN105164166A (zh) * 2013-04-18 2015-12-16 苯领集团股份公司 丙烯腈、苯乙烯和丁二烯基热塑性模塑材料
WO2018065347A1 (fr) 2016-10-04 2018-04-12 Ineos Styrolution Group Gmbh Procédé et système pour la préparation d'un polymère

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WO2000014134A1 (fr) * 1998-09-03 2000-03-16 Ciba Specialty Chemicals Holding Inc. Greffe de monomeres non satures en ethylene sur des polymeres
WO2000014135A1 (fr) * 1998-09-03 2000-03-16 Ciba Specialty Chemicals Holding Inc. Greffe de monomeres non satures en ethylene sur des polymeres
JP2002524589A (ja) * 1998-09-03 2002-08-06 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド ポリマー上へのエチレン性不飽和モノマーのグラフト化
JP2002524590A (ja) * 1998-09-03 2002-08-06 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド エチレン系不飽和モノマーのポリマーへのグラフト
US6521710B1 (en) 1998-09-03 2003-02-18 Ciba Specialty Chemicals Corporation Grafting of ethylenically unsaturated monomers onto polymers
US6525151B1 (en) 1998-09-03 2003-02-25 Ciba Specialty Chemicals Corporation Grafting of ethylenically unsaturated monomers onto polymers
CN105164166A (zh) * 2013-04-18 2015-12-16 苯领集团股份公司 丙烯腈、苯乙烯和丁二烯基热塑性模塑材料
WO2018065347A1 (fr) 2016-10-04 2018-04-12 Ineos Styrolution Group Gmbh Procédé et système pour la préparation d'un polymère
US11512149B2 (en) 2016-10-04 2022-11-29 Ineos Styrolution Group Gmbh Method and system for producing a polymer

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EP1034201A1 (fr) 2000-09-13
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