DE19745566A1 - Particulate vinyl polymer useful for fibers, films and molded articles - Google Patents

Abstract

A particulate polymer (I) has a particle size range of 0.05-100 microns and a swelling index of 1-50 and contains as anionically polymerizable components, at least one anionically polymerizable vinyl monomer and at least one monomer having two anionically polymerizable functional groups of the same and/or differing reactivity as a crosslinking agent. Independent claims are included for (i) a process for the production of (I) by polymerization of the reactants in the presence of a polymerization initiating anion, an aprotic solvent and a block or graft copolymer that is insoluble in the solvent. (ii) a polymer composition (II) containing at least 50 wt.% of a mixture of (I) and a thermoplastic composition. (iii) fibers, film, molded articles, coating, lacquer or foam containing (I) or (II).

Description

The invention relates to particulate polymer (P) with a medium Particle size range in the range of 1 to 100 microns and a swelling index from 1 to 50 and its production. Furthermore concerns the Erfin a polymer composition (PZ) that this polymer and thermopla include static masses as components (K1) and (K2). Also affects the invention the use of the particulate polymer (P) and the Polymer composition (PZ) in molded parts, fibers, foils and foams and the same as the particulate polymer (P) and / or polymerization compositions (PZ) included.

US Pat. No. 3,645,959 discloses high molecular weight vinyl polymers, for example made of polystyrene, which were produced in non-aqueous dispersions beard. Crosslinkers were also used in these polymers.

US-P 4 112 209 discloses the cationic polymerization of styrene in a molecular weight range of 200 to 5,000 and a polydispersity less than 8.

U.S. Patent No. 4,829,135 discloses anionic homopolymerization of vinyl aromatic monomers in a dispersion of a non-solvent for example hexane, the reaction taking place in three or more steps, to create spherical microparticles. In this prior art however, a crosslinker is used.  

The polymers of the prior art, especially the aforementioned Patent documents have the disadvantage in common that the resulting particles are soft or a too broad, partially bimodal particle size distribution exhibit. As a result, these polymers are poor Matting agents are suitable and usually the impact strength of the products also decreases when these polymers are added to the products.

In particular, the use of these polymers is problematic if the Pro products are manufactured in smooth-walled forms. In such a way Products use the polymers described above undesirable shiny surfaces and generally to a clear Reducing the impact resistance of these products. Furthermore, the State of the art polymers do not, the mattness of the molded body control regardless of the surface of the mold.

It is therefore an object of the invention to overcome these disadvantages by suitable means Overcome polymers (P) and polymer compositions (PZ). Ins In particular, the object of the invention is polymers (P) and To provide polymer compositions (PZ) that are suitable are, these containing products that are made in smooth-walled shapes with a matt surface and high impact strength to provide.

According to the invention, this object was achieved on the one hand by a particulate polymer (P) with a particle size range from 1 to 100 μm and a swelling index from 1 to 50, including as anionically polymerized constituents:

• - At least one anionically polymerizable vinyl monomer and  
• - At least one monomer with at least two anionic polymeri sizable functional groups of the same or different Reactivity or a mixture thereof as a crosslinker

and further by polymer compositions (PZ), which at least that contain previously described polymer (P) as component (K1), dissolved.

The particulate polymer (P) according to the invention contains generally more% by weight of the anionically polymerizable monomer as parts by weight of the crosslinking agent. About the share of crosslinkers can be a number of physical quantities in particular the swelling index and the impact strength of the particulate polymer according to the invention (P) and the polymer composition (PZ) and mixture (M) control. Each lower proportion of crosslinker in the particulate according to the invention Polymer (P) is the larger the swelling index. It was invented in accordance with the invention, in particular with regard to the particle size range and Swelling index, proven to be very advantageous, 80 to 99.99, preferably 90 to 99.98 and particularly preferably 95 to 99.97% by weight of at least one anionically polymerizable monomer and 0.01 to 20, preferably 0.02 to 10 and particularly preferably 0.03 to 5% by weight of at least one crosslinking agent, each based on the total particulate polymer (P) to use.

The swelling index is the weight gain of a polymer sample by the Inclusion of a solvent for the uncrosslinked polymer sample. He will by stirring the polymer sample in the solvent, for example toluene centrifuge, decant the solvent and determine the Ge weight difference to the polymer sample used.

The particulate polymers (P) according to the invention preferably have a particle size range of 0.05 to 90, preferably 1 to 80 and  particularly preferably 1 to 70 microns. In another preferred Aus leadership form of the particulate polymer (P) according to the invention this has a particle size range from 0.5 to 20, preferably 0.5 to 15 and particularly preferably 1 to 10. In another embodiment of the polymer (P) according to the invention has a particle size range from 10 to 80, preferably 15 to 70 and particularly preferably 20 to 65 on. Furthermore, there is a preferred embodiment of the invention particulate polymer (P) before if this has a particle size range from 5 to 40, preferably 7 to 35 and particularly preferably 8 to 32 µm.

The essentially monodisperse particle size range from 1 to 100 µm is determined by carrying out at least 50 particles as later be measured and at least 50, preferably at least 50 of these particles at least 70 and particularly preferably at least 90% a certain through knife with a deviation of maximum 30, preferably maximum 10 and more preferably at most 5% of the mean in the particle size range range from 1 to 100 µm.

The average particle size according to the invention is determined by a sample of the particulate polymer was sponged and between two Cover plates a monoparticulate film is created, which is under a micro skop is considered. When viewed microscopically, the individual particle sizes of at least 100 individual particles, added up and divided by the number of determined individual particles.

The swelling index of the particulate polymers according to the invention (P) is preferably in the range from 1.5 to 40, preferably 2 to 30 and particularly preferred 3 to 20. In a further preferred Aus  leadership form of the particulate polymer (P) according to the invention Swelling index in the range of 4 to 15.

In one embodiment of the particulate polymer according to the invention (P) this has a particle size range in µm or a swelling index from 0.5 to 20 or 1 to 15, preferably 0.5 to 15 or 2 to 10, particularly preferably 1 to 10 or 3 to 7.

Another preferred embodiment of the polymer according to the invention has a particle size range in µm or a swelling index of 0.5 to 20 or 5 to 30, preferably 0.5 to 15 or 11 to 25 and particularly preferably 1 to 10 or 12 to 20.

Furthermore, there is a preferred embodiment of the part according to the invention Chen-shaped polymer (P) with a particle size range in µm or a swelling index of 0.5 to 20 or 3 to 25, preferably 0.5 to 15 or 5 to 15 and particularly preferably 1 to 10 or 6 to 10.

Furthermore, there is a preferred embodiment of the invention Particulate polymer (P) with a particle size range in µm or a swelling index of 5 to 40 or 1 to 55, preferably 7 to 35 or 2 to 10 and particularly preferably 8 to 32 or 3 to 7.

Among anionically polymerizable monomers of the part according to the invention Cheniform polymer (P) are generally understood to mean monomers whose Polymerization can be triggered by anionic initiators. Prefers these monomers have at least one double bond. Preferred Monomers of the particulate polymer (P) according to the invention are the anionically polymerizable monomers, which are preferably aprotic, selected from the group containing vinyl aromatic monomers, preferably  example with 7 to 20 carbon atoms, conjugated dienes, preferably with 4 to 10 carbon atoms, acrylates, especially with 3 to 10 carbons Substance atoms, such as methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, n- and Isobutyl acrylate, tert-butyl acrylate and 2-ethylhexyl acrylate, with alkyl acrylates 4 to 15 carbon atoms, for example methyl methacrylate, ethyl meth acrylate, n- and isopropyl methacrylate, n- and isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate, acrylic acid anhydrides with a C-C double bond, preferably with 4 to 10 carbons Substance atoms, for example maleic anhydride and its derivatives, alkyl acrylic anhydrides with a C-C double bond, preferably with 5 to 10 Carbon atoms, acrylamides, preferably with 3 to 10 carbon atoms, alkyl acrylamides, preferably with 4 to 10 carbon atoms, Acrylonitriles, preferably having 3 to 10 carbon atoms, for example Acrylonitrile, alkyl acrylonitrile, preferably having 4 to 10 carbon atoms, for example methacrylonitrile.

Particularly suitable as the anionically polymerizable monomer of the particulate polymer (P) according to the invention are vinylaromatic monomers which generally make up at least 70, preferably at least 80 and particularly preferably at least 90 and moreover preferably 100% by weight of the total anionically polymerizable monomers. Among the vinyl aromatic monomers, the monomers of the formula I are preferred

where n has a value from 1 to 4 and R ₁ and R ₂ independently of one another are hydrogen or a C ₁ to C ₈ hydrocarbon or a C ₁ to C ₈ alkoxy group. Of the anionically polymerizable monomers covered by the formula I, α-methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene, p-methyl-α-methylstyrene and are preferred, styrene and α-methylstyrene being particularly preferred are. Of all the anionically polymerizable monomers of the particulate polymer (P) according to the invention, styrene is most preferred.

As a crosslinker of the particulate polymer (P) according to the invention at least two anionically polymerizable functional groups of the same or different reactivity or mixtures thereof can all that Crosslinkers known to those skilled in the art can be used. It is preferably the functional groups are double and / or triple bonds, preferably double bonds.

Compounds with two or more anionically polymerizable functional groups of the same reactivity are, for example, di-, trivinylbenzene, butane-diol diacrylate, mono-, di-, tri- or tetra-alkylene glycol diacrylates, preferably C ₁ -C ₄ -mono-alkylene glycol diacrylates such as ethylene glycol diacrylate, n- Propylene glycol diacrylate, 1,3-n-butylene glycol diacrylate or 1,4-n-butylene glycol diacrylate. Also suitable are mono-, di-, tri- or tetra-alkylene glycol dimethacrylates, preferably C ₁ -C ₄ -mono-alkylene glycol dimethacrylates, such as ethylene glycol dimethacrylate, n-propylene glycol dimethacrylate, 1,3-n-butylene glycol dimethacrylate or 1,4-n -Buty lenglycol dimethacrylate. Acrylates or methacrylates of glycerol, trimethylol propane, pentaerythritol, inositol or sugar alcohols are also suitable crosslinkers. Acrylic or methacrylamides of ethylenediamine or other aliphatic di- or polyamines may be mentioned as further suitable crosslinkers. In addition, diallyl maleate, diallyl fumarate or diallyl phthalate, triacryl- or trimethacrylamides, triallylcyanurate or triallyliso cyanurate can be used as crosslinkers.

Crosslinking agents according to the invention with two or more anionically polymerizable functional groups of different reactivity are dihydrodicyclopenta dienyl acrylate (DCPA).

Further crosslinkers with anionically polymerizable functional groups of different reactivity are ethylenically unsaturated monomers, such as allyl methacrylate, methallyl methacrylate, acryloylalkoxysilanes or methacryloylalkyloxysilanes of the general formula II

wherein R ^{1 is} C ₁ to C ₃ alkyl or phenyl, preferably methyl, R ^{2 is} hydrogen or methyl, n is an integer from 0 to 2 and p is an integer from 1 to 6, preferably from 1 to 4. The following may be mentioned as preferred examples:

β-methacryloyloxyethyldimethoxymethylsilane,
γ-methacryloyloxy-n-propylmethoxydimethylsilane,
γ-methacryloyloxy-n-propylmethoxymethylsilane,
γ-methacryloyloxy-n-propyltrimethoxylsilane,
γ-methacryloyloxy-n-propyldimethoxymethylsilane,
γ-methacryloyloxy-n-propyldiethoxymethylsilane,
δ-methacryloyloxy-n-butyldiethoxymethylsilane.

Furthermore, for the particulate polymers (P) according to the invention mixtures of at least two crosslinkers are also used. Here can on the one hand mixtures of at least one crosslinker with at least at least two functional groups of different reactivity with at least a crosslinker with at least two functional groups of the same reaction  vity as well as cross-linking mixtures from at least two different ones Crosslinkers with at least two functional groups of the same reactivity and crosslinker mixtures with at least two different crosslinkers with at least two functional groups of different reactivity are used, crosslinking mixtures of at least two under different crosslinkers with at least two functional groups of the same Reactivity are preferred. Crosslinker mixtures of the invention Particulate polymer (P) have at least two, preferably two, three, four, five and particularly preferably two, three and more preferred two different crosslinkers.

To the preferred crosslinker mixtures with at least two anionic polymerizable functional groups of different reactivity count preferably dihydrodicyclopentadienyl acrylate and allyl methacrylate, dihydro dicyclopentadienyl acrylate and allyl methacrylate; Dihydrodicyclopentadienyl acrylate, allyl methacrylate and β-methacryloyloxyethyldimethoxymethylsilane; Dihydroxydicyclopentadienyl acrylate and β-methacryloyloxyethyldimethoxy methylsilane.

The particularly preferred crosslinker mixtures include dihydrodicyclo pentadienyl acrylate and butanediol diacrylate; Dihydrodicyclopentadienyl acrylate and divinylbenzene; Dihydrodicyclopentadienyl acrylate and ethylene glycol diacry lat; as well as dihydrodicyclopentadienyl acrylate and tetraethylene glycol dimethacry lat. Further preferred crosslinker mixtures are dihydrodicyclopenta dienyl acrylate, butanediol diacrylate and allyl methacrylate; Dihydrodicyclopenta dienyl acrylate, butanediol diacrylate and divinylbenzene; Dihydrodicyclopenta dienyl acrylate, allyl methacrylate, β-methacryloyloxyethyldimethoxymethylsilane and divinylbenzene or diethylene glycol diacrylate or tetraethylene glycol dimethacrylate; Dihydroxydicyclopentadienyl acrylate, β-methacryloyloxyethyl  dimethoxymethylsilane and divinylbenzene or diethylene glycol diacrylate or Tetraethylene glycol dimethacrylate.

Compared to all of the above crosslinkers and crosslinker mixtures is a particulate polymer (P) according to the invention which has at least 70 preferably 80 and particularly preferably 90 and more preferably 100% by weight, based on the total crosslinker, of at least one, preferably only one monomer with two or more functional groups same reactivity, particularly preferably trivinylbenzene, divinylbenzene and particularly preferably there is divinylbenzene.

The particulate polymer (P) according to the invention generally contains 80 up to 99.99% by weight of anionically polymerizable monomer and 0.01 to 20 % By weight crosslinker, preferably 90 to 99.9% by weight anionically polymerized bares monomer and 0, 1 to 10 wt .-% crosslinker and especially before adds 95 to 99.5% by weight of anionically polymerizable monomer and 0.5 to 5% by weight crosslinker, in each case based on the total polymer.

The particulate polymer (P) according to the invention can be obtained from a Process in which the constituents of the polymer are preferred at least anionically polymerizable monomer and crosslinker, in counter were at least one anion initiating the polymerization, at least an aprotic solvent and at least one essentially in the solvent insoluble at least from two different polymer chains existing block or graft copolymer or mixtures thereof be polymerized.

In one embodiment of the method for producing the Invention According to the particulate polymer (P), the polymerization takes place in the area from 0 to 100, preferably 10 to 70 and particularly preferably 40 to 60 ° C.  

All of the anions known to the person skilled in the art for initiating anionic polymerizations can be used in the process for producing the particulate polymer (P) according to the invention. These anionic initiators include, in particular, initiators of anionic polymerization, for example metal alkyls, and initiators of group transfer polymerization, for example silyl ketene ketals. This includes, for example, the anions of the initiators for anionic polymerization or for group transfer polymerization. In the process according to the invention, the polymerization is preferably initiated by C ₁ to C ₂₀ , preferably C ₁ to C ₁₀ and particularly preferably C ₁ to C ₅ hydrocarbon anions. In the process according to the invention, the anions of methyl, ethyl, propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isobutyl or mixtures thereof are particularly preferred. In a particularly preferred embodiment of the process according to the invention, however, the polymerization is initiated by only one anion.

As cations for initiating the polymerization according to the invention Anions come all organic and inorganic known to those skilled in the art cations used in anionic polymerization into consideration. Cations of the first, second, third and fourth main group, preferably the first and second and especially preferably the first main group. Among the cations of the first major groups are preferably lithium for the process according to the invention, Sodium and potassium and particularly preferably lithium.

In a preferred embodiment of the method according to the invention is the anionic polymerization by methyl lithium, ethyl lithium, n- Butyllithium, sec-butyllithium and tert-butyllithium, preferably n-butylli thium, sec.-butyllithium and tert.-butyllithium and particularly preferably sec.- Butyllithium initiated.  

For the process for producing the particulate according to the invention Polymers (P) are generally suitable for all those known to the person skilled in the art aprotic solvent. However, when choosing the solvent preferably make sure that solvents and block or graft copolymer or their mixture are coordinated so that at least least part of the graft or block copolymer or a mixture thereof does not dissolve in the solvent or solvent mixture used.

In one embodiment of the process according to the invention, the polymerization is carried out in the presence of at least one solvent selected from the group comprising hydrocarbons, ethers having 2 to 10 carbon atoms, for example dimethyl ether or tetrahydrofuran, sulphoxides having 2 to 10 carbon atoms, preferably dimethyl sulphoxide, the C ₄ - to C ₁₀ - hydrocarbons are preferred. The C ₄ - to C ₁₀ hydrocarbons preferably include the isomers and cyclic compounds of butane, pentane, hexane, heptane, octane, nonane and decane and at least two of these mixtures. n-Hexane or cyclohexane or their mixture are particularly preferred as solvents in the process according to the invention.

As block or graft copolymers or a mixture thereof, Ver drive for the production of the particulate polymer (P) according to the invention all block or graft copolymers known to the person skilled in the art or their mixtures be used as long as these in the solvents or in not the solvent mixtures used for the polymerization are soluble.

According to the invention, block copolymers are copolymers with at least two, preferably two or three or four or five and particularly preferably two polymer chains formed from different monomers, for example polymer chain (A) and polymer chain (B). For the preferred case according to the invention that the block polymer is formed from two different monomers, namely polymer block (A), polymer block (B), the polymer chain combinations [AB] _n , A [BA] _n and B [AB] _n with n from 1 to 20, preferably 1 to 10 and particularly preferably 1 to 5, preferred. Polymer chain arrangements with AB or ABA or BAB are also preferred, with AB being particularly preferred.

According to the invention, a graft copolymer is a polymer with a Main chain understood from the at least one other block that is not starts from the ends of the main chain. For example a graft copolymer preferably has a main block (A) of at most 50 % By weight, and one or two or more side blocks (B) preferably to contain at least 30 wt .-%, based on the total copolymer.

The process according to the invention is preferably carried out in the presence of mind at least one block or graft copolymer, at least consisting of one Polymer block A consisting of a vinyl aromatic monomer and a polymer block B from a diene. In the block or graft copolymers of the inventions According to the method according to the invention, polymer blocks A and B preferably have the shares in the block or resulting from the following Table I Graft copolymer.

Table 1

Furthermore, it is preferred in the process according to the invention that the block or graft copolymer from a polymer block A consists of a C ₈ to C ₂₀ , preferably C ₈ to C ₁₅ and particularly preferably C ₈ to C ₁₀ vinyl aromatic monomer formed polymer, preferably polystyrene and a polymer block B consists of a polydiene formed from a C ₄ - to C ₂₀ -, preferably C ₅ - to C ₁₅ - and particularly preferably C ₅ - to C ₁₀ - diene, preferably polybutadiene, with particular preference the block or graft copolymer consists only of a polymer block A and a polymer block B. In a further embodiment of the process according to the invention, it is preferred that only block copolymers, preferably block copolymers, of a polymer chain A and a polymer chain B, preferably of polystyrene and polybutadiene, are used.

It is further preferred according to the invention that the diene content is at least increased 50, preferably at least 80 and particularly preferably at least 90 % By weight is not hydrogenated. The use of hydrogenated polydiene as a poly merblock in a block or graft copolymer is only advantageous if when large particulate polymers are sought.

Furthermore, it is preferred in the process according to the invention that the Block or graft copolymer from a polymer chain A of at least 60, preferably at least 80 and particularly preferably 100% by weight, based on the polymer chain, from a vinyl aromatic monomer, preferably one vinyl aromatic monomer according to formula I and particularly preferred Styrene and a polymer chain B of at least 60, preferably at least 80 and particularly preferably 100% by weight, based on the polymer chain a conjugated diene, preferably selected from the group of butadiene and Isoprene and particularly preferably butadiene, preferably that Block or graft copolymer only from a polymer chain A and a poly Merkette B exists.  

Furthermore, it is preferred according to the invention that the non-hydrogenated diene Proportion of at least 50, preferably at least 70 and especially before adds at least 90% by weight in the form of the cis isomer.

The block copolymers used in the process according to the invention have a weight average molecular weight (M _w ) from 1000 to 500,000, preferably from 10,000 to 400,000 and particularly preferably from 100,000 to 300,000 g / mol.

The determination of the molecular weight, in particular the weight average of the molecular weight is carried out according to the invention via gel permeation chro matography (GPC) against a polystyrene standard in one of the below Seeking polymer sufficient solvent.

In the process according to the invention, the copolymers are used as dispersers yaw used, the properties of the dispersion by the amount of the copolymer used depends. According to the invention, it has proven to be proven advantageous, the block copolymer in an amount of 0.1 to 10, preferably from 0.1 to 5 and particularly preferably from 1 to 4% by weight, based on the solvent used.

Furthermore, the properties of the dispersion are of the mono ratio depending on solvent. It has proven advantageous according to the invention proven the monomer or monomers, especially styrene, in one Amount from 10 to 90, preferably 30 to 70 and particularly preferably 40 to 60 wt .-%, based on the solution used in the polymerization medium to use.

The molecular weight of the Particulate polymer (P) according to the invention can be controlled. It has  for the particulate polymer (P) and the Ver drive to its manufacture proven advantageous, initiator, in particular sec-butyllithium, in an amount of 0.5 to 10, preferably 1 to 5 and particularly preferably use 1.5 to 4 mmol.

This is invented by the method according to the invention described here Particulate polymer (P) according to the invention is available. Beyond that preferred embodiments of the particulate according to the invention Polymers (P) by the following preferred embodiments of the inventions method according to the invention available.

In a preferred embodiment of the process according to the invention, copolymers, preferably with a polystyrene block fraction (A) and a polybutadiene block fraction (B) according to Table 1, are used as dispersants in% by weight, based on the amount of solvent used, with an M _w (g / mol) , or monomer, especially styrene, in% by weight, based on the amount of solvent used, or crosslinking agent, in particular divinylbenzene, in% by weight, based on the amount of monomer used, or initiator, especially sec-butyllithium, in mmol / mol of the sum of monomer and crosslinking agent, used in the range from 1 to 10 with 100,000 to 500,000 or 10 to 90 or 0.01 to 1 or 2.5 to 5, preferably 0.5 to 5 with 200,000 up to 400,000 or 30 to 70 or 0.05 to 0.5 or 3 to 4.5 and particularly preferably 1 to 4 with 250,000 to 300,000 or 40 to 60 or 0.07 to 0.1 or 3 , 5 to 4.

In a further preferred embodiment of the invention The above parameters are adhered to with the method Difference that 0.5 to 3, preferably 1 to 2.5 and particularly preferred 1.5 to 2 mmol / mol of the total of monomer and crosslinking agent initiator, especially sec-butyllithium can be used.  

Furthermore, one embodiment of the process according to the invention is that, in contrast to the information from the penultimate section, the copolymer used as the dispersant has a molecular weight (M _w ) in (g / mol) of 50,000 to 300,000, preferably 70,000 to 200,000 and particularly preferably 100,000 to 150,000 having.

Polymer compositions (PZ) according to the invention contain at least 50, preferably 80 and particularly preferably 90% by weight of a mixture (M), based on the total polymer composition (PZ), with at least one of the particulate polymers (P) according to the invention as a component (K1) and at least one thermoplastic composition as component (K2), includes.

The components KI and K2 are contained in this mixture (M) Ranges from 0.1 to 50 or 50 to 99, preferably 0.2 to 30 or 70 to 99.8, particularly preferably 0.3 to 20 or 80 to 99.7 and above also preferably from 0.5 to 15 or 85 to 99.5% by weight, based on the entire mixture (M). Furthermore contains the invention Composition in addition to this mixture (M) 0 to 40, preferably 0 to 30 and particularly preferably 0 to 20% by weight of at least one fiber or part cheniform filler and 0 to 20, preferably 0 to 10 especially before adds 0 to 5% by weight of at least one additive or one processing processing aid, in each case based on the total polymer composition (PZ).

Have been particularly advantageous for the combination according to the invention setting the use of thermoplastics from the group containing ABS (Terluran®), SAN (Luran®) ASA polymers (Luran S®), polystyrenes, blow tough polystyrenes (IPS), polymethyl methacrylates (Lucryl L®), PVC polymers (Vinuran®), polycarbonates, polyester carbonates (Macrolon®), polyester (Ul  tradur®), polyamides (Ultramid®), polyvinylene ethers, polyaryl ether sulfones (Ultrason®), polyoxoalcylene, polyoxymethylene (Ultraform®) and polyarylene sulfides and polyphenylene ethers, preferably their blends, for example with polystyrenes or polyamides.

Coming as vinyl and (meth) acrylic polymers for component K2 preferably the following homopolymers or copolymers into consideration, such as Polystyrene, polymethyl methacrylate, styrene-acrylonitrile copolymers; α-methyl styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene vinylmaleimide copolymers, styrene-methyl methacrylate copolymers, methylme thacrylate-acrylonitrile copolymers, styrene-acrylonitrile-maleic anhydride copoly mers, styrene-acrylonitrile-vinylmaleimide copolymers, α-methylstyrene-acrylonitrile methyl methacrylate copolymers, α-methylstyrene-acrylonitrile-tert-butyl methacrylate copolymers, styrene-acrylonitrile-tert-methyl methacrylate copolymers. Of these Homopolymers or copolymers are styrene homopolymers and ABS or ASA Polymers particularly preferred as components K2.

Furthermore, the thermoplastic material to be matted can be used as a component (K2) in the composition (PZ) according to the invention also follows in the the amorphous and partially crystalline polymers described alone or in Mixture can be used as component K2.

Suitable polycarbonates are, for example, those based on diphenols of the general formula II

HO-Ar-A-Ar-OH (II)

where Ar = aryl radical (phenyl, phenylalkyl, halogen-substituted aryl), A = single bond, C ₁ - to C ₃ -alkylene, C ₂ - to C ₃ -alkylidene, C ₃ - to C ₆ - cyclyalkylidene groups as well as -S- or - SO ₂ - mean.

Preferred diphenols of the general formula (II) are, for example, hydro quinone, resorcinol, 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclo hexane. 2,2-bis (4-hydroxyphenyl) propane and 1,1- Bis (4-hydroxyphenyl) cyclohexane.

The diphenols of the general formula (II) are known per se or according to known methods can be produced.

The diphenols of the general formula (II) can be used either individually or can be used in a mixture to produce the polycarbonates.

As is known, the suitable polycarbonates can be branched, preferably wise by incorporating 0.05 to 2.0 mol%, based on the sum the diphenols used, at least trifunctional compounds, for example those with three or phenolic OH groups.

Polycarbonates which have relative viscosities µ _rel on from 1.10 to 1.50, in particular from 1.25 to 1.40, measured in 0.5% by weight solution in dichloromethane at 25 ° C. have proven to be particularly suitable. This corresponds to average molecular weights M _w (weight average) of 10,000 to 200,000, preferably 20,000 to 80,000.

The polycarbonates can be prepared, for example, by reacting the Diphenols of the general formula (II) with phosgene after the phase boundary surface process or with phosgene according to the process in homogeneous phase (the so-called pyridine process), which must be adjusted in each case de molecular weight in a known manner by the appropriate amount of known chain terminators is achieved (with respect to polydiorganosiloxane polycarbonates containing see for example DE-A 33 34 782).  

Suitable chain terminators are, for example, phenol, but p-tert-butylphenol also long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, according to DE-A 28 42 005 or monoalkylphenols or dialkylphenols with a total 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472, for example p-nonylphenol, 3,5-di-tert-butylphenol, p-tert-octyl phenol, p-dodekylphenyl, 2- (3,5-dimethyl-heptyl) phenol and 4- (3,5-dimethyl heptyl) phenol.

Polycarbonate-polysiloxane blocks can also be used as thermoplastic polymers copolymers, polycarbonate-polyether block copolymers and polycarbonate-polyes ster block copolymers are used.

According to the invention, component K2 can furthermore be polyester, preferably wise aromatic polyesters and polyester carbonates are used. she consist of at least one aromatic bisphenol of the general Formula II and from at least one aromatic dicarboxylic acid and optionally from carbonic acid or its derivatives, such as phosgene, dialkyl and diaryl carbonate. Suitable aromatic dicarboxylic acids are, for example Orthophthalic acid, tetraphthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-dipheryldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarbonate acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, Trimethyl-3-phenylindane-4,5-dicarboxylic acid.

Of the aromatic carboxylic acids, terephthalic acid and / or Isophthalic acid is particularly preferably used. The same applies to the Preferred bisphenols according to formula II mentioned here Likewise.  

Aromatic polyesters and polyester carbonates can be produced by processes as they are for polyester and polyester carbonate production are generally known to those skilled in the art from the literature. This includes for example, processes in homogeneous solution, the melt transesterification method as well as the phase interface method. Enamel is preferred transesterification process (acetate process and phenyl ester process, for example as described in U.S. Patent Nos. 3,494,885, 4,386,186; EP-A 26 120, 26 121, 26 684, 28 030, 39 854, 79 075, 91 602, 97 970, 146 887, 156 103, 234 913, 234 919, 240 301) and in particular as a two-phase interface ver drive (described for example EP-A 68 014, 88 322, 134 898, 151 750, 182 189, 219 708, 272 426) applied.

Aliphatic-aromatic polyesters are, for example, amorphous polyesters Cyclohexane-1,4-dimethanol and terephthalic acid and / or isophthalic acid, the as comonomers, other dicarboxylic acids and aliphatic dihydroxy May contain compounds condensed, for example glycol, propy lenglycol and butylene glycol. Examples of such polyesters are cyclohexane 1,4-di-methanol terephthalic acid polyester, cyclohexane 1,4-di-methanol terephthal isophthalic acid copolyester and cyclohexane-1,4-di-methanol terephthal thalsäureethylenglykol-copolyester. Such polyesters are, for example in EP-A 273 151, 273 152, 155 989, 226 974, 185 309, 152 852, 226 189, 272,416 and U.S. Patent Nos. 4,188,314 and 4,634,737.

Semi-crystalline aromatic-aliphatic can also be used as component K2 Polyester can be used. Examples are polyalkylene terephthalates and Polyalkylene naphthalates, in particular based on ethylene glycol, propanediol 1,3, 1,4-butanediol, 1,6-hexanediol and 1,4-bishydroxymethylcyclohexane. Polyethylene terephthalates, polybutylene terephthalates, Polymethylene naphthalates and copolymers from cyclohexane-1,4-di-methanol and  Ethylene glycol and terephthalic acid related. Also preferred polybutylene terephthalate is used.

The M _{w of} these polyalkylene terephthalates are generally in the range from 10,000 to 500,000, preferably from 10,000 to 80,000. The preparation, in particular by transesterification, is described, for example, in US Pat. No. 2,647,885, 2,643,989, 2,534,028, 2,578,660, 2,742,494 and 2,901,466.

Polyamides are also suitable as component K2. These are for example by polycondensation of diamines, such as ethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylene diamine, m- and p-xylylenediamine, bis- (4-aminocyclohexyl) methane, mixtures of 4,4'- and 2,2'-diaminodicyclo hexylmethanes, 2,2-bis (4-aminocyclohexyl) propane, 3,3, -dimethyl-4,4 '-diami nodicyclohexyl) propane, 3,3'-dimethyl-4,4'-diaminocyclohexylmethane, 3-ami noethyl-3,5,5-trimethylcyclohexylamine, 2,5-bis (aminomethyl) norbonane, 2,6- Bis (aminomethyl) norbonane and 1,4-diaminomethylcyclohexane as well as any mixtures of these diamines with dicarboxylic acids, such as with oxalic acid, malonic acid, succinic acid, adipic acid, acelaic acid, Decanedicarboxylic acid, dodecanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- Trimethyladipic acid, 2,4,4-trimethyladipic acid, isophthalic acid and tereph thalic acid and with any mixture of these carboxylic acids available. Accordingly, the polyamides also include amorphous copolyamides which pass through Polycondensation of several of the above diamines and / or dicarbon Acid are obtained, and amorphous copolyamides, which Mitverwen tion of ω-aminolauric acid and their lactams are produced.

Particularly suitable, amorphous thermoplastic polyamides are those which from isophthalic acid, hexamethylenediamine and other diamines, such as 4,4'- Diaminodicyclohexyimethane, isophoronediamine, 2,2,4- and / or 2,4,4-tri  methylhexamethylene diamine, 2,5- and / or 2,6-bis (aminomethyl) norbonane are available, those from isophthalic acid, 4,4'-diamino-di-cyclohexyl methane and ω-caprolactam are available, those consisting of isophthalic acid, 3,3'-Dimethyl-4,4'diaminodicyciohexylmethane and ω-Lauriniactam available are, and those made from terephthalic acid and 2,2,4- and / or 2,4,4-trime thylhexamethylene diamine are available.

Instead of the pure 4,4'-diaminodicyclohexylmethane, mixtures can also be used of the positional isomers diaminodicyclohexylmethane can be used.

The amorphous polyamides and their preparation are general to the person skilled in the art known, it is exemplified on Ullmann, encyclopedia of technical Chemie, Volume 19, p. 50.

Suitable thermoplastics are, for example, also semi-crystalline polyamides, especially polyamide-6 (polycaprolactam), polyamide-6,6 (polyhexamethylene adipic acid amide), polyamide-4,6, polyamide-6,12 and partially crystalline copolyami de based on these components. Semi-crystalline are also suitable Polyamides, the acid component of which is wholly or partly (for example in addition to ε-caprolactam) from adipic acid and / or terephthalic acid and / or isophthal acid and / or suberic acid and / or sebacic acid and / or acelaic acid and / or dodecanedicarboxylic acid and / or a cyclohexyldicarboxylic acid consists, and their diamine component in whole or in part in particular m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine and / or isophorone diamine consists and their compositions in principle from the prior art nik are familiar to a person skilled in the art, for example from the encyclope dia of Polymers, Volume 11, p. 315ff.  

In addition, partially crystalline polyamides are suitable which are made up entirely or partially Lactams with 6 to 12 carbon atoms, optionally with Mitver using one or more of the above diamines.

Particularly preferred partially crystalline polyamides are polyamide 6 and polyamide 6,6 or copolyamides with a small proportion, preferably up to about 10% by weight %, on other co-components.

Also suitable as component K2 are polyether ketones, for example as in GB 1 078 234; US-P 4 010 147; EP 135 938, 292 211, 275 035, 280 998, 165 406 and in the publication by C.K. Sham et al Polymer 29/6, 1016-1020 (1988). This Polyether ketones can be obtained, for example, by the bisphenols with bis (haloaryl) ketones in polar aprotic solvents in Presence of alkali carbonates, especially lithium carbonate, implemented become. An example is the reaction of hydroquinone with 4,4'-difluoro called benzophenone.

Polyether sulfones and polysul are also suitable as component K2 fone.

In addition, as component K2 are polyoxyalkylenes, such as that Suitable for polyoxymethylene. Furthermore as component K2 are polymethylene Preferred copolymers which, for example, as comonomers are ethylene oxide, 1,2- Propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxalane and 1,3-dioxepane as cyclic ether and linear oligo- and polyformals such as polydioxoalane or polydioxepane.

Furthermore come as component K2 polyarylene sulfides, especially that Polyphenylene sulfide. Their manufacture is generally known, and  for example in US-P 3,354,129, 3,786,035, 3,853,824, 3,856,560, 3 862 095 and EP-A 171 021.

The composition according to the invention can be used as further constituents Contain additives such as those used in particular for thermoplastic molding compositions are common. As such, for example, antistatic agents, antioxidants, Flame retardants, lubricants, dyes and pigments called.

The particulate polymer (P) according to the invention and the invention according polymer composition (PZ) or their mixture are for Fibers, foils, molding compounds, coatings, lacquers and foams with matt Surface used so that fibers, foils, molding compounds, coatings, Lacquers and foams are created that have at least one part according to the invention cheniform polymer (P) or at least one polymer according to the invention composition (PZ) or mixtures thereof. The inventive Particulate polymer (P) and / or the polymer according to the invention together setting (PZ) can be done by Ver drive extrusion, spinning, injection molding etc. to fibers, Process foils, moldings and foams.

The shaped bodies usually obtained by extrusion or injection molding could have a wide variety of shapes, for example fen ster profiles, garden furniture, boats, signs, lamp covers, automo Parts, children's toys, housings of household appliances, as well as office and Information technology (BIT) housings and parts.

Examples Production of the dispersion articles Regulation for examples (see table 1)

A g of a dispersant B were used as dispersants under inert gas in C g styrene, containing D g divinylbenzene, dissolved and this mixture was then stirred into D g n-hexane. All impurities were removed titrated sec-butyllithium and then the polymerization was at 26 ° C started by adding G mmol sec-butyllithium. The tempera The reaction mixture was regulated to 63 ° C. and the reaction Leave at this temperature for 1.5 hours. To stop the reaction excess ethanol (10ml) was added. The disperse mixture was filtered off and dried in a vacuum drying cabinet at 65 ° C. for 12 hours net. Data received: sales <99%; Particle size: H µm.  

Table 2

Particle size determination

The samples are slurried in immersion oil and between two Cover plate in transmission under the microscope (Carl Zeiss model: Axiophot) examined.

Swelling index measurement of the particles

0.7 g of the sample are dissolved in 50 ml of toluene in a tared centrifuge beaker with a magnetic stirrer. After a dissolving time of two hours, the solution is separated for 60 minutes at 14,000 rpm in a laboratory centrifuge. The excess toluene is decanted and the centrifuge cup is immediately weighed back (total weight - tare = W1). After drying (90 min, 1400 C, 15 min. 215 ° C and vacuum) the cooled cup is weighed back (total weight - tare = W2). The swelling index then results in:

QI = (W2 × 100): W1.

The swelling indices of the above examples are summarized in Table 2:

Table 3

Production of the blends

A crystal-clear polystyrene (BASF, PS 168 N, M _w = 330,000 g / mol) was used as the base material.

Example 5

The dry dispersion polymer from Example 1 was differentiated into concentrations with the crystal-clear polystyrene on an extruder (ZSK 25) compounded at 200 ° C and the properties on injection molded determined his test specimens. The concentrations of the dispersion polymer Risates and the resulting properties are summarized in Table 3 posed.

Example 6

The dry dispersion polymer from Example 2 was differentiated into concentrations with the crystal-clear polystyrene on an extruder  (ZSK 25) compounded at 200 ° C and the properties on injection molded determined his test specimens. The concentrations of the dispersion polymer Risates and the resulting properties are summarized in Table 3 posed.

Comparative Example 7

The dry dispersion polymer from Comparative Example 5 was in different concentrations with the crystal clear polystyrene on one Extruder (ZSK 25) compounded at 200 ° C and the properties injection molded specimens determined. The concentrations of the dispersion polymers and the resulting properties are shown in Table 3 compiled.  

Table 4

Properties of the blend from Example 7-9

From Table 3 it can be seen that the molding compositions according to the invention slight decrease in transmission a significant decrease in gloss  and thus almost constant with increasing matting of the surface Have transparency (determined as transmission). At the same time increases Contrary to comparative experiment 9 with the non-inventive much larger particles the impact strength clearly.

Claims (19)

1. Particulate polymer (P) with a particle size range of 0.5 to 100 microns and a swelling index of 1 to 50, containing as anionically polymerized components

• - At least one anionically polymerizable vinyl monomer and
• - At least one monomer with at least two anionically polymerizable functional groups of the same or different reactivity or a mixture thereof as a crosslinking agent.

2. Polymer (P) according to claim 1, containing 80 to 99.99 wt .-% minde at least one anionically polymerizable monomer and 0.01 to 20 % By weight of at least one crosslinker, in each case based on the total Polymer. 3. Polymer (P) according to claim 1 or 2, wherein the anionic polymeri Sizable monomer is selected from the group containing vinylaro Matic monomers, conjugated dienes, acrylates, alkyl acrylates, alkyl acrylic anhydrides with a double bond, alkyl acid anhydrides with a double bond, acrylamides, alkyl acrylamides and halogenated α- Olefins.   4. Polymer according to one of the preceding claims, wherein the anionically polymerizable monomer contains at least 70% by weight, based on the total anionically polymerizable monomer, of at least one vinyl aromatic monomer of the formula I.
where n has a value from 1 to 4 and R ₁ and R ₂ independently of one another are hydrogen or a C ₁ to C ₈ hydrocarbon group or a C ₁ to C ₈ alkoxy group. 5. Polymer (P) according to any one of the preceding claims, wherein the Ver Crosslinker from at least 70 wt .-% of a monomer with two or more anionically polymerizable functionalities of the same reactivity consists. 6. Polymer (P) according to any one of the preceding claims, wherein the Monomer is styrene and the crosslinker is divinylbenzene. 7. A method for producing a polymer (P) according to any one of the preceding claims, wherein the components of the polymer in the presence

• at least one anion initiating the polymerization,
• - At least one aprotic solvent and
• - At least one block or graft copolymer which is essentially insoluble in the solvent, at least one consisting of at least two polymer chains

be polymerized. 8. The method of claim 7, wherein the polymerization in a Tempe temperature range from 0 to 100 ° C. 9. The method according to claim 7 or 8, wherein the polymerization is initiated with at least one C ₁ to C ₂₀ hydrocarbon anion. 10. The method according to claim 7 to 9, wherein the polymerization in counter were at least one aprotic solvent selected from the Group containing hydrocarbons, ethers, sulphoxides, each with 2 to 10 carbon atoms. 11. The method according to any one of claims 7 to 10, wherein the polymerisa tion in the presence of at least one block copolymer, at least the best starting from a polymer block (A) from a vinyl aromatic mono mer and a polymer block (B) from a diene. 12. The method of claim 12, wherein the polymerization in the presence a block copolymer consisting of a 1 to 50 wt .-% of at least one Polymer block (A) and 50 to 99 wt .-% of at least one polymer block (B), based in each case on the entire block copolymer, he follows. 13. The method according to any one of claims 7 to 12, wherein the polymerization in the presence of an AB or ABA or BAB block copolymer.   14. The method according to any one of claims 7 to 13, wherein the polymerisa tion in the presence of a block polymer with a molecular weight of 1000 to 500,000 takes place. 15. Polymer (P) according to any one of claims 1 to 6, obtainable by a Method according to one of claims 7 to 14. 16. Polymer composition (PZ) containing at least 50% by weight of a mixture (M), based on the total polymer composition (PZ), with the components

• - At least one polymer (P) according to one of claims 1 to 6 and 15 as component (K1) and
• - At least one thermoplastic mass as component (K2)

includes. 17. Polymer composition (PZ) according to claim 16, based on the total mixture (M) containing 0.1 to 50 wt .-% (K1) and 50 to 99.9% by weight (K2), and 0 to 40% by weight of at least one fiber or particulate filler or a mixture thereof and 0 to 20% by weight at least one additive or processing aid or their mixture. 18. Use of a polymer (P) according to any one of claims 1 to 6 and 15 or according to a polymer composition (PZ) according to one of the Claims 16 and 17 or their mixtures for fibers, films, Molding compounds and foams with a matt surface.   19. Fibers, foils, molding compounds, coatings, lacquers and foams comprising at least one polymer (P) according to one of claims 1 to 6 and 15 or at least one polymer composition (PZ) one of claims 16 and 17 or mixtures thereof.