WO2010034778A1 - Compositions thermoplastiques à propriétés d'aptitude au traitement - Google Patents

Compositions thermoplastiques à propriétés d'aptitude au traitement Download PDF

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Publication number
WO2010034778A1
WO2010034778A1 PCT/EP2009/062393 EP2009062393W WO2010034778A1 WO 2010034778 A1 WO2010034778 A1 WO 2010034778A1 EP 2009062393 W EP2009062393 W EP 2009062393W WO 2010034778 A1 WO2010034778 A1 WO 2010034778A1
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component
weight
components
particularly preferably
iii
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PCT/EP2009/062393
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German (de)
English (en)
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Leonie Felicitas Braun
Maarten Staal
Axel Gottschalk
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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
    • 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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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

Definitions

  • the present invention relates to compositions containing
  • (I) at least one molding composition selected from molding compositions containing the components (A) and (B), and molding compositions containing the component (B '); as component (I);
  • thermoplastic copolymer from 20 to 90% by weight, based on the sum of components A and B, of a thermoplastic copolymer
  • thermoplastic copolymer B '
  • At least one wax as component (III) containing at least one component selected from the group consisting of polyethylene waxes, hydrocarbon waxes, fatty acid derivatives and mixtures thereof;
  • component (VI) optionally one or more fillers and / or reinforcing agents as component (VI);
  • composition according to the invention a process for the preparation of the composition according to the invention, the use of the composition according to the invention for the production of molded articles pern, foils, foams or fibers and moldings, films, foams or fibers containing the composition according to the invention.
  • compositions based on styrene-acrylonitrile polymers (SAN), acrylonitrile-butadiene-styrene (ABS) polymers, methacrylate-acrylonitrile-butadiene-styrene polymers (MABS) and acrylate-styrene-acrylonitrile polymers (ASA) are known in the prior art. known for various applications.
  • SAN styrene-acrylonitrile polymers
  • ABS acrylonitrile-butadiene-styrene
  • MABS methacrylate-acrylonitrile-butadiene-styrene polymers
  • ASA acrylate-styrene-acrylonitrile polymers
  • EP 0 450 485 A2 relates to thermoplastic molding compositions which are based on two different graft copolymers based on acrylate (A and B) and a hard matrix of one or more copolymers of styrene, ⁇ -methylstyrene, acrylonitrile, methyl methacrylate and / or phenylmaleimide are. These molding compositions are characterized by a high surface gloss and good colorability.
  • the processing of the molding compositions is carried out by extrusion or injection molding.
  • EP 0 450 485 A2 contains no information regarding the processing properties of the molding compositions.
  • the example in EP 0 450 485 A2 mentions the use of diethyl phthalate as lubricant.
  • DE 200 21 356 111 relates to mixtures containing polyvinyl chloride and ring-hydrogenated phthalate plasticizers.
  • DE 200 21 356 U1 mentions that these mixtures also contain other plastics, i.a. ABS or SAN.
  • Mixtures which furthermore contain at least one wax containing at least one component selected from the group consisting of fatty acid derivatives, hydrocarbon waxes, polyethylene waxes and mixtures thereof are not disclosed in DE 200 21 356 U1.
  • DE 200 21 356 U1 contains no information regarding the processing properties of the molding compositions.
  • DE 10 2005 028 752 A1 relates to mixtures which contain diisononyl esters of cyclohexanedicarboxylic acid, the degree of branching of the isononyl radicals of the diisononyl esters being 1.2 to 2.0.
  • the description in DE 10 2005 028 752 A1 mentions a great number of different (theoretical) possible applications of the mixtures.
  • One application concerns the use in plastics. Many different plastics are listed, including ABS and SAN.
  • DE 10 2005 028 752 A1 contains only one example in which a diisononyl ester of cyclohexanedicarboxylic acid in PVC is used.
  • SAN styrene-acrylonitrile polymers
  • ABS acrylonitrile-butadiene-styrene
  • MABS methacrylate-acrylonitrile-butadiene-styrene polymers
  • ASA acrylate-styrene-acrylonitrile polymers
  • compositions are multicomponent systems
  • the individual components of the compositions must be mixed to prepare the compositions and moldings, films, foams or fibers obtainable therefrom and, according to the known processes of thermoplastic processing, e.g. by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering.
  • thermoplastic processing e.g. by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering.
  • This processing is generally energy intensive.
  • In the production of moldings, films, foams or fibers by extrusion large forces must be expended.
  • it is desirable to provide compositions in which processing into moldings, films, foams or fibers is possible with the least possible expenditure of energy.
  • the object of the present invention is therefore to provide compositions in which processing into moldings, films, foams or fibers is possible with the least possible expenditure of energy. Furthermore, it is particularly desirable that components are used in the compositions, which are suitable for contact with food, as well as for use in medical devices and / or children's toys, so that the compositions themselves are suitable for these applications.
  • compositions comprising
  • thermoplastic copolymer B a thermoplastic copolymer obtainable by reacting b1) 60 to 100 wt .-%, based on component B, at least one vinyl aromatic monomer, more preferably styrene and / or ⁇ -methyl styrene, b2) 0 to 40 wt .-%, based on component B, acrylonitrile, and b3) 0 to 40% by weight, based on component B, of at least one further monoethylenically unsaturated monomer;
  • thermoplastic copolymer obtainable by reacting b'1) from 50 to 95% by weight, based on component B', of at least one vinylaromatic monomer, b'2) from 5 to 50% by weight, based on component B ' , Acrylonitrile, b'3) from 0 to 35% by weight, based on component B ', of at least one further monoethylenically unsaturated monomer;
  • R 1 is C 1 -C 10 -alkyl or C 3 -C 8 -cycloalkyl, m is O, 1, 2 or 3, n is 2, 3 or 4, and
  • R is hydrogen or C 1 -C 30 -alkyl; or the group - (COOR) n forms an anhydride of the formula
  • At least one wax as component (III) containing at least one component selected from the group consisting of polyethylene waxes, hydrocarbon waxes, fatty acid derivatives and mixtures thereof, preferably selected from the group consisting of polyethylene waxes, hydrocarbon waxes and mixtures comprising Hydrocarbon waxes and polyethylene waxes;
  • component (VI) optionally one or more fillers and / or reinforcing agents as component (VI).
  • compositions of the invention generally contain
  • component (i) 90 to 99.98% by weight, preferably 82 to 99.8% by weight, more preferably 86 to 99% by weight of component (I);
  • components I, II and III being 100% by weight; (iv) from 0 to 50% by weight, preferably from 0 to 20% by weight, particularly preferably from 0.05 to 15% by weight, based in each case on the total weight of components I, II and III, of component (IV) ; (v) 0 to 50% by weight, preferably 0 to 40% by weight, particularly preferably 0.05 to 30% by weight, in each case based on the total weight of components I, II and III, of component (V) ; and
  • the molding compositions contained in the compositions according to the invention generally contain the components A and B (embodiment 1), or the molding compositions contain the component B '(embodiment 2), wherein mean
  • thermoplastic copolymer obtainable by reacting b'1) 50 to 95, preferably 55 to 80 and particularly preferably 60 to 70% by weight, based on component B', of at least one vinylaromatic monomer, b'2) 5 to 50, preferably 20 to 45 and particularly preferably 30 to 40 wt .-%, based on component B ', acrylonitrile, b'3) 0 to 35, preferably 0 to 20 and particularly preferably 0 to 15 wt .-%, based on component B ', at least one further monoethylenically unsaturated monomer.
  • (meth) acrylic acid or (meth) acrylate used below is understood as meaning acrylic acid and / or methacrylic acid or acrylate and / or methacrylate.
  • the molding compositions according to the invention comprise in one embodiment (embodiment 1) 10 to 80 wt .-%, preferably 20 to 70 wt .-%, particularly preferably 25 to 60 wt .-% of the component A as a graft copolymer, and
  • thermoplastic copolymer From 20 to 90% by weight, preferably from 30 to 80% by weight, particularly preferably from 40 to 75% by weight, of the component B as thermoplastic copolymer (the percentages by weight are in each case based on the total weight of the components A and B).
  • the graft copolymer A comprises as a graft base
  • component A 10 to 70 wt .-%, preferably 20 to 60 wt .-%, particularly preferably 30 to 55 wt .-% of component a2 (the wt .-% are each based on the weight of component A).
  • the graft base a1 is obtainable by reaction of
  • wt .-% 0 to 10 wt .-%, preferably 0.01 to 5 wt .-%, particularly preferably 0.02 to 2 wt.
  • Component a1.3 (the wt .-% are each based on the weight of component a1).
  • the graft a2 is available by reaction of
  • Component a2.2 and 0 to 35 wt .-%, preferably 0 to 15 wt .-%, particularly preferably 0 to 5 wt .-%
  • Component a2.3 (the wt .-% are each based on the weight of component a2), in the presence of the graft a1.
  • thermoplastic copolymer B is obtainable by reacting 60 to 100% by weight, preferably 60 to 85% by weight, particularly preferably 65 to 82% by weight of component b1,
  • wt .-% preferably 15 to 40 wt .-%, particularly preferably 18 to 35 wt .-% of component b.2, and 0 to 40 wt .-%, preferably 0 to 25 wt .-%, especially preferably 0 to 17% by weight Component b.3 (the wt .-% are each based on the weight of component B).
  • component a1.1 one or more (C 1 -C 10 -alkyl) esters of (meth) acrylic acid and / or one or more conjugated dienes can be used according to the invention.
  • Preferred (CrCio-alkyl) esters of (meth) acrylic acid used as components a1.1 are methyl, butyl, hexyl, octyl or 2-ethylhexyl (meth) acrylate or mixtures thereof, in particular n-butyl or 2-ethylhexyl (meth) acrylate or mixtures thereof. Very particular preference is given to n-butyl acrylate and methyl methacrylate.
  • Preferred conjugated dienes used as components a1.1 are butadiene, isoprene, chloroprene or mixtures thereof. Preference is given to using butadiene or isoprene or mixtures thereof, particularly preferably butadiene.
  • the graft base a1 can contain crosslinking monomers a1.2.
  • Suitable polyfunctional, crosslinking monomers a1.2 are monomers having at least two ethylenically unsaturated, non-1,3-conjugated double bonds.
  • Examples include triallyl cyanurate, divinylbenzene, divinyl esters of dicarboxylic acids such as diallyl maleate, diallyl fumarate, diallyl phthalate, allyl acrylate and methacrylate, Dihydrodicyclopentadienacrylat, di-allyl ether and divinyl ether bifunctional alcohols such as ethylene glycol and 1, 4-butanediol, diesters of polyhydric alcohols with acrylic and methacrylic acid such as butanediol diacrylate, ethylene glycol diacrylate, hexanediol dimethacrylate.
  • Examples of further monoethylenically unsaturated monomers a1.3 which may be used are: vinylaromatic monomers such as styrene or styrene derivatives such as C 1 to C 8 alkylstyrene, for example ⁇ -methylstyrene, acrylonitrile, methacrylonitrile; furthermore also the glycidyl esters, glycidyl acrylate and methacrylate; N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexylmaleimide; Acrylic acid; methacrylic acid; furthermore dicarboxylic acids such as maleic acid; Nitrogen-functional monomers such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate; Vinylimidazole, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole, vinylaniline; aromatic and araliphatic esters of acrylic acid and methacrylic
  • At least one (meth) acrylic acid Ci_io-alkyl ester is used as component a1.1.
  • acrylic esters derived from alcohols having 1 to 8 carbon atoms such as methyl methacrylate, ethyl acrylate, n-butyl acrylate and / or ethylhexyl acrylate.
  • These acrylic esters may optionally be used together with up to 10% by weight of the crosslinking polyfunctional monomers mentioned as component a1.2).
  • the weather-resistant ASA polymers are then produced.
  • up to 50% by weight of at least one further monoethylenically unsaturated monomer a1.3 may be present during the polymerization together with the at least one (meth) acrylic acid C 1-10 -alkyl ester.
  • a graft base is prepared, based on a1),
  • a1.1 from 70 to 99.9% by weight, preferably from 90 to 99% by weight of butadiene, and a1.3) from 0.1 to 30% by weight, preferably from 1 to 10% by weight, of styrene.
  • styrene As component a2.1 styrene, ⁇ -methylstyrene or a mixture of these compounds is used, preference is given to styrene.
  • Component a.2.2 is acrylonitrile.
  • Suitable compounds are, for example, the monoethylenically unsaturated monomers (other than styrene, ⁇ -methylstyrene and acrylonitrile) already mentioned as components a1.1 and a1.3, where Methyl methacrylate, glycidyl acrylate, or methacrylate are preferred.
  • monoethylenically unsaturated monomers it is also possible to use, as component a2.3, crosslinking and / or graft-active compounds which contain two or more double bonds capable of copolymerization.
  • crosslinking and / or graft-active compounds examples include the compounds described as component a1.2, but also other crosslinkers or graft-active compounds known to the skilled person or described in the literature, for example dienes such as butadiene or isoprene.
  • crosslinkers or graft-active compounds can generally be used in amounts of 0 to 10% by weight, preferably 0 to 5% by weight, in each case based on the total weight of component a2.3, as component a2.3. In a particularly preferred embodiment of the invention, however, component a2.3 contains no compounds acting as crosslinking and / or grafting agents.
  • styrene As component b1, styrene, ⁇ -methylstyrene or a mixture of these compounds is used, preference is given to styrene.
  • Component b2 is acrylonitrile.
  • the unsaturated monomers already mentioned as component a2.3 are suitable.
  • Preferred components B are polystyrene, SAN, poly- ⁇ -methylstyrene-acrylonitrile or mixtures thereof.
  • Component A is a graft copolymer comprising a graft base a1 and at least one graft a2.
  • the graft copolymer A can have a more or less perfectly pronounced core-shell structure (graft base a1 represents the core, the graft a2 the shell), but it is also possible that the graft a2 encloses the graft base a1 only incomplete or covered or else the graft support a2 completely or partially penetrates the graft base a1.
  • the graft base a1 may in one embodiment of the invention contain a so-called core, which may be formed from a soft elastomeric polymer or a hard polymer;
  • the core is preferably formed from a hard polymer, in particular polystyrene or a styrene copolymer.
  • Such Graft cores and their preparation are known to the person skilled in the art and are described, for example, in EP-A 535456 and EP-A 534212.
  • graft bases a1 which differ from each other, for example, in their composition or in particle size.
  • Such mixtures of different grafting bases can be prepared by methods known per se to those skilled in the art, for example by separately preparing two or more rubber latices and mixing the corresponding dispersions. The wet rubbers are separately precipitated from the corresponding dispersions and mixed, for example, in an extruder or the corresponding dispersions are worked up completely separately and the graft bases obtained are subsequently mixed.
  • the graft copolymer A may have one or more further graft layers or shells between the graft base a1 and the graft base a2 - for example with other monomer compositions - but preferably the graft copolymer A has no further graft layers except the graft a2. envelopes or shells on.
  • the polymer of the graft base a1 usually has a glass transition temperature below 0 0 C, preferably a glass transition temperature below -20 0 C, in particular below -30 ° C.
  • a polymer of the graft a2 forming monomers usually has a glass transition temperature of more than 30 0 C, in particular more than 50 ° C (each determined according to DIN 53765).
  • the graft copolymers A usually have an average particle size d 50 of from 50 to 1200 nm, preferably from 50 to 1000 nm and particularly preferably from 50 to 850 nm. These particle sizes can be achieved if, as graft base a1, particle sizes of 50 to 1000 nm are preferred of 50-700 nm, and more preferably 50-600 nm. According to one embodiment of the invention, the particle size distribution is monomodal.
  • the particle size distribution of component A is bimodal, wherein 60-90 wt .-% have a mean particle size of 50-200 nm and 10-40 wt .-% have an average particle size of 200-850 nm on the total weight of component A.
  • the mean particle size or particle size distribution are the sizes determined from the integral mass distribution. These and the other mean particle sizes mentioned in the context of the present invention are in all cases, the weight average particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymere 250 (1972), pages 782-796.
  • the preparation of the molding compositions according to embodiment 1 comprises at least the following process steps:
  • the preparation of the graft base a1 can be achieved by emulsion, solution, mass or suspension polymerization of the components a1.1, a1.2 and a1.3, - application of a graft a2 by polymerization of the components a2.1, a2.2 and a2. 3 in the presence of the graft base a1, and melt blending of the graft copolymer A with a separately prepared thermoplastic copolymer B take place.
  • the graft copolymers A can be prepared by graft polymerization of the components a2.1, if appropriate a2.2 and optionally a2.3, onto at least one of the abovementioned grafting bases a1.
  • Suitable preparation processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers A are preferably prepared by free radical emulsion polymerization in the presence of latices of component a1 at temperatures of 20 0 C - 90 0 C using water-soluble or oil-soluble initiators such as peroxodisulfate or benzoyl peroxide, or by means of redox initiators. Redox initiators are also suitable for polymerization below 20 0 C.
  • Suitable polymerization processes are described in WO 02/10222, DE-A 28 26 925, 31 49 358 and in DE-C 12 60 135.
  • the structure of the graft is preferably carried out in the emulsion polymerization process, as described in DE-A 32 27 555, 31 49 357, 31 49 358, 34 14 1 18.
  • the defined setting of the particle sizes of 50-1200 nm according to the invention preferably takes place after the processes which are described in DE-C 12 60 135 and DE-A 28 26 925, and Applied Polymer Science, Volume 9 (1965), page 2929.
  • the use of polymers having different particle sizes is known, for example from DE A 28 26 925 and US Pat. No. 5,196,480.
  • the graft base a1 is prepared by using the (meth) acrylic ester (s) and / or diene a1.1 and / or dienes a1.1 used according to one embodiment of the invention Pfropfagenz acting optionally present compound a1.2, optionally together with the other monoethylenically unsaturated monomers a1.3, in aqueous emulsion in a conventional manner at temperatures between 20 and 100 0 C, preferably between 50 and 90 0 C, be polymerized.
  • the customary emulsifiers such as, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or rosin soaps.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are used.
  • the emulsifiers are used in amounts of from 0.5 to 5% by weight, in particular from 0.7 to 2% by weight, based on the monomers used in the preparation of the graft base a1.
  • a weight ratio of water to monomers of 4: 1 to 0.6: 1 is used.
  • the polymerization initiators are in particular the customary persulfates, such as potassium persulfate. However, redox systems can also be used.
  • the initiators are generally used in amounts of from 0.1 to 1% by weight, based on the monomers used in the preparation of the graft base a1.
  • Further polymerization auxiliaries may be the customary buffer substances which are used to adjust pH values of preferably 6-9, such as sodium bicarbonate and sodium pyrophosphate, and 0-3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric ⁇ -methylstyrene be used in the polymerization.
  • the exact polymerization conditions in particular the type, dosage and amount of the emulsifier, be determined within the ranges specified above in detail so that the resulting latex of the optionally crosslinked (meth) acrylic acid ester polymer and / or diene polymer a1 d 5 o value in Range of about 50 - 1000 nm, preferably 50 - 700 nm, more preferably in the range of 50 - 600 nm possesses.
  • the particle size distribution of the latex should preferably be narrow.
  • the graft polymer A is then in a next step in the presence of the resulting latex of the optionally crosslinked (meth) acrylic ester polymer and / or diene polymer a1 according to one embodiment of the invention RPg a monomer mixture of component a2.1, preferably styrene, Component a2.2, acrylonitrile, and optionally polymerized component a2.3.
  • the monomers a2.1, a2.2 and optionally a2.3 can be added individually or in a mixture with one another. For example, one can first graft styrene alone, and then a mixture of styrene and acrylonitrile.
  • graft copolymerization on the optionally crosslinked (meth) acrylic acid ester polymer which serves as the graft base and / or Diene polymer again in aqueous emulsion under the usual conditions described above.
  • the graft copolymerization may suitably be carried out in the same system as the emulsion polymerization for the preparation of the graft base a1, wherein, if necessary, further emulsifier and initiator may be added.
  • the monomer mixture to be grafted on in accordance with one embodiment of the invention can be added to the reaction mixture all at once, batchwise in a plurality of stages, for example to build up a plurality of graft coatings or preferably continuously during the polymerization.
  • the graft copolymerization of the mixture of components a2.1, a2.2 and optionally a2.3 in the presence of the crosslinking acrylic ester polymer a1 is conducted in such a way that a degree of grafting of 10 to 70% by weight, preferably 20 to 60% by weight, is achieved. %, in particular 30-55 wt .-%, based on the total weight of component A, in the graft copolymer A results. Since the graft from prey in the graft copolymerization is not 100%, a slightly larger amount of the monomer mixture of a2.1, a2.2 and optionally a2.3 must be used in the graft copolymerization, as it corresponds to the desired degree of grafting.
  • the control of the graft from prey in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A is familiar to the expert and can be done, for example, by the metering rate of the monomers or by control addition (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 et seq .).
  • the emulsion graft copolymerization generally about 5-15% by weight, based on the graft copolymer, of free, ungrafted copolymer of the components a2.1, a2.2 and optionally a2.3 are formed.
  • the proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization can be determined, for example, by the method described in US-A 2004/0006178.
  • the preparation of the grafting base a1 can be carried out in the presence of seed particles and / or after the preparation of the grafting base a1 and before the application of the grafting layer a2, an agglomeration step can be carried out.
  • an agglomeration step can be carried out.
  • Seed particles generally have a particle size d 50 of 10 to 200 nm, preferably from 10 to 180 nm, particularly preferably from 10 to 160 nm. It is preferred to use seed particles which have a narrow width of the particle size distribution. Of these, seed particles which have a monomodal particle size distribution are particularly preferred.
  • the seed particles may in principle be composed of monomers forming elastomeric polymers, for example 1,4-butadiene or acrylates, or of a polymer whose glass transition temperature is more than 0 ° C., preferably more than 25 ° C.
  • the preferred monomers on which these seed particles are based include vinyl aromatic monomers such as styrene, ring-substituted styrenes or ⁇ -methylstyrene, including preferably styrene, acrylonitrile, alkylacrylic acid, alkyl acrylates, including preferably n-butyl acrylate. Also suitable are mixtures of two or more, preferably two, of the monomers mentioned. Very particular preference is given to seed particles of polystyrene or n-butyl acrylate.
  • seed particles are preferably obtained by particle-forming heterogeneous polymerization processes, preferably by emulsion polymerization.
  • the seed particles are submitted according to the invention, whereby it is possible to first prepare the seed particles separately, work up and then use them. However, it is also possible to prepare the seed particles and then add them without prior workup, the monomer mixture from a1.1, if necessary a1.2 and possibly a1.3.
  • agglomeration processes for the partial or complete agglomeration of the graft base a1 are known to the person skilled in the art or the agglomeration can be carried out by methods known per se to the person skilled in the art (see, for example, Keppler et al., Angew Markomol Chemistry, 2, 1968, No. 20, pp. 1-25 ).
  • the agglomeration method is not limited in principle. Thus, physical processes such as freeze or pressure agglomeration processes can be used. However, it is also possible to use chemical methods to agglomerate the graft base. The latter include the addition of electrotes or of inorganic or organic acids.
  • the agglomeration is preferably carried out by means of an agglomeration polymer. As such, for example, polyethylene oxide polymers, polyvinyl ethers or polyvinyl alcohols may be mentioned.
  • Suitable agglomeration polymers include the further copolymers which comprise C 1 - to C 12 -alkyl acrylates or C 1 - to C 12 -methalkyl acrylates and polar monomers such as acrylamide, methacrylamide, ethacrylamide, n-butylacrylamide, maleic acid amide or (meth) acrylic acid.
  • these copolymers can be made up of further monomers, including dienes, such as butadiene or isoprene.
  • the Agglomerisationspolymerisate may have a multi-stage structure and z.
  • B have a core / shell construction.
  • the core for example, come polyacrylates such as polyethyl acrylate and shell as particles on (meth) alkyl acrylates and said polar comonomers into consideration.
  • Particularly preferred Agglomerisationspoly- merisat is a copolymer of 92 to 99 wt .-% ethyl acrylate or - methacrylate and 1 to 8 wt .-% of (meth) acrylamide and / or (meth) acrylic acids.
  • the Agglomerisationspolymerisate are usually used in the form of a dispersion. In the agglomeration of from 0.1 to 5, preferably from 0.5 to 3 parts by weight of Agglomerisationspolymerisate are used per 100 parts by weight of the graft base generally.
  • the novel graft copolymers A can be used as they are obtained in the reaction mixture, for example as latex emulsion or dispersion. Alternatively and as it is preferred for most applications, but they can also be worked up in a further step. Measures for processing are known to the person skilled in the art. This includes z. B, that the graft copolymers A are isolated from the reaction mixture, e.g. by spray-drying, shearing or by precipitation with strong acids or by nucleating agents such as inorganic compounds e.g. Magnesium sulfate. However, the graft copolymers A present in the reaction mixture can also be worked up by dehydrating them in whole or in part. It is also possible to carry out the workup by means of a combination of the measures mentioned.
  • thermoplastic copolymers B can be prepared by processes known per se, such as by bulk, solution, suspension or emulsion polymerization, preferably by solution polymerization (see GB-A 14 72 195). Preference is given to copolymers B having molecular weights M w of 60,000 to 300,000 g / mol, determined by light scattering in dimethylformamide.
  • component B is isolated after production by processes known to those skilled in the art, and preferably processed into granules.
  • thermoplastic copolymer B ' is obtainable by reacting
  • b'2 from 5 to 50, preferably from 20 to 45 and particularly preferably from 30 to 40,% by weight of acrylonitrile, b'3) 0 to 35, preferably 0 to 20 and particularly preferably 0 to 15 wt .-% of at least one further monoethylenically unsaturated monomer (the wt .-% are each based on the weight of component B ').
  • Styrene, ⁇ -methylstyrene or a mixture of these compounds is used as component b'1, preference being given to styrene.
  • Component b'2 is acrylonitrile.
  • Suitable components b'3 are, for example, the monoethylenically unsaturated monomers already mentioned as components a1.1 and a1.3 (with the exception of styrene, .alpha.-methylstyrene and acrylonitrile), preference being given to methyl methacrylate, glycidyl acrylate or methacrylate.
  • suitable components b'3 are also crosslinking and / or graft-active compounds which contain two or more double bonds capable of copolymerization.
  • suitable crosslinking and / or graft-active compounds as component b'3 are, for example, the compounds described as component a1.2, but also other crosslinkers or graft-active compounds known to the skilled person or described in the literature, for example dienes such as butadiene or isoprene.
  • crosslinkers or graft-active compounds can generally be used in amounts of 0 to 10 wt .-%, preferably 0 to 5 wt .-%, each based on the total weight of component b'3, as component b'3. In a particularly preferred embodiment of the invention, however, component b'3 contains no compounds acting as crosslinking and / or grafting agent.
  • the preferred component B ' is SAN.
  • thermoplastic copolymers B can be prepared by methods known per se, such as by bulk, solution, suspension or emulsion polymerization, preferably by solution polymerization (see GB-A 14 72 195). Preference is given to copolymers B having molecular weights M w of 60,000 to 300,000 g / mol, determined by light scattering in dimethylformamide.
  • component B is isolated after production by processes known to those skilled in the art, and preferably processed into granules.
  • compositions according to the invention have at least one cyclohexanepolycarboxylic acid derivative of the formula (I):
  • R 1 is C 1 -C 10 -alkyl or C 3 -C 8 -cycloalkyl, m is 0, 1, 2 or 3, n is 2, 3 or 4, and
  • R is hydrogen or C 3 -alkyl, CrC preferably 2 -alkyl, more preferably d-Ci 8 alkyl, most preferably Ci-C 3 alkyl, in particular C 8 -C 3 -alkyl, where at least one radical R represents Ci-C 30 alkyl, preferably -C 2 -alkyl, more preferably d-Ci 8 alkyl, most preferably Ci-C 3 alkyl, in particular C 8 -C 3 -alkyl; or the group - (COOR) n forms an anhydride of the formula
  • the cyclohexanepolycarboxylic acid derivatives according to the invention are in particular mono-, di-, tri-, tetra-esters and anhydrides of the cyclohexanepolycarboxylic acids.
  • all carboxylic acid groups are esterified, ie R is preferably dC 3 o-alkyl.
  • the dC 3 o-alkyl radical can be linear, branched or, in the case of an alkyl radical having 3 to 30 C atoms, cyclic.
  • the dC 3 o-alkyl radical may furthermore be substituted, for example, by C 1 -C 10 -alkoxy groups.
  • the C 1 -C 30 -alkyl radical is particularly preferably a linear or branched alkyl radical which comprises 1 to 30, preferably 1 to 20, particularly preferably 1 to 18, very particularly preferably 1 to 13, in particular 8 to 13, carbon atoms.
  • Ci-C 30 alkyl, CrC preferably 2 O-, particularly preferably CRCI 8 -, very particularly preferably CrCl 3 -, in particular C 8 -C 3 alkyl radical may furthermore be mixtures of different alkyl radicals which differ in the number of carbon atoms and / or in their degree of branching.
  • the iso-nonyl, iso-decyl, iso-undecyl, iso-dodecyl and iso-tridecyl radicals mentioned below are mixtures of variously branched alkyl radicals, as known to those skilled in the art.
  • Cyclohexanpolycarbonklarederivate of formula (I) which differ in their alkyl radicals R, for example in the number of carbon atoms and / or in the degree of branching of the alkyl radicals.
  • the n radicals R in a cyclohexanepolycarboxylic acid derivative of the formula (I) can also be different (mixed esters) (or the same) in the case where n ⁇ 2.
  • R is preferably -C 2 -alkyl, particularly preferably Ci-C 8 alkyl, most preferably -C 2 -alkyl, in particular very particularly preferably Ci-C 8 alkyl, more in particular very particularly preferably Ci-C 3 - Alkyl and in particular C 8 -C 3 alkyl.
  • alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl , n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl, iso-dodecyl, n-tridecyl, iso-tridecyl, stearyl, and n-eicosyl.
  • Very particularly preferred alkyl groups R are 2-ethylhexyl, isononyl and iso-decyl.
  • n is 2.
  • R 1 When m is 2 or 3, the radicals R 1 may be the same or different.
  • the C 1 -C 1 0-alkyl or Ci-C 30 alkyl groups may be straight or branched.
  • R 1 represents an alkyl group, it is preferably a -C 8 - alkyl group, particularly preferably a Ci-C 6 alkyl group.
  • alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl ,
  • n 0.
  • the at least one cyclohexanepolycarboxylic acid derivative is preferably selected from the group consisting of ring-hydrogenated mono- and dialkyl esters of phthalic acid, isophthalic acid and terephthalic acid, ring-hydrogenated mono-, di- and trialkyl esters of trimellitic acid, of trimesic acid and of hemimellitic acid or mono-, di-, tri- and Tetraalkyl esters of pyromellitic acid, wherein the alkyl groups may be linear or branched and each having 1 to 30, preferably 2 to 10, more preferably 3 to 18 carbon atoms, and mixtures of two or more thereof.
  • Suitable cyclohexanepolycarboxylic acid derivatives are disclosed, for example, in WO99 / 32427.
  • cyclohexane-1 2-dicarboxylic acid alkyl esters, alkyl cyclohexane-1, 4-dicarboxylates and cyclohexane-1, 3-dicarboxylic acid alkyl esters, i. n in formula (I) is very particularly preferably 2 and the 2 COOR groups are arranged in ortho, meta or para positions relative to one another. Suitable radicals R are mentioned above.
  • Suitable cyclohexanepolycarboxylic acid derivatives are, in particular, the cyclohexane-1,2-dicarboxylic acid esters disclosed in WO 99/32427 and listed again below:
  • Cyclohexane-1,2-dicarboxylic acid di (isopentyl) ester obtainable by hydrogenating diisopentyl phthalate with the Chemical Abstracts Registry Number ('CAS No.') 84777-06-0;
  • Di (isoheptyl) cyclohexane-1,2-dicarboxylic acid obtainable by hydrogenating diisopropylheptophthalate with CAS No. 71888-89-6;
  • Cyclohexane-1,2-dicarboxylic acid di (isononyl) ester obtainable by hydrogenating a diisononyl phthalate with CAS No. 68515-48-0;
  • Di (isononyl) cyclohexane-1,2-dicarboxylic acid obtainable by hydrogenating a diisononyl phthalate with CAS No. 28553-12-0, based on n-butene;
  • Di (isononyl) cyclohexane-1,2-dicarboxylic acid obtainable by hydrogenating a diisononyl phthalate with CAS No. 28553-12-0 based on isobutene;
  • a 1,2-di-C9-ester of cyclohexanedicarboxylic acid obtainable by hydrogenating a di (nonyl) phthalate with CAS No. 68515-46-8;
  • di (isodecyl) cyclohexane-1,2-dicarboxylic acid obtainable by hydrogenating a diisodecyl phthalate with CAS No. 68515-49-1;
  • a 1, 2-di-C7-1 1 -ester of cyclohexanedicarboxylic acid obtainable by hydrogenation of the di-C7-1 1-phthalates with the following CAS no. 1 11 381-89-6, 1 11 381 90-9, 1 11 381 91-0, 68515-44-6, 68515-45-7 and 3648-20-2;
  • a 1,2-di-C9-1 1 ester of cyclohexanedicarboxylic acid obtainable by hydrogenating a di-C9-1 1-phthalate with CAS No. 98515-43-6;
  • a 1,2-di (isodecyl) cyclohexanedicarboxylic acid ester obtainable by hydrogenating a diisodecyl phthalate mainly consisting of di (2-propylheptyl) phthalate;
  • a 1,2-di-C7-9 cyclohexanedicarboxylic acid ester obtainable by hydrogenating the corresponding phthalic acid ester of the branched-chain or linear C7-9 alkyl ester groups; corresponding phthalates useful as starting materials, for example, have the following CAS #: di-C7.9 alkyl phthalate having the CAS No. 1111381-89-6; Di-C7 alkyl phthalate with CAS No. 68515-44-6; and di-C9 alkyl phthalate having CAS No. 68515-45-7.
  • palatinol AH (CAS No. 1 17-81-7), palatinol 71 1 (CAS no No. 68515-42-4), palatinol 91 1 (CAS No. 68515-43-5), palatinol 1 1 (CAS No. 3648-20-2), palatinol Z (CAS No. 26761-40-0) and palatinol DIPP (CAS No. 84777-06-0) is to be assessed as suitable for the purposes of the present invention.
  • compositions according to the invention particularly suitable cyclohexane polycarboxylic acid derivatives are 1, 2-Cyclohexandicarbonklareester selected from the group consisting of 1, 2-Diisobutylcyclohexandicarbonklareester, 1, 2-di- (2-ethylhexyl) cyclohexanedicarboxylic, 1, 2-Diisononylcyclohexandicarbon- acid ester and 1 , 2-Diisodecylcyclohexandicarbonklaester, most particularly preferred are 1, 2-di- (2-ethylhexyl) cyclohexanedicarboxylic esters and 1, 2-Diisononylcyclohexandicarbonklar and most particularly preferred is 1, 2-Diisononylcyclohexandicarbonklaer.
  • diisononylcyclohexanedicarboxylic acid ester (diisononylcyclohexane-1,2-dicarboxylate), which is also commercially available under the name Hexamoll® DINCH (from BASF AG).
  • the preparation of the cyclohexanepolycarboxylic acid derivatives preferably takes place according to the process disclosed in WO 99/32427.
  • This method comprises hydrogenating a benzene polycarboxylic acid or a derivative thereof or a mixture of two or more thereof by contacting the benzene polycarboxylic acid or the derivative thereof or the mixture of two or more thereof with a hydrogen-containing gas in the presence of a catalyst of at least one metal as the active metal the VIII.
  • Subgroup of the Periodic Table, alone or together with at least one metal of the I or VII subgroup of the Periodic Table, applied on a support comprises, wherein the support has macropores.
  • the hydrogenation of benzenepolycarboxylic acid or a derivative thereof or an overall premix of two or more thereof is generally conducted at a temperature of 50 to 250 0 C, preferably 70-220 0 C, particularly preferably from 80 to 170 0 C.
  • the pressures used are generally ⁇ 10 bar, preferably 20 to 300 bar.
  • the process according to the invention can be carried out either continuously or batchwise, the continuous process being preferred.
  • hydrogenation gases it is possible to use any gases which contain free hydrogen and have no harmful amounts of catalyst poisons, such as CO, for example.
  • catalyst poisons such as CO
  • reformer exhaust gases can be used.
  • pure hydrogen is used as the hydrogenation gas.
  • the hydrogenation can be carried out in the absence or presence of a solvent or diluent, i. H. it is not necessary to carry out the hydrogenation in solution.
  • the hydrogenation may be e.g. also be carried out in the gas phase.
  • a solvent or diluent is used. Any suitable solvent or diluent may be used as solvent or diluent. The choice is not critical, as long as the solvent or diluent used is capable of forming a homogeneous solution with the benzene dicarboxylic acid (ester) to be hydrogenated.
  • the solvents or diluents may also contain water.
  • suitable solvents or diluents include the following: straight chain or cyclic ethers, such as tetrahydrofuran or dioxane, and aliphatic alcohols in which the alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 6 carbon atoms.
  • preferably usable alcohols are i-propanol, n-butanol, i-butanol and n-hexanol. Mixtures of these or other solvents or diluents may also be used.
  • the amount of solvent or diluent used is not particularly limited and may be chosen freely as required, but those amounts are preferred which lead to a 10 to 70 wt .-% - solution of the (the) benzenedicarboxylic acid (esters).
  • Particular preference is given to using the product formed in the hydrogenation, ie the corresponding cyclohexane derivative, as solvent, if appropriate in addition to other solvents or diluents.
  • a part of the product formed in the process may be admixed with the benzene polycarboxylic acid to be hydrogenated or the derivative thereof.
  • the cyclohexanepolycarboxylic acid derivatives used in the compositions according to the invention are prepared according to the following process:
  • R 1 is C 1 -C 10 -alkyl or C 3 -C 8 -cycloalkyl, m is 0, 1, 2 or 3, and n is 2, 3 or 4,
  • R 3 dC o-alkyl, CrC preferably 2 o-alkyl, particularly preferably Ci-C 8 -alkyl, very particularly preferably Ci-C 3 alkyl, in particular C 8 -C 3 alkyl,
  • R 1 , m, n and R are mentioned above with respect to the cyclohexanepolycarboxylic acid according to formula I.
  • benzene polycarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, hemimellitic acid and pyromellitic acid. Very particular preference is given to using phthalic acid.
  • the aforementioned acids are commercially available.
  • the alcohols used are preferably the alcohols corresponding to the radicals R of the cyclohexanepolycarboxylic acid derivatives of the formula I.
  • the alcohols R-OH used for the esterification with the benzene polycarboxylic acids can each be the individual isomers of the alcohols corresponding to the abovementioned radicals R or mixtures of different alcohols with isomeric alkyl radicals having the same number of carbon atoms and / or mixtures of different alcohols different number of carbon atoms.
  • the alcohols or alcohol mixtures suitable for reaction with the benzene polycarboxylic acids can be prepared by all processes known to the person skilled in the art. Suitable processes for the preparation of alcohols or process steps used in the production of alcohols are, for example:
  • carboxylic acids and carboxylic acid esters in particular fatty acids and fatty acid esters, for example as disclosed in US 5,463,143, US 5,475,159, WO 94/10112, CA 2,314,690, WO 94/06738, JP-A 06 065 125 and US 3,361,832;
  • a process comprising a telomerization step for example as disclosed in EP-A 0 330 999, DE-A 1 138 751, US 5,908,807, NE-6,603,884 and US 3,091,628;
  • a process comprising an isomerization step for example as disclosed in DE-A 42 28 887;
  • Alcohols are preferably employed are - as mentioned above - alcohols Ci-Ci alkyl groups having 3, more preferably C 8 -C 3 -alkyl radicals. I ke the longer-chain C 8 -Ci 3 - alcohols or alcohol mixtures containing these alcohols are particularly preferably prepared by catalytic hydroformylation (also referred to as oxo reaction) of olefins and subsequent hydrogenation of the aldehydes formed. Suitable hydroformylation processes are known to the person skilled in the art and are disclosed in the abovementioned documents.
  • C 5 -alcohols or mixtures which contain C 5 -alcohols, particularly preferably n-pentanol can be prepared, for example, by hydroformylating butadiene in the presence of an aqueous solution of a rhodium compound and a phosphine as catalyst. Such a method is disclosed, for example, in EP-A 0 643 031.
  • Suitable C 7 -alcohol mixtures which can be used for esterification with the benzene polycarboxylic acids are disclosed, for example, in JP-A 2000/319 444.
  • the C 7 -alcohol mixture is prepared by hydroformylation with subsequent hydrogenation of the aldehydes formed.
  • C 9 -alcohols or mixtures comprising C 12 -alkanols are preferably prepared by dimerization of butenes, hydroformylation of the octenes obtained and subsequent hydrogenation of the resulting C 9 aldehyde.
  • Suitable processes and mixtures containing Cg-alcohols are described, for example, in WO 92/13818, DE-A 20 09 505, DE-A 199 24 339, EP-A 1 1 13 034, WO 2000/63151, WO 99/25668, JP -A 1 160 928, JP-A 03 083 935, JP-A 2000/053803, EP-A 0 278 407 and EP-A 1 178 029.
  • Cio-alcohols and mixtures containing these alcohols are disclosed, for example, in WO 2003/66642, WO 2003/18912, EP-A 0 424 767, WO 2002/68369, EP-A 0 366 089 and JP-A 2001/002829.
  • C 3 alcohols, and mixtures containing these alcohols are for example disclosed in DE-A 100 32 580, DE-A 199 55 593 and WO 2002/00580.
  • alkyl radicals R of the cyclohexanepolycarboxylic acid esters are C 1 - to C 4 -alkyl radicals
  • these are prepared by reacting the benzene-polycarboxylic acids of the formula II with methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec .- Butanol or tert-butanol obtained.
  • mixtures of the stated propanols or butanols or individual isomers may be used to prepare benzene polycarboxylic acid esters in which R 3 or 4.
  • individual isomers of propanol or butanol are used.
  • the preparation of the aforementioned Cr to C 4 -AlkOhOIe is known in the art.
  • alkyl radicals R of the cyclohexanepolycarboxylic C 5 - to C 3 alkyl radicals preferably C 8 -C 3 -alkyl radicals, preferably C 5 - to C 3 -alcohols, most preferably C 8 -C 3 alcohols, especially preferably C 8 -, C 9 - and / or Cio alcohols used
  • the degrees of branching (ISO index) of generally 0.1 to 4, preferably 0.5 to 3, particularly preferably 0.8 to 2 and in particular at 1 to 1, 5, ie, in general, the respective alcohols are mixtures of different isomers.
  • the ISO index is a dimensionless quantity determined by gas chromatography.
  • Sample preparation 3 drops of the sample are maintained in 1 ml MSTFA and for 60 minutes at 80 0 C.
  • Injector temperature 250 0 C
  • Detector temperature 250 0 C
  • Injection volume 0.5 microliter
  • the isoindex thus calculated from the degree of branching of the components contained in the alcohol mixture and the amount of the corresponding components (determined by gas chromatography).
  • the C 5 - to C 3 -alcohols are prepared according to the methods mentioned above.
  • cyclohexanepolycarboxylic esters in which R is C 9 -alkyl which are very particularly preferably used in the compositions according to the invention, it is particularly preferable to use a nonanol mixture in which 1 to 20% by weight, preferably 3 to 18% by weight.
  • %, more preferably 5 to 16 wt .-% of the nonanol mixture have no branching, 10 to 90 wt .-%, preferably 15 to 80 wt .-%, particularly preferably 20 to 70 wt .-%, a branching, 5 to 40 wt .-%, preferably 10 to 35 wt .-%, particularly preferably 15 to 30 wt .-% of two branches, 0.1 to 10 wt .-%, preferably 0.1 to 8 wt .-%, especially preferably 0.1 to 5 wt .-% have three branches and 0 to 4 wt .-%, preferably 0 to 3 wt .-%, particularly preferably 0.1 to 2 wt .-%. are other components. Other components are generally nanomans with more than three branches, decanols or octanols. Wherein the sum of said components 100 wt .-% results.
  • 0.70 to 2.70 wt.% Preferably 0.90 to 2.50 wt.%, Particularly preferably 1.20 to 2.20 wt.% Of 3,6,6-trimethylhexanol; From 1.96 to 3.96% by weight, preferably from 2.16 to 3.76% by weight, more preferably
  • nonanol mixture which is used for the preparation of cyclohexanepolycarboxylic acid derivatives which are preferably used has the following composition: From 6.0 to 16.0% by weight, preferably from 7.0 to 15.0% by weight, particularly preferably from 8.0 to 14.0% by weight of n-nonanol;
  • Cyclohexanpolycarbonklarivate are thus 1, 2 Diisononylcyclohexandicarbonklareester.
  • the isononyl radical in the 1,2-diisononylcyclohexanedicarboxylic acid esters is preferably based on the abovementioned nonanols used for preparing the 1,2-diisononylcyclohexanedicarboxylic acid esters.
  • it may be 1, 2-diisononylcyclohexanedicarboxylic acid ester (diisononylcyclohexane-1,2-dicarboxylate), which is also commercially available under the name Hexamoll® DINCH (from BASF AG).
  • Component (III) is also commercially available under the name Hexamoll® DINCH (from BASF AG).
  • the waxes used in the compositions according to the invention are waxes comprising at least one component selected from polyethylene waxes, hydrocarbon waxes, fatty acid derivatives and mixtures thereof, preferably selected from polyethylene waxes, hydrocarbon waxes and mixtures comprising hydrocarbon waxes and polyethylene waxes.
  • hydrocarbon waxes are understood to mean long-chain hydrocarbons or preferably long-chain hydrocarbon mixtures, "long-chain hydrocarbons” generally to be understood as meaning hydrocarbons having 18 to 60 carbon atoms
  • the hydrocarbon waxes are generally solid at room temperature and preferably melt in the range from 50 to 200 ° C., particularly preferably from 70 to 180 ° C., very particularly preferably from 94 to 150 ° C.
  • Suitable hydrocarbon waxes are saturated hydrocarbons or mixtures of saturated hydrocarbons which may be branched or unbranched and cyclic or, preferably, acyclic, in waxes (which are also to be understood as isoparaffins.)
  • Suitable paraffin waxes are known to the person skilled in the art Particularly preferred paraffin waxes are saturated hydrocarbons or mixtures of saturated hydrocarbons having 18 to 60 carbon atoms.
  • so-called microcrystalline waxes (micro waxes) or ozokerite are suitable as hydrocarbon waxes. Suitable microcrystalline waxes and ozokerite are known in the art.
  • microcrystalline waxes compared to paraffin waxes, which are mainly composed of unbranched saturated hydrocarbons, a higher proportion of branched aliphatic hydrocarbons (isoparaffins) and optionally naphthenic hydrocarbons. Furthermore, the microcrystalline waxes are characterized by the higher fineness of their crystals compared to the paraffin waxes.
  • Polyethylene waxes are polymers which preferably contain at least 30% by weight, in particular at least 50% by weight, more preferably at least 60% by weight and most preferably at least 70% by weight of ethylene.
  • the polyethylene waxes are generally solid at room temperature, preferably in the range of 50 to 200 0 C, particularly preferably 70 to 180 0 C, most preferably 100 to 150 ° C melting polyethylene waxes.
  • the polyethylene waxes may contain, in addition to ethylene, other monomers, for example ole fi ns such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 1-decene; C1 to C20 Alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols having 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds; Monomers with carboxylic acid, sulfonic acid or phosphonic acid groups, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid; Hydroxyl-containing monomers, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates or (meth) acrylamide, phen
  • the polyethylene wax preferably has a weight-average molecular weight Mw of from 1,000 to 40,000 g / mol, more preferably from 1,000 to 20,000 g / mol, more preferably from 3,000 to 18,000 g / mol, and most preferably from 5,000 to 15,000 g / mol (determined by gel permeation chromatography ).
  • the polyethylene waxes preferably have a density of from 0.8 to 1.0 g / cm 3 , preferably from 0.90 to 0.96 g / cm 3 and particularly preferably from 0.93 to 0.95 g / cm 3 , measured at 23 ° C.
  • the melt viscosities are preferably in the range from 20 to 20000 centi Stokes (cSt), preferably in the range from 800 to 2000 cSt, measured at 120 ° C.
  • the molecular weight distribution is preferably in the range of 2 to 10.
  • Polyethylene waxes are produced by polymerization or copolymerization of ethylene.
  • the processes for the preparation can be roughly divided into low-pressure processes carried out at 20 to 100 bar, and high-pressure processes carried out at 500 to 4000 bar.
  • the high pressure process is a free radical polymerization process that generally works without a catalyst.
  • To start the radical chain reaction one usually uses one or more organic peroxides, for example the Akzo Nobel Trigonox® or PerkadoxO grades, or air or atmospheric oxygen.
  • Suitable molecular weight regulators are hydrogen.
  • Other commonly used regulators are carbon monoxide CO and alkanes such as ethane or propane.
  • aliphatic or alicyclic ketones are suitable as molecular weight regulators, as mentioned in DE 100 64 800 A1.
  • fatty acid derivatives are meant, for example, bis-stearamides, for example N, N'-ethylene-bis-stearamide (N- [2- (octadecanoylamino) ethyl] octadecanamide).
  • the waxes are generally used in bulk.
  • waxes approved for food contact, medical devices and / or toys are used. Suitable waxes approved for contact with food, for medical devices and / or for toys are known to the person skilled in the art. Particularly suitable waxes are non-polar polyethylene waxes or mixtures containing non-polar polyethylene waxes or hydrocarbon waxes or mixtures containing hydrocarbon waxes. Examples of waxes suitable as component (III) include i.a. Basewax®, in particular the mixture of hydrocarbon waxes Basewax® H 187 from Paramelt B.V. and Advawax®, in particular the non-polar Adwawax® C11 1 polyethylene wax from Rohm & Haas.
  • Basewax® in particular the mixture of hydrocarbon waxes Basewax® H 187 from Paramelt B.V.
  • Advawax® in particular the non-polar Adwawax® C11 1 polyethylene wax from Rohm & Haas.
  • compositions according to the invention may contain as further polymers (component (IV)) in particular partially crystalline polyamides, partly aromatic copolyamides, polyesters, polyoxyalkylenes, polycarbonates, polyarylene sulfides, polyether ketones and / or polyvinyl chlorides.
  • further polymers (component (IV)) are polycarbonate and polyamide. It is also possible to use mixtures of two or more of the stated polymers (component (IV)).
  • the further polymers (component (IV)) are generally present in amounts of from 0 to 50% by weight, preferably 0-20% by weight, in each case based on the total weight of components I, II and III.
  • plastic-compatible additives known to those skilled in the art can be used in amounts of from 0 to 50% by weight, preferably 0-40% by weight, in each case based on the total weight components I, II and III.
  • Conventional additives V are all substances which dissolve well in the components I, II and III, or are readily miscible with these.
  • Suitable additives (component (V)) include dyes, stabilizers, lubricants and antistatic agents.
  • particulate or fibrous fillers or reinforcing materials in particular glass fibers and calcium carbonate, which are usually present in amounts of from 0 to 50% by weight, preferably 0-40% by weight, can be present in the molding compositions according to the invention. %, in each case based on the total weight of components I, II and III.
  • compositions according to the invention from components I, II, III and, if desired, further polymers (component (IV)), additives (component (V)) and / or fillers or reinforcing materials (component (VI)) can be carried out in any desired manner done by all known methods.
  • the mixing of the components by melt mixing, for example, common extrusion, kneading or rolling of the components, z. B.
  • the graft copolymers A of the component I can be mixed as moist crumbs with a granulate of the thermoplastic copolymer B of the component I, in which case the complete drying takes place during mixing to the graft copolymers used as component I according to embodiment 1.
  • compositions according to the invention can be processed into molded parts, such as plates or semi-finished products, films or fibers, or else into foams.
  • the compositions according to the invention can be used in applications in which they come into contact with food, as well as in medical products or children's toys.
  • thermoplastic processing from the molding compositions of the invention.
  • compositions of the invention are characterized in that they - due to the special combination of components (I), (II) and (III) - have improved processability over comparable compositions without adversely affecting the other properties of the compositions.
  • an improved processability is to be understood in particular that the Force in the extrusion or other processing methods of the compositions of the invention is substantially lower than comparable compositions.
  • a substantial energy saving can be achieved with simultaneously reduced wear of the devices used for processing.
  • Another particular advantage of the compositions according to the invention is that they are used in applications in which they come into contact with food, as well as in medical products or children's toys.
  • Example 1 (comparative): containing composition
  • component (I) 97.5 wt .-% of component (I), which is a commercially available
  • ASA polymer is (Luran® S 757 G from BASF SE); (ii) 1.5% by weight of component (II), which is a commercially available
  • Phthalate is (Palatinol® 10P from BASF SE)
  • component (III) 1.0% by weight of component (III), which is a commercially available polyethylene wax (Paracerin® H 100).
  • Example 2 (according to the invention): composition containing
  • component (I) 97.5 wt .-% of component (I), which is a commercially available
  • ASA polymer is (Luran® S 757 G from BASF SE);
  • component (Ii) 1, 5 wt .-% of component (II), which is a commercially available 1, 2-cyclohexanedicarboxylic acid diisononyl ester (Hexamoll DINCH ® BASF
  • component (III) 1.0% by weight of component (III), which is a commercially available hydrocarbon wax blend (Basewax® H187 from Paramelt B.C.).
  • Example 3 Composition containing
  • component (i) 97.5% by weight of component (I) which is a commercially available ASA polymer (Luran® S 757 G from BASF SE); 1.5% by weight of component (II), which is a commercially available 1, 2-cyclohexanedicarboxylic acid diisononyl ester (Hexamoll DINCH® from BASF SE);
  • component (III) 1, 0 wt .-% of component (III), which is a commercially available non-polar polyethylene wax (Advawax® C1 1 1 from Rohm & Haas).
  • compositions mentioned in Comparative Example 1 and Examples 2 and 3 according to the invention are extruded and the force required for mixing is measured.
  • the force [N] given in Table 1 is understood to mean the force that has to be expended in the extruder to promote the particular composition. All of the compositions mentioned in Examples 1 to 3 were extruded under identical conditions, so that the respective forces to be used are directly comparable with one another. The results are shown in Table 1.
  • the experiments are carried out on a DSM Xplore 5 & 15 micro compounder DSM extruder.
  • the mixtures are compounded at 220 ° C. at 80 rpm with a twin screw.
  • Table 1 shows that, in order to convey the compositions according to the invention in the extruder, a significantly lower force is required than for conveying the comparative composition.

Abstract

L’invention concerne des compositions, contenant (i) au moins un matériau à mouler choisi parmi les matériaux à mouler qui contiennent les composants (A) et (B), et les matériaux à mouler qui contiennent le composant (B’); en tant que composant (I); avec les significations suivantes; pour le matériau à mouler contenant les composants (A) et (B) : A) 10 à 80 % en poids, par rapport à la somme des composants A et B, d’un copolymère greffé; B) 20 à 90 % en poids, par rapport à la somme des composants A et B, d’un copolymère thermoplastique; et pour le matériau à mouler contenant le composant (B’) : B’) un copolymère thermoplastique; (ii) au moins un dérivé d’acide cyclohexanepolycarboxylique; (iii) au moins une cire en tant que composant (III) contenant au moins un composant choisi dans le groupe constitué des cires de polyéthylène, des cires d’hydrocarbures, des dérivés d’acides gras et leurs mélanges; (iv) éventuellement un ou plusieurs polymères supplémentaires en tant que composant (IV); éventuellement un ou plusieurs additifs en tant que composant (V); et (vi) éventuellement une ou plusieurs charges et/ou substances renforçantes en tant que composant (VI). L’invention concerne également un procédé de fabrication de la composition selon l’invention, l’utilisation de la composition selon l’invention pour la fabrication de corps moulés, de feuilles, de mousses ou de fibres, et des corps moulés, des feuilles, des mousses ou des fibres contenant la composition selon l’invention.
PCT/EP2009/062393 2008-09-29 2009-09-24 Compositions thermoplastiques à propriétés d'aptitude au traitement WO2010034778A1 (fr)

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EP08165358.6 2008-09-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110291040A1 (en) * 2010-06-01 2011-12-01 Basf Se Process for producing expandable styrene polymer compositions
WO2011151301A1 (fr) * 2010-06-01 2011-12-08 Basf Se Procédé de production de compositions expansibles à base de polymère de styrène

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0450485A2 (fr) * 1990-04-06 1991-10-09 BASF Aktiengesellschaft Masse à mouler thermoplastique
DE10116812A1 (de) * 2001-04-04 2002-10-17 Basf Ag Kunststoffe mit kernhydrierten Phthalat-Weichmachern
US6683030B2 (en) * 2000-03-13 2004-01-27 Basf Aktiengesellschaft Agrotechnical formulation
WO2006136471A1 (fr) * 2005-06-22 2006-12-28 Oxeno Olefinchemie Gmbh Melange d'esters diisononyliques de l'acide 1,2- cyclohexandicarboxylique, procede pour produire ces melanges et utilisation associee
DE102005037329A1 (de) * 2005-08-04 2007-02-08 Basf Ag Thermoplastische Formmassen auf Basis von Polyestern und Styrolcopolymeren
WO2007082904A1 (fr) * 2006-01-19 2007-07-26 Basf Se Copolymere n-ba/alcene en tant que bases greffees pour polymere abs
US7591887B2 (en) * 2003-03-14 2009-09-22 Basf Se Printing inks comprising cyclohexane polycarboxylic acid derivatives

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0450485A2 (fr) * 1990-04-06 1991-10-09 BASF Aktiengesellschaft Masse à mouler thermoplastique
US6683030B2 (en) * 2000-03-13 2004-01-27 Basf Aktiengesellschaft Agrotechnical formulation
DE10116812A1 (de) * 2001-04-04 2002-10-17 Basf Ag Kunststoffe mit kernhydrierten Phthalat-Weichmachern
US7591887B2 (en) * 2003-03-14 2009-09-22 Basf Se Printing inks comprising cyclohexane polycarboxylic acid derivatives
WO2006136471A1 (fr) * 2005-06-22 2006-12-28 Oxeno Olefinchemie Gmbh Melange d'esters diisononyliques de l'acide 1,2- cyclohexandicarboxylique, procede pour produire ces melanges et utilisation associee
DE102005037329A1 (de) * 2005-08-04 2007-02-08 Basf Ag Thermoplastische Formmassen auf Basis von Polyestern und Styrolcopolymeren
WO2007082904A1 (fr) * 2006-01-19 2007-07-26 Basf Se Copolymere n-ba/alcene en tant que bases greffees pour polymere abs

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110291040A1 (en) * 2010-06-01 2011-12-01 Basf Se Process for producing expandable styrene polymer compositions
WO2011151301A1 (fr) * 2010-06-01 2011-12-08 Basf Se Procédé de production de compositions expansibles à base de polymère de styrène
US8889748B2 (en) * 2010-06-01 2014-11-18 Basf Se Process for producing expandable styrene polymer compositions

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