DE102008001825A1 - Use of organosilicone copolymers as impact modifiers - Google Patents

Abstract

The invention relates to the use of organosilicone copolymers as toughening modifiers, characterized in that the organosilicone copolymers comprise a) one or more polysiloxane units and b) one or more vinyl polymer units and the units a) and b) covalently with one another linked to form a comb, block or ladder structure; and (meth) acrylic ester-silicone copolymers having a comb, block or conductor structure, obtainable by free-radically initiated substance or solution polymerization of a) one or more (meth) acrylic esters, b) one or more mono- or polyethylenically unsaturated polyorganosiloxanes and optionally c) one or more other ethylenically unsaturated monomers with the proviso proviso that none of the components a) to c) is selected from the group comprising alkoxy-substituted ethylenically unsaturated silanes, hydroxy-substituted (meth) acrylic acid esters , Hydroxy-substituted (meth) acrylic acid amides, amino-substituted (meth) acrylic acid esters, unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, and polyorganosiloxanes bearing free hydroxyl groups.

Description

The This invention relates to the use of organosilicone copolymers as an impact modifier, impact modified therewith Polymer compositions and molding compositions and (meth) acrylic acid ester silicone copolymers.

molding compounds can be made of thermoplastic polymers by means of thermoplastic Forming techniques, such as injection molding, extrusion, Pressing or deep drawing, are produced. To the mechanical Properties of molding compounds, such as their impact strength, often become impact modifiers used. The impact resistance is a measure of the resistance of a material to breakage, for example is loaded by a blow or impact. The impact resistance is measured as energy required to break per area and serves as a parameter for the strength of molding compounds. The impact resistance of molding compounds is strongly dependent on temperature. In particular, far below the Glass transition temperature of their polymeric constituents Molding compounds become brittle and break accordingly, which is easy drastically restrict their potential uses.

Examples for impact modifiers are rubbery Additives, such as graft copolymers having a core-shell structure, an elastomeric siloxane or organopolymer core and a on it grafted polymer shell included. The cores are mostly highly cross-linked and elastic and have a particulate character. Of the elastomeric core is able to be registered by impact To absorb and dissipate energy. The grafted polymer shell ensures compatibilization and compatibility Impact modifier with the individual components the impact modified polymer composition and acts thus contrary to a phase separation.

The US 4918132 describes core-shell polymers for toughening polyester resins. The core-shell polymers were obtained by graft-copolymerizing organic vinyl monomers onto crosslinked cores which are composites of organosilicon compounds and ethylenically unsaturated organic monomers. The EP-A 537014 describes impact modified polycarbonates containing particles with a polysiloxane / organopolymer core and an organopolymer shell.

The WO-A 02/36682 and WO-A 02/36683 teach molding compositions of polymethyl methacrylate (PMMA) with improved impact strength at low temperatures. As impact modifiers silicone elastomers are used, which carry a PMMA shell.

adversely on the core-shell polymers is their complex and usually multi-step synthesis. In addition, the production takes place the core-shell polymers generally in heterogeneous, aqueous phase, usually a residual moisture remains in the polymerization. Residual moisture may be present when processing the impact modifier with the thermoplastic polymers such as polyesters lead to a hydrolytic degradation of the polymer chains and thus a deterioration of the mechanical properties thereof cause the available molding compounds.

One Another disadvantage of common impact modifiers based on siloxane polymers is the corresponding during mixing Core-shell polymers frequently occurring clouding thermoplastic polymers based on different refractive indices the thermoplastic polymers and the impact modifier can be returned.

Furthermore there is a need for impact modified polymer compositions, in comparison to the said, conventionally impact-modified Polymer compositions to molding compositions with higher impact strength to lead.

It it was therefore an object to provide impact modifiers, which do not have the above-mentioned disadvantages and with which Moldings with high impact resistance accessible become.

Surprisingly this problem has been solved with organosilicone copolymers, which have a comb, block or ladder structure.

Organosilicone copolymers have hitherto been used, for example, as coating compositions, water repellents or as additives for paints, cosmetics or building chemical products, such as those described in US Pat WO-A 03/085035 or the DE-A 102005034121 described organosilicone copolymers based on Vinyl esters and ethylenically unsaturated polyorganosiloxanes. The EP-A 0352339 discloses curable coating compositions comprising crosslinkable organosilicone copolymers which, in addition to (meth) acrylate and organosilicone units, also contain crosslinkable silane units. The EP-A 1375605 discloses organosilicone copolymers as flow control agents for coating compositions wherein the siloxane units of the organosilicone copolymers bear hydroxy-substituted radicals. The EP-A 1193303 and the DE-A 102006054158 describe crosslinkable coating compositions containing crosslinkable organosilicone copolymers having hydroxy, amino or carboxylic acid groups substituted monomer units.

• a) ein oder mehrere Polysiloxan-Einheiten und
• b) ein oder mehreren Vinylpolymer-Einheiten enthalten und

die Einheiten a) und b) kovalent so miteinander verknüpft sind, dass sie eine Kamm-, Block- oder Leiter-Struktur bilden.The invention relates to the use of organosilicone copolymers as toughening modifiers, characterized in that the organosilicone copolymers

• a) one or more polysiloxane units and
• b) contain one or more vinyl polymer units and

the units a) and b) are covalently linked together to form a comb, block or ladder structure.

polymers with comb, block or ladder structure are known in the art. Block polymers are known to contain at least two different polymer units as recurring units, the in a statistical or defined sequence a substantially linear Forming a chain. In polymers with comb or ladder structure form the said repeating units take the form of a comb or a ladder to. In polymers with comb, block or ladder structure are the Thus, individual polymer units are essentially not cross-linked and have no core-shell structure.

The organosilicone copolymers can be obtained by means of free-radically initiated substance or solution polymerization of one or more mono- or polyethylenically unsaturated polyorganosiloxanes and
one or more ethylenically unsaturated monomers selected from the group comprising (meth) acrylic esters, vinyl esters, vinyl aromatics, vinyl ethers, vinyl halides and olefins.

The Preparation of organosilicone copolymers by means of substance or Solution polymerization is essential to copolymers with To obtain comb, block or ladder structure.

Preferred mono- or polyethylenically unsaturated polyorganosiloxanes are those of the general formula (1) (SiO _4/2 ) _k (R ¹ SiO _3/2 ) _m (R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _1/2 SiR ³ ₂ -L x] _s [O _1/2 H] _t (1), in which
L is a bivalent aromatic, heteroaromatic or aliphatic group, optionally monosubstituted or polysubstituted with R ⁴ ,
R ¹ , R ³ , R ⁴ each independently represent a hydrogen atom or a monovalent optionally with -CN, -NCO, -NR ² ₂ , -COOH, -COOR ² , -PO (OR ² ) _{2 ,} -halo, -acrylic, Epoxy, -SH, -OH or -CONR ² ₂ substituted hydrocarbon radical having 1 to 20 C-atoms or a Kohlenwasserstoffoxyrest having 1 to 20 C-atoms, in which in each case one or more, not adjacent methylene units by groups -O-, -CO-, -COO-, -OCO-, or -OCOO-, -S-, or -NR ² - and one or more mutually non-adjacent methine units by groups -N =, -N = N-, or -P = can be replaced,
X is an ethylenically unsaturated radical,
R ^{2 is} hydrogen or a monovalent optionally substituted hydrocarbon radical,
s integer values of at least 1,
t 0 or integer values,
and the sum of k + m + p + q means integer values of at least 2.

Preferred radicals R ¹ , R ² , R ³ , R ⁴ are aromatic, saturated or unsaturated, straight-chain or branched aliphatic radicals having 1 to 20 C atoms, preferably 1 to 12 C atoms, particularly preferably 1 to 6 C atoms where optionally a carbon atom may be replaced by an oxygen atom, and wherein the free valencies carry hydrogen atoms. Particularly preferred radicals R ¹ , R ² , R ³ , R ⁴ are methyl, ethyl, phenyl and vinyl. The radical R ³ is most preferably a methyl radical. The radical R ⁴ most preferably represents a hydrogen atom.

The group L is preferably a methylene, ethylene, propylene or phenylene group or for a covalent bond.

The radical X is an ethylenically unsaturated radical having preferably 1 to 20 C atoms, particularly preferably 1 to 12 C atoms. For example, the radical X is a vinyl radical, in particular -C ₂ H ₃ , acrylic radical, in particular -OCOC ₂ H ₃ , or a methacrylic radical, in particular -OCOC ₂ H ₂ CH ₃ . The radicals X can be arranged terminally or in the chain of the polyorganopolysiloxanes of the formula (1). Preferably, the polyorganopolysiloxanes are terminally substituted by 1 or 2 radicals X.

In preferred polyorganosiloxanes of formula (1) are the ethylenic unsaturated groups consisting of the group L and the Rest X via an Si-C bond to a silicon atom of the polyorganosiloxane bound.

s is preferably 1 or 2, more preferably 1.

t is preferably ≦ 10, more preferably 0.

The Sum of the values of k, m, p, q, s and t is preferably a number from 3 to 20,000, especially 8 to 1,000.

The polyorganosiloxanes of the formula (1) may be cyclic, branched, crosslinked or preferably linear; ie the polyorganosiloxane of the formula (1) is preferably composed essentially of R ₂ SiO _2/2 units, more preferably exclusively of R ₂ SiO _2/2 . Accordingly, the quotient of p and the sum of k, m, p and q is preferably 0.95 to 1.00.

Examples for polyorganosiloxanes of the formula (1) are α, ω-divinyl-polydimethylsiloxanes, α, ω-di- (3-acryloxypropyl) polydimethylsiloxanes, α, ω-di- (3-methacryloxypropyl) polydimethylsiloxanes, α, ω-di- (acryloxymethyl) -polydimethylsiloxanes, α, ω-di- (methacryloxymethyl) -polydimethylsiloxanes, α-monovinyl-polydimethylsiloxanes, α-mono- (3-acryloxypropyl) -polydimethylsiloxanes, α-mono- (3-methacryloxypropyl) -polydimethylsiloxanes, α- Mono (acryloxymethyl) -polydimethylsiloxanes, α-mono (methacryloxymethyl) -polydimethylsiloxanes. Preference is given to α, ω-divinylpolydimethylsiloxanes, α-mono- (methacryloxymethyl) -polydimethylsiloxanes or α, ω-di- (methacryloxymethyl) -polydimethylsiloxanes.

Suitable but are also polyorganosiloxanes of the formula (1), in which k and / or m are different from zero. Examples of these are polyorganosiloxanes of the formula (1) in which the ratio of the sum of k and m to the sum of k, m, p and q is 0.50 to 1.00, preferably 0.90 to 1.00.

The Polyorganosiloxanes of the formula (1) are preferably from 1 to 90 Wt .-%, particularly preferably 20 to 75 wt .-% and most preferably 25 to 70 wt .-%, based on the total weight of the ethylenic unsaturated polyorganosiloxanes and the ethylenically unsaturated Monomers for the preparation of organosilicone copolymers.

preferred ethylenically unsaturated monomers from the group of acrylic esters or methacrylic esters are esters of unbranched or branched alcohols having 1 to 15 carbon atoms. examples for preferred methacrylic esters or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, Propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Particularly preferred Methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate.

Preferred vinyl esters are vinyl esters of linear or branched monocarboxylic acids having 1 to 15 carbon atoms. Examples of preferred Vinylester are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and Vinylester of α-branched monocarboxylic acids having 9 to 11 carbon atoms, for example VeoVa9 ^® or VeoVa10 ^® (from Resolution). Particularly preferred are vinyl acetate and Vinylester of α-branched monocarboxylic acids having 9 to 11 carbon atoms, for example VeoVa9 ^® or VeoVa10 ^®. Most preferred is vinyl acetate.

When Vinylaromatics preferred are styrene, alpha-methylstyrene, the isomers Vinyltoluenes and vinylxylenes and divinylbenzenes. Especially preferred is styrene. Preferred olefins are ethene, propene, 1-alkylethene and polyunsaturated alkenes, such as 1,3-butadiene and isoprene. Particularly preferred are ethene and 1,3-butadiene. A preferred one Vinyl ether is methyl vinyl ether. A preferred vinyl halide is vinyl chloride.

Prefers be used for the preparation of organosilicone copolymers as ethylenically unsaturated monomers also mixtures of at least two (meth) acrylic esters, such as n-butyl acrylate and methyl (meth) acrylate; n-butyl acrylate and 2-ethylhexyl acrylate and / or methyl (meth) acrylate; (Meth) acrylic acid and hydroxypropyl (meth) acrylate; or mixtures of styrene and one or more monomers from the group comprising methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl acrylate; or mixtures of 1,3-butadiene and styrene and / or methyl (meth) acrylate.

Preferably be 10 to 99 wt .-% of ethylenically unsaturated monomers, particularly preferably 50 to 80 wt .-% used, based on the Total weight of the ethylenically unsaturated polyorganosiloxanes and of the ethylenically unsaturated monomers for the preparation the organosilicone copolymers.

Optionally, it is also possible to use from 0.1 to 20% by weight, preferably from 0.1 to 10% by weight, of ethylenically unsaturated auxiliary monomers, based on the total weight of the ethylenically unsaturated monomers for the preparation of the organosilicone copolymers. When using one or more auxiliary monomers, preferably 0.5 to 2.5% by weight, based on the total weight of the ethylenically unsaturated monomers for preparing the organosilicone copolymers, are used per auxiliary monomer. Examples of auxiliary monomers are ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid amides and nitriles, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid such as diethyl and diisopropyl esters and maleic anhydride, ethylenically unsaturated sulfonic acids or their salts, preferably vinylsulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid. Further examples are post-crosslinking comonomers, for example acrylamidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, alkyl ethers such as isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrylamide and N -Methylolallylcarbamats. Also suitable are epoxide-functional ethylenically unsaturated comonomers such as glycidyl methacrylate and glycidyl acrylate. Also mentioned are ethylenically unsaturated monomers having hydroxyl or CO groups, for example methacrylic acid and acrylic acid hydroxyalkyl esters such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate, and also compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate. Furthermore, unsaturated silanes are copolymerizable ethylenically called as vinyl silanes such as vinyltrimethoxysilane or vinyltriethoxysilane or (meth) acrylosilanes, such as GENIOSIL ^® GF-31 (methacryloxypropyl trimethoxysilane), XL-33 (methacryloxymethyl), XL-32 (Methacryloxymethyldimethylmethoxysilan), XL-34 (Methacryloxymethylmethyldimethoxysilan) and XL-36 (methacryloxymethyltriethoxysilane) (each trade name of Wacker Chemie).

• a) einem oder mehreren (Meth)acrylsäureestern,
• b) einem oder mehreren einfach oder mehrfach ethylenisch ungesättigten Polyorganosiloxanen, und gegebenenfalls
• c) einem oder mehreren weiteren ethylenisch ungesättigten Monomeren

mit der Maßgabe (proviso), dass keine der Komponenten a) bis c) ausgewählt wird aus der Gruppe umfassend mit Alkoxy-Resten substituierte ethylenisch ungesättigte Silane, Hydroxy-substituierte (Meth)acrylsäureester, Hydroxy-substituierte (Meth)acrylsäureamide, Amino-substituierte (Meth)acrylsäureester, ungesättigte Carbonsäuren, ungesättigte Carbonsäureanhydride und Polyorganosiloxane, die Reste mit freien Hydroxygruppen tragen.Another object of the invention are (meth) acrylic acid ester silicone copolymers with comb, block or conductor structure obtainable by free-radically initiated substance or solution polymerization of

• a) one or more (meth) acrylic esters,
• b) one or more mono- or polyunsaturated ethylenically unsaturated polyorganosiloxanes, and optionally
• c) one or more further ethylenically unsaturated monomers

with the proviso that none of components a) to c) is selected from the group comprising alkoxy-substituted ethylenically unsaturated silanes, hydroxy-substituted (meth) acrylic esters, hydroxy-substituted (meth) acrylamides, amino-substituted (Meth) acrylic acid esters, unsaturated carboxylic acids, unsaturated carboxylic anhydrides and polyorganosiloxanes which carry radicals having free hydroxy groups.

to Preparation of the (meth) acrylic ester-silicone copolymers are the same ethylenically unsaturated polyorganosiloxanes and (meth) acrylic acid esters are suitable, preferred and especially suitable preferred for preparing the organosilicone copolymers according to and the proviso of the (meth) acrylic acid ester silicone copolymers fulfill.

At the Most preferred (meth) acrylic acid esters here are methyl (meth) acrylate, n-butyl methacrylate or 2-ethylhexyl acrylate.

When further ethylenically unsaturated monomers for the preparation the (meth) acrylic ester-silicone copolymers are the same Vinyl esters, vinyl aromatics, vinyl ethers, vinyl halides or olefins suitable, preferred and particularly preferred, for the production the organosilicone copolymers are listed accordingly, and the proviso the (meth) acrylic ester-silicone copolymers fulfill.

ethylenically unsaturated, alkoxy-substituted silanes are preferably silicon compounds having a silicon atom which is at least bears a residue with an ethylenically unsaturated group and at least one alkoxy radical having 1 to 20 carbon atoms.

Preferably for the preparation of the (meth) acrylic ester-silicone copolymers none with ethylenically unsaturated, with alkoxy radicals substituted silanes and no monomers used above as Hilfsmonomere are designated. Particularly preferred for the preparation of (Meth) acrylic ester-silicone copolymers are not ethylenic used unsaturated monomers which are suitable for crosslinking are.

to Preparation of the (meth) acrylic ester-silicone copolymers will preferably be preferably 1 to 90% by weight, especially preferably from 30 to 80% by weight, very particularly preferably from 40 to 80% by weight and most preferably 45 to 80% by weight of ethylenically unsaturated Polyorganosiloxanes used, based on the total weight of Components a), b) and c) for the preparation of (meth) acrylic ester-silicone copolymers.

The Molecular weight Mw of the organosilicone copolymers or of the (meth) acrylic ester-silicone copolymers is preferably from 10,000 to 50,000 g / mol and especially preferably from 15,000 to 40,000 g / mol, each determined by means Gel permeation chromatography on polystyrene standards.

The selection of the components and their weight fractions for the preparation of the organosilicone copolymers or the (meth) acrylic acid ester silicone copolymers is preferably carried out so that in general a glass transition temperature Tg of ≤ 100 ° C, preferably between -50 ° C and +80 ° C results. The glass transition temperature Tg of the organosilicone copolymers can be determined in a known manner by means of differential scanning calorimetry (DSC). The Tg can also be approximated by the Fox equation. To Fox TG, Bull. Physics Soc. 1, 3, page 123 (1956) the following applies: 1 / Tg = x1 / Tg1 + x2 / Tg2 + ... + xn / Tgn, where xn is the mass fraction (wt .-% / 100) of the monomer n, and Tg _{n is} the glass transition temperature in Kelvin of the homopolymer of Monomers n is. Tg values for homopolymers are, for example, in the Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) listed.

The Preparation of the organosilicone copolymers or the (meth) acrylic ester-silicone copolymers takes place by radical substance or solution polymerization of the ethylenically unsaturated components in the presence of radical initiators. In this case, the polymerization products during the polymerization also in the form of a dispersion available. The solution polymerization is preferred.

suitable organic solvents are, for example, alcohols 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol or i-propanol, Ketones, such as acetone or methyl ethyl ketone, esters, such as methyl acetate, ethyl acetate, Propyl acetate, butyl acetate or methoxypropyl acetate, or aromatic Hydrocarbons having 6 to 15 carbon atoms, such as xylene.

Suitable are also mixtures of several organic solvents, such as isopropanol / ethyl acetate or methoxypropyl acetate / isopropanol mixtures.

in the Generally, no water is used as the solvent component for the polymerization added. The content of water is preferably ≦ 10 Wt .-%, more preferably ≤ 1 wt .-% and most preferably ≤ 0.01 Wt .-%, each based on the total mass of the organic used Solvent.

The individual components for the preparation of the organosilicone copolymers are under normal conditions DIN 50014 in the solvents or mixtures of several organic solvents each preferably at least 1 wt .-%, more preferably at least 10 wt .-% soluble.

The Polymerization is preferably carried out at temperatures of 0 ° C up to 150 ° C, preferably from 20 ° C to 130 ° C, particularly preferably carried out from 30 ° C to 120 ° C. The polymerization may be batchwise or continuously, under Presentation of all or individual components of the reaction mixture, with partial presentation and subsequent dosing of individual components the reaction mixture or after the dosing without template be performed. All dosages are preferably carried out depending on the consumption of the respective component. Especially preferred is a polymerization in which the silicone building blocks submitted and the remaining reactive components of the polymerization be dosed.

The initiation of the polymerization takes place by means of the usual initiators or redox initiator combinations. Examples of initiators are the sodium, potassium and ammonium salts of peroxydisulphuric acid, Hydrogen peroxide, t-butyl peroxide, t-butyl hydroperoxide, potassium peroxodiphosphate, t-butyl peroxypivalate, cumene hydroperoxide, t-butyl peroxobenzoate, isopropylbenzene monohydroperoxide and azobisisobutyronitrile. The initiators mentioned are preferably used in amounts of from 0.01 to 4.0% by weight, based on the total weight of the monomers used, for the preparation of the organosilicone copolymers. The redox initiator combinations used are the abovementioned initiators in conjunction with a reducing agent. Suitable reducing agents are sulfites and bisulfites of monovalent cations, for example sodium sulfite, the derivatives of sulfoxylic acid such as zinc or Alkaliformaldehydsulfoxylate, for example Natriumhydroxymethansulfinat and ascorbic acid. The amount of reducing agent is preferably 0.15 to 3 wt .-% of the monomers used for the preparation of organosilicone copolymers.

In addition, small amounts of a metal compound which is soluble in the polymerization medium and whose metal component is redox-active under the polymerization conditions, for example based on iron or vanadium, can be introduced. Particularly preferred initiators are t-butyl peroxypivalate, and t-butyl peroxobenzoate, and the peroxide / reducing agent combinations ammonium persulfate / sodium hydroxymethanesulfinate and potassium persulfate / sodium hydroxymethanesulfinate. An overview of other suitable initiators in addition to the representatives just described can be found in Handbook of Free Radical Initiators, ET Denisov, TG Denisova, TS Pokidova, 2003, Wiley Publishing

The Isolation of the organosilicone copolymers from the solvent after polymerization, by removal of the solvent by distillation, by precipitation and filtration of Organosilicone copolymers by addition of a non-solvent, by decantation or by a combination of these methods. The organosilicone copolymers of the invention are in isolated form generally in the form of a solid or a high viscosity oil. Preferably, the Organosilicone copolymers optically transparent.

• a) ein oder mehrere Polysiloxan-Einheiten und
• b) ein oder mehreren Vinylpolymer-Einheiten enthalten und

die Einheiten a) und b) kovalent so miteinander verknüpft sind, dass sie eine Kamm-, Block- oder Leiter-Struktur bilden.Another object of the invention are impact-modified polymer compositions containing one or more organosilicone copolymers, one or more thermoplastic polymers and optionally one or more additives, characterized in that the organosilicone copolymers

• a) one or more polysiloxane units and
• b) contain one or more vinyl polymer units and

the units a) and b) are covalently linked together to form a comb, block or ladder structure.

suitable thermoplastic polymers are, for example, polyolefins, such as polyethylene, Polypropylene, polystyrene, polyamides, polyvinyl halides, such as polyvinyl chloride, Polyoxymethylene, polycarbonates, poly (meth) acrylic esters, such as polymethyl methacrylate, aromatic polyesters, such as polyalkylene terephthalates, aliphatic polyesters such as polyhydroxybutyric acid, polycaprolactone or polylactic acid.

When other additives for impact-modified Polymer compositions may, for example, be fibrous Reinforcing materials (glass fibers, carbon fibers, chemical fibers, such as polyester or polyamide, natural fibers such as cotton or cellulose), mineral fillers such as chalk, clays, pigments, dyes, stabilizers, Flame retardants and other other polymers are used.

In the impact modified polymer compositions the proportion of organosilicone copolymers is preferably 2 to 50% by weight, particularly preferably 5 to 40 wt .-%, based on the total weight the impact modified polymer composition.

In an alternative embodiment, the Organosilicone copolymers via covalent bonds to the Tethered thermoplastic polymers. This can, among other things a separation of the components of impact-modified Counteracted polymer compositions and thus the storage stability the toughened polymer compositions become. Such bonds occur, for example, when using Organosilicone copolymers containing one or more units auxiliary monomers, such as hydroxyethyl (meth) acrylate, Hydroxypropyl methacrylate or (meth) acrylic silanes for impact modification of thermoplastic polymers such as polyesters.

The production of impact-modified polymer compositions is carried out by customary processes by processing one or more thermoplastic polymers, one or more organosilicone copolymers and optionally further additives, for example in roll kneaders or extruders. Here, the thermoplastic polymer, for example in the form of granules, with the organosilicone copoly mer and optionally further additives are mixed, melted and thereby mixed. Likewise, the thermoplastic polymer, the organosilicone copolymer and optionally other additives can be melted separately and then blended. Preferably, the mixing is carried out under high shear, whereby a particularly homogeneous mixture of the components can be achieved.

The Mixing temperature and mixing time depends on the characteristics the respective components of the impact-modified polymer compositions and is usually chosen so that a homogeneous Distribution of the components is guaranteed and the thermal Stress on the composition kept as low as possible becomes.

The Impact-modified polymer compositions can then directly in the form of their melt thermoplastic be further processed. Alternatively, the mixture can be converted into granules, which thermoplastically processed at a later date can be.

One Another object of the invention are molding compositions available by thermoplastic deformation of impact-modified Polymer compositions.

to thermoplastic forming can those known in the art Methods are used, such as injection molding, Extrusion, pressing or deep drawing.

In the impact-modified according to the invention Polymer compositions, the thermoplastic polymer is typically as a continuous phase in which the organosilicone copolymers as discontinuous phases (domains) are distributed. The domains preferably have a diameter of 10 to 10,000 nm, more preferably from 10 to 100 nm, especially preferably 10 to 250 nm, and most preferably from 10 to 40 nm. The size of the invention Domains has an advantageous effect for producing transparent impact-modified polymer compositions or molding compositions out. Alternatively, the organosilicone copolymers can be used in the toughened polymer compositions the continuous Training phase. In this case, the thermoplastic polymer lies as a discontinuous phase in the form of domains.

One repeated melting of the impact-modified polymer compositions typically does not cause segregation of the continuous and discontinuous phases.

The Organosilicone copolymers containing molding compositions have high impact strength, especially high low-temperature impact strengths, and high notched impact strengths. The use of organosilicone copolymers does not cause turbidity of the impact modified Polymer compositions or molding compositions. According to the invention Impact-modified polymer compositions with low or without residual water content accessible, so that a hydrolytic Degradation during further processing can be excluded. In addition, the organosilicone copolymers act in the Impact modified polymer compositions and the Fire-retardant molding compounds. On the weathering and aging resistance as well as the temperature stability of molding compounds have an effect the organosilicone copolymers also advantageous.

The The following examples serve for a detailed explanation of the invention and are in no way limiting to understand.

Examples

Synthesis of Organosilicone Copolymers

Examples 1a-1f:

It were 30 parts by weight of the respective polyorganosiloxane (Table 1) dissolved in 390 parts by weight of methoxypropyl acetate and in a jacketed shell reactor with additional De-cooling and an anchor agitator under nitrogen atmosphere heated to 120 ° C. Then within 0.5 hours 0.5 Parts by weight of tertiary butyl peroxybenzoate dissolved added in 10 parts by weight of methoxypropyl acetate. The dosage The monomers (Table 1) were started and carried out simultaneously during 2 hours. After initiator dosing were another 0.2 parts by weight of radical initiator metered intermittently. It was stirred for one hour at 120 ° C.

• a) BMA: n-Butylmethacrylat; MMA: Methylmethacrylat; MAS: Methacrylsäure; HPMA: Hydroxypropylmethacrylat.
• b) MA-PDMS1: α-Methacryloxymethylpolydimethylsiloxan mit Mn 3000 g/mol; MA-PDMS2: α-Methacryloxymethylpolydimethylsiloxan mit Mn 1000 g/mol; X-PDMS-X: lineares α,ω-Dibrompropionyl-polydimethylsiloxan 1200 g/mol; MA-PDMS-MA: lineares α,ω-Bis-(Methacryloxymethyl)polydimethylsiloxan mit Mn 3000 g/mol.

Subsequently, the solvent was completely removed under reduced pressure. The respective organosilicone copolymer was obtained in the form of a transparent solid. Table 1: Composition and Structure of the Organosilicone Copolymers of Examples 1a to 1g: example Monomer ^a) ([% by weight]) Polyorganosiloxane ^b) ([% by weight]) Polymer structure 1a MMA (70) MA-PDMS1 (30) Comb 1b BMA (70) MA-PDMS1 (30) Comb 1c BMA (5), MMA (21) MA-PDMS1 (74) Comb 1d BMA (21) MMA (5) MA-PDMS1 (74) Comb 1e MAS (65), HPMA (5) MA-PDMS2 (30) Comb 1f MMA (70) MA-PDMS-MA (30) ladder 1g MMA (80) X-PDMS-X (20) block

• a) BMA: n-butyl methacrylate; MMA: methyl methacrylate; MAS: methacrylic acid; HPMA: hydroxypropyl methacrylate.
• b) MA-PDMS1: α-methacryloxymethylpolydimethylsiloxane with Mn 3000 g / mol; MA-PDMS2: α-methacryloxymethylpolydimethylsiloxane with Mn 1000 g / mol; X-PDMS-X: linear α, ω-dibromopropionyl-polydimethylsiloxane 1200 g / mol; MA-PDMS-MA: linear α, ω-bis (methacryloxymethyl) polydimethylsiloxane with Mn 3000 g / mol.

Example 1g:

20 Parts by weight of the polyorganosiloxane (Table 1) and 80 parts by weight of the previously purified by distillation monomer (Table 1) were presented in 100 parts by weight of xylene. The solution was three times by applying a vacuum and embroidering oxygen freed. Subsequently, Cu (I) Br and PMDETA (pentamethyldiethylenetriamine) added and the resulting reaction mixture for 6 h at Kept at 100 ° C. Subsequently it became insoluble Catalyst filtered and the organosilicone copolymer by addition From 500 parts by weight of methanol precipitated, isolated and dried.

Production of impact-modified Polymer compositions and molding compositions and determination of notched impact strengths:

The thermoplastic polymer polylactic acid (manufacturer Fa. NatureWorks, type PLA4032D) was used in a roll kneader (Rheomix OS 3000, Thermo-Fisher Scientific), if necessary with the respective impact modifier (Table 2) and at a temperature of 180 ° C. at 20 rpm for 20 minutes to an optionally impact modified Processed polymer composition.

From the impact-modified polymer compositions of Comparative Examples 2 to 4 and Examples 5 to 11, respectively DIN EN ISO 19-1eC standard-compliant test specimens, ie molding compounds produced on the basis of which the notched impact strength after DIN EN ISO 19-1eC was determined. The molding compositions thus obtained were transparent.

Out the data in Table 2 impact resistance and fracture pattern shows that the molding compositions of the invention (Table 2, Examples 4, 8 to 10) similar or even have far better properties than conventional impact modifiers containing molding compositions (Table 2, Comparative Examples 2 and 3).

One significant advantage of the procedure according to the invention is that the impact modifiers according to the invention, d. H. the silicone organocopolymers, by simple copolymerization the individual ethylenically unsaturated monomers and the Polyorganosiloxanes are obtained, whereas the production of core-shell copolymers is expensive.

• a) Angabe in Gew.-% bezogen auf das Gewicht des thermoplastischen Polymers Polymilchsäure.
• b) bestimmt nach DIN EN ISO 19-1eC .
• c) bestimmt mittels Transmissionselektronenmikroskopie
• d) Kern-Schale-Siliconacrylat der Firma Mitsubishi-Rayon
• e) Kern-Schale-Siliconacrylat der Firma Wacker Chemie

In the molding compositions of Examples 5 to 8, 10 and 11 (Table 2) came with the (meth) acrylic acid ter-silicone copolymers impact modifiers are used, which contain only low-cost methacrylic ester monomer units and are thus economically particularly interesting. Table 2: Impact-modified polymer compositions and testing of corresponding molding materials: Impact modifier ([wt%]) ^a) Impact strength [kJ / m ² ] ^b) fracture pattern average diameter of the silicon domains ^c) [nm] CEx. 2 - 2.1 Broken - CEx. 3 Metablen®d ⁾ (15% by weight) 14 opened not determined CEx. 4 GENIOPERL ^®e) (15% by weight) 12.5 Broken 100-250 Example 5 Copolymer from Example 1a (15% by weight) 30.7 opened 40-250 Example 6 Copolymer from Example 1b (15% by weight) 5.5 opened 100-1500 Example 7 Copolymer from Example 1c (15% by weight) 4.1 opened 100-5000 Ex. 8 Copolymer from Example 1d (15% by weight) 4.3 opened 100-10000 Ex. 9 Copolymer from Example 1e (15% by weight) 42.5 opened 30-500 Ex. 10 Copolymer from example 1f (15% by weight) 29.7 opened 80-200 Ex. 11 Copolymer from Example 1g (15% by weight) 21.0 opened 50-170

• a) in wt .-% based on the weight of the thermoplastic polymer polylactic acid.
• b) determined by DIN EN ISO 19-1eC ,
• c) determined by transmission electron microscopy
• d) core-shell silicone acrylate from Mitsubishi Rayon
• e) core-shell silicone acrylate from Wacker Chemie

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 4918132 [0004]
• - EP 537014 A [0004]
• WO 02/36682 A [0005]
• WO 02/36683 A [0005]
• WO 03/085035 A [0011]
• - DE 102005034121 A [0011]
• EP 0352339 A [0011]
• - EP 1375605 A [0011]
• - EP 1193303 A [0011]
• - DE 102006054158 A [0011]

Cited non-patent literature

• - Fox TG, Bull. Physics Soc. 1, 3, page 123 (1956) [0042]
• J. Wiley & Sons, New York (1975) [0042]
• - DIN 50014 [0047]
• "Handbook of Free Radical Initiators", ET Denisov, TG Denisova, TS Pokidova, 2003, Wiley Publishing [0050]
• - DIN EN ISO 19-1eC [0070]
• - DIN EN ISO 19-1eC [0070]
• - DIN EN ISO 19-1eC [0073]

Claims (10)

Use of organosilicone copolymers as toughening modifiers, characterized in that the organosilicone copolymers a) comprise one or more polysiloxane units and b) one or more vinyl polymer units and the units a) and b) are covalently linked to one another such that they forming a comb, block or ladder structure. Use of organosilicone copolymers according to claim 1, characterized in that the organosilicone copolymers obtained be by means of free radical initiated substance or solution of one or more than one or more ethylenically unsaturated Polyorganosiloxanes and one or more ethylenically unsaturated Monomers selected from the group comprising (meth) acrylic esters, Vinyl esters, vinyl aromatics, vinyl ethers, vinyl halides and olefins. Use of organosilicone copolymers according to Claim 2, characterized in that ethylenically unsaturated polyorganosiloxanes of the general formula (1) (SiO _4/2 ) _k (R ¹ SiO _3/2 ) _m (R ¹ ₂ SiO _2/2 ) _p (R ¹ ₃ SiO _1/2 ) _q [O _1/2 SiR ³ ₂ -L x] _s [O _1/2 H] _t (1), where L is a bivalent aromatic, heteroaromatic or aliphatic, optionally mono- or polysubstituted with R ⁴ group, R ¹ , R ³ , R ^{4 are} each independently a hydrogen atom or a monovalent optionally with -CN, -NCO, -NR ² ₂ , -COOH, -COOR ² , -PO (OR ² ) ₂ , -halo, -acryl, -epoxy, -SH, -OH or -CONR ² ₂ substituted hydrocarbon radical having 1 to 20 C atoms or a hydrocarbonoxy radical having 1 to 20 carbon atoms, in each of which one or more, non-adjacent methylene units represented by groups -O-, -CO-, -COO-, -OCO-, or -OCOO-, -S-, or -NR ² - and one or more mutually non-adjacent methine units can be replaced by groups -N =, -N = N-, or -P =, X is an ethylenically unsaturated radical, R ^{2 is} hydrogen or a monovalent optionally substituted hydrocarbon radical, s are integer values of at least 1 , t 0 or integer values, and the sum of k + m + p + q integer We mean at least 2. Use of organosilicone copolymers according to claim 2 or 3, characterized in that as polyorganosiloxanes α, ω-divinyl-polydimethylsiloxanes, α, ω-di- (3-acryloxypropyl) polydimethylsiloxanes, α, ω-di- (3-methacryloxypropyl) polydimethylsiloxanes, α, ω- Di- (acryloxymethyl) -polydimethylsiloxanes, α, ω-di- (methacryloxymethyl) -polydimethylsiloxanes, α-monovinyl-polydimethylsiloxanes, α-mono (3-acryloxypropyl) -polydimethylsiloxanes, α-mono (3-methacryloxypropyl) -polydimethylsiloxanes, α-mono (acryloxymethyl) polydimethylsiloxanes or α-mono (methacryloxymethyl) polydimethylsiloxanes used become. Use of organosilicone copolymers according to claim 2 to 4, characterized in that the polyorganosiloxanes to 1 to 90 wt .-% are used, based on the total weight the ethylenically unsaturated polyorganosiloxanes and the ethylenically unsaturated monomers for the preparation of Organosilicone copolymers. Use of organosilicone copolymers according to claim 2 to 5, characterized in that the radically initiated Polymerization in an alcohol with 1 to 6 carbon atoms, ketone, ester or aromatic hydrocarbon having 6 to 15 carbon atoms becomes. (Meth) acrylic ester-silicone copolymers having a comb, block or conductor structure obtainable by free-radically initiated substance or solution polymerization of a) one or more (meth) acrylic esters, b) one or more mono- or polyethylenically unsaturated polyorganosiloxanes, and optionally c) one or more further ethylenically unsaturated monomers with the proviso that none of components a) to c) is selected from the group consisting of alkoxy-substituted ethylenically unsaturated silanes, hydroxy-substituted (meth) acrylic esters, Hydroxy-substituted (meth) acrylic acid amides, amino-substituted (meth) acrylic acid esters, unsaturated carboxylic acids, unsaturated carboxylic anhydrides and polyorganosiloxanes which carry radicals having free hydroxy groups. Impact modified polymer compositions containing one or more organosilicone copolymers, one or more a plurality of thermoplastic polymers and optionally one or more Additives, characterized in that the organosilicone copolymers a) one or more polysiloxane units and b) one or more Contain vinyl polymer units and the units a) and b) covalently are linked together in such a way that they form a comb, block or make ladder structure. Impact modified polymer compositions according to claim 8, characterized in that as thermoplastic Polymeric polyolefins, polystyrene, polyamides, polyvinyl halides, Polyoxymethylene, polycarbonates, poly (meth) acrylic esters, aromatic polyesters, aliphatic polyesters, polycaprolactone or polylactic acid be used. Molding compounds obtainable by thermoplastic Forming of impact-modified polymer compositions according to claim 8 or 9.