EP3083856A1 - Cross-linkable silicone composition - Google Patents

Cross-linkable silicone composition

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Publication number
EP3083856A1
EP3083856A1 EP20130814093 EP13814093A EP3083856A1 EP 3083856 A1 EP3083856 A1 EP 3083856A1 EP 20130814093 EP20130814093 EP 20130814093 EP 13814093 A EP13814093 A EP 13814093A EP 3083856 A1 EP3083856 A1 EP 3083856A1
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Prior art keywords
radicals
silicone
acid
compound
groups
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EP20130814093
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German (de)
French (fr)
Inventor
Andreas KÖLLNBERGER
Erich Pilzweger
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Wacker Chemie AG
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Wacker Chemie AG
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/38Polysiloxanes modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/12Polysiloxanes containing silicon bound to hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/20Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • C09D183/06Polysiloxanes containing silicon bound to oxygen-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/14Polysiloxanes containing silicon bound to oxygen-containing groups

Abstract

The invention relates to a modified silicone composition and to silicone elastomers produced therefrom in a curing process, said elastomers preventing or delaying the formation of a biofilm on their surface.

Description

CURABLE SILICON COMPOSITION

The present invention relates to a modified silicone composition, and the silicone elastomers produced therefrom by curing which prevent or delay the formation of a biofilm on its surface.

In the medical field, numerous products from silicone are used, for example, face masks, valves, hoses, catheters, lining materials, bandages, prostheses, dressings, implants, etc. In all applications can be carried out over the useful life of a colonization of the surface with bacteria, which in some cases can lead to infection. Here antibiotic-resistant strains of bacteria are a growing problem, as they result in difficult to treat infections. The first step of colonization is the adherence of the bacteria to the exogenous surface. After colonization may lead to biofilm formation, which is particularly problematic because the body's immune system or antibiotics can be very difficult to attack the bacteria by protecting the biofilm.

The incorporation or coating bactericidal active substances is one of medical devices to the prior art, wherein just the gift non-lethal doses of antibiotics promotes the proliferation of resistant bacteria. Often antibiotics, quaternary ammonium compounds, silver ions or silver or iodine are added, the water-solubility leads to leaching of the active substances, resulting in a controlled release system for killing bacteria in the area of ​​the implant or of the component. By leaching the active substance is gradually consumed, so that the entire system can not have an antibacterial effect after some time.

The O2009 / 019477A2 describes a further possibility to coat a medical implant with a biodegradable layer, which consists of a polymer and an acid-acting additive which is mixed into the polymer. A disadvantage of this technology is the ineffectiveness of a damaged area when the coating is released from the substrate. In addition, the active substance is washed out by contact with body fluids again and loses a certain amount of time their effectiveness.

In WO98 / 50461 a coating of elemental silver is added as a powder in order to achieve an antimicrobial effect. For products containing silver is a danger that the contact with SH-group-containing

Body fluids reduces the effective concentration of silver ions, and the lethal dose can not be achieved, which in turn leads to a non antimicrobial product. EP0022289B1 describes antimicrobial

Polymer compositions, which are used in the medical field. Here, the polymer base materials is added to a releasable amount of an Carboxylatmittels. This also leads to the above-mentioned disadvantages. The Patentschrif WO2008 / 140753A1 describes an implant that is antibacterial and fungicidal provided by the impregnation with parabens. By the lack of covalent bonding to the matrix of the implant, the active substance is released also in this application within a short time to the environment (Drug Release System). All previously proposed in the prior art solutions against bacteria of medical devices to prevent the formation of biofilms show the great disadvantage that the antimicrobial substances are washed by contact with media such as water or body fluids. Characterized the active groups or molecules or ions depleted in the surface of the medical products and the superficial inhibition of biofilm formation is reduced in its effect.

It is an object of the present invention therefore to provide silicone compositions available that are capable, bacterial and / or fungal or algal growth on the surface produced therefrom, crosslinked

to suppress or inhibit silicone elastomers and without leaching or extraction of the active component is performed. Such cross-linked products are thus protected from the colonization and the attack of microorganisms.

This object has been achieved by a crosslinkable silicone composition containing at least one silicone compound (X) of the general formula (I)

R 1

Formula (I) in which

R 1 is a hydrogen, a monovalent, optionally heteroatom-containing radical such as alkyl, aryl, arylalkyl, alkylaryl, SiR 7 3 -, polydimethylsiloxane,

R 2 are identical or different, represent a hydrogen, a monovalent, optionally heteroatom-containing radicals such as alkyl, aryl, arylalkyl, alkylaryl, R ^ OOR 1,

Containing R 3 are identical or different, represent a hydrogen, a monovalent radical optionally containing heteroatoms such as alkenyl, alkenylaryl, alkyl, aryl, arylalkyl, alkylaryl, -OSiR 7 3,

R 7 is a monovalent, optionally heteroatom-containing radical such as alkenyl, alkenylaryl, alkyl, aryl, arylalkyl, alkylaryl, -OSiR 7 3,

R 8 is a divalent alkyl radical, n is a number between 1 and 30 m a number between 0 and 6000, mean, with the proviso that, per molecule of the compound (X) at least R 3 is an aliphatically unsaturated double bond or a hydrogen atom; preferably at least two R 3 is an aliphatically unsaturated double bond or an

Are hydrogen, more preferably at least three R 3 are an aliphatic unsaturated double bond or a hydrogen atom, and with the proviso that the silicone compound (X) is used in amounts such that the silicone composition is between 0.005 mmol / g and 2 mmol / g of carboxylic acid groups or . Carbonsäureester hydrolyzable to carboxylic acids or

Carboxylic anhydrides, based on the acid group containing; preferably between 0.01 mmol / g, and 1 mmol / g, more preferably between 0.02 mmol / g and 0.085 mmol / g and particularly preferably between 0.04 mmol / g and 0.7 mmol / g.

The silicone compound (X) contains at least one functional group in the siloxane, which carries out a connection to the silicone matrix during crosslinking. The product of the crosslinking reaction is thus a silicone elastomer, for example a polydimethylsiloxane network, which is modified by azide groups. The antimicrobial agents or groups are covalently attached to the silicone matrix and the Siliconelsatomer shows characterized not mentioned in the prior art mentioned disadvantages. So that the leaching or extraction is no longer possible the active component. Another advantage is that an undesirable contamination of objects or media, which are in contact with the silicone elastomer is prevented.

The effect of the azide compound (X) based on the fact that it contains a carboxylic acid function, which may be either unprotected or as Carbonsäureester.

Examples of R 1 are alkyl groups are methyl, ethyl, propyl, isopropyl, tert. -butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. Pentyl, n-octyl, 2 -Ethylhexyl -, 2, 2, -Trimethylpentyl -, n-nonyl and octadecyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl,

Adamantylethyl- or Bornylrest; Aryl or alkaryl radicals such as phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl; Aralkyl radicals such as benzyl, 2 - phenylpropyl or phenylethyl radical. Examples of R 1 with hetero atoms are halogenated and / or functionalized with organic groups derivatives of the above radicals, such as 3, 3, 3 -Trifluorpropyl-, 3-lodopropyl-, 3-lsocyanatopropyl-, aminopropyl, methacryloxymethyl - or cyanoethyl, silyl radicals such as trimethylsilyl, tert-butyl-dimethylsilyl, Tetraethylsilyl, triisopropylsilyl, tert-butyl diphenylsilyl, polydimethylsiloxane radicals such as trimethylsilyl or vinyldimethylterminierte polydimethylsiloxanes trimethylsilyl - or vinyldimethylterminierte polydimethylsiloxane vinylmethylsiloxane copolymers, trimethylsilyl or vinyldimethylterminierte polydimethylsiloxane hydrogenmethylsiloxane copolymers, trimethylsilyl - or vinyldimethylterminierte polydimethylsiloxane phenylmethyl copolymers or trimethylsilyl or vinyldimethylterminierte Polydimethyls iloxan-

Phenylmethyl-methylhydrogensiloxane copolymers. For the case that R 1 is hydrogen and simultaneously R 2 contains a carboxyl group, the anhydride of the two carboxyl groups can be formed or used. For the case that R 1 is hydrogen and simultaneously R 2 contains a hydroxy group, the potential of the two functionalities internal ester (lactone =) may be formed and used.

Preferred radicals R 1 are methyl, ethyl, phenyl, silyl, and polydimethyl siloxane as well as anhydrides or lactones from further present in the same molecule, carboxyl or hydroxyl groups. Particularly preferred radicals R 1 are silyl and polydimethylsiloxane as well as anhydrides or lactones from further present in the same molecule, carboxyl or hydroxyl groups. R 2 Examples of alkyl radicals are methyl, ethyl, propyl, isopropyl, tert. -butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. Pentyl, n-octyl, 2 -Ethylhexyl-, 2, 2, 4 -Trimethylpentyl-, n-nonyl and octadecyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl,

Adamantylethyl- or Bornylrest; Aryl or alkaryl radicals such as phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl; Aralkyl radicals such as benzyl, 2 -Phenylpropyl- or phenylethyl. Examples of R 2 with hetero atoms are halogenated and / or functionalized with organic groups derivatives of the above radicals, such as 3, 3, 3 -Trif luorpropyl-, 3-lodopropyl-; 3-lsocyanatopropyl-, aminopropyl, methacryloxymethyl or cyanoethyl, alkylcarboxy radicals such as - (CH 2) n -COOH, - (CH 2) n -COOSiMe 3, - (CH 2) n - COOSiEt 3, - (CH 2) n -COOSi i Pr 3, - (CH 2) n - COOSd ^ Bua, - (CH 2) n -COO- or trimethylsilyl vinyldimethylterminierte

Polydimethylsiloxanes, - (CH 2) n trimethylsilyl -C00- or vinyldimethylterminierte polydimethylsiloxane vinylmethylsiloxane copolymers, - (CH) n trimethylsilyl -C00- or vinyldimethylterminierte polydimethylsiloxane hydrogenmethylsiloxane copolymers, - (CH 2) n -COO ~ trimethylsilyl- or vinyldimethylterminierte polydimethylsiloxane

Phenylmethylsiloxane copolymers, - (CH 2) n -COO ~ or trimethylsilyl vinyldimethylterminierte polydimethylsiloxane phenylmethylsiloxane-methylhydrosiloxane copolymer,

Hydroxyalkyl such as - (CH 2) n -OH, where n can assume the values listed above.

For the case that R 1 is hydrogen and simultaneously R 2 contains an unreacted carboxyl group to Carbonsäureestern, the anhydride of the two carboxyl groups can be formed or used. For the case that R 1 is hydrogen and simultaneously R 2 contains a hydroxy group, the potential of the two functionalities internal ester (lactone =) may be formed and used.

Preferred radicals R 2 are hydrogen, methyl, ethyl, phenyl, silyl, and polydimethylsiloxane radicals as well as anhydrides or lactones from further present in the same molecule, carboxyl or hydroxyl groups. Particularly preferred radicals R 2 are silyl and polydimethylsiloxane radicals as well as anhydrides or lactones from further present in the same molecule, carboxyl or hydroxyl groups. Examples of R 3 are alkyl groups are methyl, ethyl, propyl, isopropyl, tert. -butyl, n-pentyl, iso-pentyl, neo-pentyl tert. Pentyl, n-octyl, 2-ethylhexyl, 2,2,4-

Trimethylpentyl, n-nonyl and octadecyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or Adamantylethyl- Bornylrest; Aryl or alkaryl radicals such as phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl; Aralkyl radicals such as benzyl, 2 -Phenylpropyl- or phenylethyl. Examples of R 3 in part, with hetero atoms are halogenated and / or functionalized with organic groups derivatives of the above radicals, such as 3, 3, 3 -Trifluorpropyl-, 3-lodopropyl-, 3-lsocyanatopropyl-, aminopropyl, methacryloxymethyl or cyanoethyl alkenyl and / or alkynyl radicals such as vinyl, allyl, isopropenyl, 3-butenyl, 2, 4 -Pentadienyl-, butadienyl, 5- hexenyl, undecenyl, ethynyl, propynyl and Hexinylrest; Cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, 3- Cyclohexenylethyl-, 5 -Bicycloheptenyl -, norbornenyl, cyclooctenyl or 4- Cyclooctadienylrest; Alkenylaryl, such as styryl or styrylethyl, as well as halogenated and / or heteroatom-containing derivatives of the above radicals, such as 2 -Bromvinyl-, 3-bromo-1-propynyl, l-chloro-2-methylallyl, 2- (chloromethyl) allyl -, styryloxy, Allyloxypropyl-, 1- Methoxyvinyl-, cyclopentenyloxy, 3 -Cyclohexenyloxy-,

Acryloyl, acryloyloxy, methacryloyl or

Methacryloyloxy, and -0-SiR third Preferred radicals R 3 are hydrogen, methyl, phenyl, vinyl and 3,3,3-trifluoropropyl radical, whereby the radical -0-SiR 3 of these residues is preferred. Particularly preferred R 3 are the methyl and the vinyl radical, and the ~ 0-SiR 3 radical these radicals being preferred.

Examples of R 7 are alkyl radicals such as methyl, ethyl, propyl, isopropyl, tert. -butyl, n-pentyl, iso-pentyl, neo-pentyl tert. Pentyl, n-octyl, 2-ethylhexyl, 2,2,4-

Trimethylpentyl, n-nonyl and octadecyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or Adamantylethyl- Bornylrest; Aryl or alkaryl radicals such as phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl; Aralkyl radicals such as benzyl, 2 -Phenylpropyl- or phenylethyl. Further examples of R 7 are halogenated and / or functionalized with organic groups lodopropyl- derivatives of the above radicals, such as 3, 3, 3 -Trifluorpropyl-, 3-, 3 -lsocyanatopropyl-, aminopropyl,

Methacryloxymethyl or cyanoethyl, alkenyl and / or alkynyl radicals such as vinyl, allyl, isopropenyl, 3-butenyl, 2, 4 -Pentadienyl-, butadienyl, 5-hexenyl, undecenyl, ethynyl, propynyl and Hexinylrest; Cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, 3 -Cyclohexenylethyl-, 5- bicycloheptenyl, norbornenyl, 4 or -Cyclooctenyl-

Cyclooctadienylrest; Alkenylaryl, such as styryl or styrylethyl, as well as halogenated and / or heteroatom-containing derivatives of the above radicals, such as 2-bromovinyl, 3-bromo-1-propynyl, l-chloro-2-methylallyl, 2- (chloromethyl) allyl - styryloxy, Allyloxypropyl-, 1-

Methoxyvinyl-, cyclopentenyloxy, 3 -Cyclohexenyloxy-,

Acryloyl, acryloyloxy, methacryloyl or methacryloyloxy. R 7 Preferred radicals are methyl, ethyl, isopropyl, tert-butyl, phenyl. Particularly preferred R 7 are methyl, ethyl, and phenyl.

Examples of R 8 are divalent alkyl radicals such as methylene, ethylene, Proyplen-, butylene, pentylene or hexylene, and halogenated and / or functionalized with organic groups derivatives of the above radicals. Preferred radicals R 8 are the methylene and ethylene radical. Particularly preferably the methyl radical. The index n is a number between 1 and 30 preferably between 1 and 18, more preferably between 1 and 5. The index m relates to the degree of polymerization of the siloxane part, where m is a number between 0 and 6000, preferably between 0 and 1000, and more preferably between 1 to 100.

The preparation of compound (X) can be done in various ways, wherein the synthetic pathway does not affect the efficacy. It can use any synthetic routes that were previously described in textbooks and / or publications.

As a starting material class for the synthesis of compound (X) carboxylic acids and their derivatives may be used, which are reacted in one or more stages to the compound (X). Non-limiting examples of suitable carboxylic acids and their derivatives are: formic acid, acetic acid, Oxoethansäure, propanoic acid, propenoic acid,

Propionic acid, butyric acid, 2 -butenoic acid, 2 -Butinsäure, 3-butenoic acid, 3 -Butinsäure, crotonic acid, fumaric acid,

Cyclopropanecarboxylic acid, 2 -Methylpropansäure, acetylene dicarboxylic acid, 2, 4 pentadienoic acid, 2-pentenoic acid, 3- pentenoic acid, -pentenoic acid, 2 -Pentinsäure, 3 -Pentinsäure, 4-pentynoic acid, 2 -Pentendisäure, 2 -Methylenbernsteinsäure,

Acrylic acid, methacrylic acid, 3, 3 -Dimethylacrylsäure,

Maleic acid, methylmaleic, succinic acid, allyl succinic acid, cyclobutane acid, ethyl malonic acid, Ethenylmalonsäure, Ethinylmalonsäure, glutaric acid, 2-

Methylglutaric acid, 2 -Ethenylglutarsäure, 2-Ethinylglutarsäure, trimethylsilyl, Vinyldimethylsilylessigsäure, 2,4-hexadienoic acid, propene-1, 2, 3 - tricarboxylic acid, 1-

Cyclopentene, 3 -Cyclopentencarbonsäure, 2 hexynoic, sorbic acid, Allylmalonic,

Allylmalonsäureandhydrid, 3-methyl-4-pentenoic acid, 2-

Hexenoic acid, 3 -hexenoic, 4 -hexenoic, 3-

(Trimethylsilyl) ropinsäure, 3- (dimethylvinylsilyl) propynoic, 2 -Methylglutarsäure, 2- Vinylglutarsäure, 2 -Allylglutarsäure, 3 -Vinylglutarsäure, 2- Allylglutarsäure, dichlorobenzoic acid, dibromobenzoic acid,

Diiodobenzoic acid, bromo-chlorobenzoic acid, bromine

Fluorobenzoic acid, bromine iodobenzoic acid, 6 -Heptinsäure, 2,2-dimethyl-4 -pentenoic acid, 6-heptenoic acid, 2,2-dimethylglutaric acid, 3, 3 -Dimethylglutarsäure, heptanedioic acid, bromomethylbenzoic acid, chloromethylbenzoic acid, octenoic acid, phenylpropionic acid, sebacic acid, decanoic acid, decenoic acid, 10- bromodecanoic, 2 -Bromdecansäure, undecanoic, 10-

Undecenoic acid, 10-undecynoic acid, dodecanoic acid, dodecanedioic acid, 12 -Bromdodecansäure, 2 -Bromdodecansäure, 2 -Bromhexadecansäure, 16-bromohexadecanoic acid, linolenic acid, elaidic acid, oleic acid, arachidonic acid, erucic acid, 3 -Allyldihydrofuran-2, 5 -dione, 3- Vinyldihydrofuran- 2, 5-dione, as well as the methyl, ethyl, trimethylsilyl, triethylsilyl, siloxy ester of the above carboxylic acids. Preferably, the carboxylic acid used contains a hydrosilylation accessible unsaturated group. With the help of

Hydrosilylation catalysts, preferably those containing platinum, is reacted with Si-H-containing cyclo, oligo- or polysiloxanes. Carboxylic acid derivatives are preferably used which no acidic hydrogen atom in the molecule have more (Carbonsäureester, anhydrides, lactones). In a second reaction step, the vinyl group or vinyl groups can be introduced by suitable reactions in compound (X). An example of this is the known prior art equilibration between siloxanes. The compound obtained in the first step of carboxylic acid or derivatives thereof is reacted with a cyclo, oligo- or polysiloxane through the choice of equilibrating to siloxanes, which can carry both terminal and / or catenary, aliphatically unsaturated groups.

The inventive silicone compositions can peroxide, addition-or condensation

Silicone compositions are used if they contain corresponding amounts of components (X).

In a preferred embodiment, the silicone compositions of the invention are addition-curing and comprising, besides components (X)

- at least one compound (A), (B) and (D),

- at least one compound (C) and (D), and

- at least one compound (A), (B), (C) and (D) wherein

(A) an organic compound or a

Organosilicon compound containing at least two radicals having aliphatic carbon-carbon multiple bonds,

(B) an organosilicon compound containing

at least two Si-bonded hydrogen atoms, (C) an organosilicon compound containing SiC-bonded radicals with aliphatic carbon-carbon - multiple bonds and Si-bonded hydrogen atoms, and

(D) a hydrosilylation catalyst

mean.

In the inventive addition-

it can be either one-component silicone compositions silicone compositions as well as to two- or multi-component silicone compositions.

In two-component compositions the individual components of the inventive compositions may contain all ingredients in any combination, generally with the proviso that a component does not simultaneously siloxanes having an aliphatic multiple bond, siloxanes having Si-bonded hydrogen and a catalyst, thus essentially not simultaneously comprise the constituents (A ), (B) and (D) or (C) and (D). Preferably, however, the inventive compositions are one-component compositions.

The compounds used in the inventive compositions (A) and (B) and (C) are known to be chosen so that crosslinking is possible. For example, compound (A) at least two aliphatically unsaturated radicals and (B) at least three Si-bonded hydrogen atoms, or compound (A) has at least three aliphatically unsaturated radicals and siloxane (B) at least two Si-bonded hydrogen atoms, or instead of compound (A) and (B) siloxane is used (C), which is aliphatically unsaturated radicals and Si-bonded

having the hydrogen atoms in the abovementioned ratios. Also included are mixtures of (A) and (B) and (C) with the abovementioned ratios of aliphatically unsaturated radicals and Si-bonded hydrogen atoms.

In the inventively used compound (A) may be a silicon-free organic compound having preferably at least two aliphatically unsaturated groups and organosilicon compounds having preferably at least two aliphatically unsaturated groups or also mixtures thereof.

Examples of silicon-free organic compound (A) are 1, 3, 5-trivinylcyclohexane, 2, 3 -dimethyl- 1, 3 -butadiene, 7-methyl-3-methylene-l, 6-octadiene, 2-methyl-l, 3-butadiene, 1, 5-hexadiene, 1, 7-octadiene, 4, 7-methylene-4, 7,8, 9-tetrahydroindene,

Methyl cyclopentadiene, norbornene 5-vinyl-2,

Bicyclo [2.2.1] hepta-2, 5 -diene, 1, 3 -Diisoproppenylbenzol, vinyl group-containing polybutadiene, 1, 4 -Divinylcyclohexan,

1.3.5 -Triallylbenzol, 1, 3, 5 -Trivinylbenzol, 1,2,4-trivinylcyclohexane, 1, 3, 5 -Triisopropenylbenzol, 1,4-divinylbenzene, 3-methyl-heptadien- (1, 5), 3 - phenyl-hexadiene (1.5), 3-vinyl-hexadiene (1, 5 and 4, 5-dimethyl-4, 5-diethyl-octadiene (1, 7), N 'methylene-bis-acrylamide , 1,1,1-tris (hydroxymethyl) propane triacrylate, 1,1,1-tris (hydroxymethyl) propane trimethacrylate, Tripropylenglykol- diacrylate, diallyl ether, diallyl amine, diallyl carbonate, Ν, Ν'- diallylurea, triallyl amine, tris (2 -methylallyl) amine,

2.4.6 -Triallyloxy- 1, 3, 5-triazine, triallyl-s-triazine-2, 4, 6 (1H, 3H, 5H) -trione, Diallylmalonsäureester, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, poly (propylene glycol) methacrylate.

Preferably, the inventive

Silicone compositions as the component (A) at least one aliphatically unsaturated organosilicon compound, all used in addition-curing compositions previously aliphatically unsaturated organosilicon compounds can be used, such as silicone block copolymers having urea segments, silicone block copolymers having amide segments and / or imide segments and / or ester-amide segments and / or polystyrene segments and / or silarylene segments and / or carborane segments, and silicone graft copolymers having ether groups.

As organosilicon compounds (A) which have SiC-bonded radicals with aliphatic carbon-carbon multiple bonds, are preferably linear or branched organopolysiloxanes comprising units of the general formula (II)

R 4 a R 5 b SiO used (4-ab) / 2 (II) wherein

R 4 independently of one another, identical or different, free of aliphatic carbon-carbon multiple bonds, organic or inorganic radical,

R 5 independently of one another, identically or differently, a monovalent, substituted or unsubstituted, SiC-bonded hydrocarbon radical having at least one aliphatic carbon-carbon multiple bond, a is 0, 1, 2 or 3, and

b is 0, 1 or 2

mean, with the proviso that the sum a + b is less than or equal to 3 and at least 2 radicals R 5 are present per molecule.

The radical R 4 may be mono- or polyvalent radicals, said polyvalent radicals such as divalent, trivalent and tetravalent radicals are several, such as two, three or four, siloxy units of the formula (II) to one another ,

Further examples of R 4 are the monovalent radicals -F, -Cl, - Br, OR 6, -CN, -SCN, -NGO and SiC-bonded, substituted or unsubstituted hydrocarbon radicals (with the oxygen atoms or the group -C O ) - may be interrupted, as well as divalent, both sides of the formula (II) Si-bonded radicals. If it is 4 radical R is an SiC-bonded, substituted hydrocarbon groups, preferred substituents are halogen atoms, phosphorus-containing radicals, cyano radicals, -OR 6, -NR 6 -, -NR 6 2, -NR 6 -C (0) -NR 6 2, -C (0) -NR 6 2, -C (0) R 6, -C (0) OR 6, -S0 2 Ph, and -C 6 F. 5 Here, R 6 are independently the same or different signify a hydrogen atom or a monovalent hydrocarbon radical having 1 to 20

Carbon atoms, and Ph is the phenyl radical.

Examples of radicals R 4 are alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-Bulyl-, tert-butyl, n-pentyl, iso-pentyl , neo-pentyl, tert-pentyl,

Hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and isooctyl radicals such as the 2, 2, 4 -Trimethylpentylrest, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl and octadecyl radicals such as the n-octadecyl, cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals,

Aryl radicals such as phenyl, naphthyl, anthryl and phenanthryl radicals, alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl, and aralkyl groups such as benzyl, a- and ß-phenylethyl radical.

Examples of substituted radicals R 4 are haloalkyl, such as 3, 3, 3-trifluoro-n-propyl, 2,2,2,2 ', 2, 2, - the heptafluoroisopropyl radical,

Haloaryl radicals such as the o-, m- and p-chlorophenyl, - (CH 2) - N (R 6) C (0) NR 6 2, - (CH 2) o -C (0) NR e 2, - ( CH 2) 0 -C (O) R 6, - (CH 2) 0 - C (O) OR 6, - (CH 2) o -C (0) NR 6 2, - (CH 2) -C (O ) - (CH 2) p C (0) CH 3; - (CH 2) -O-CO-R 6, (CH 2) -NR 6 - (CH 2) p-NR 6 2, - (CH 2) o -0- (CH 2) p CH (OH) CH 2 OH,

(CH 2) o (0CH 2 CH 2) p 0R 6, - (CH 2) o -S0 2 Ph, and - (CH 2) o -0-C 3 F 5, wherein R e and the Ph as above corresponds to and have the meaning o and p are identical or different integers between 0 and 10. FIG.

Examples of R 4 is divalent, Formula both sides according to (II) Si-bonded radicals are those derived from the previously mentioned for R 4 is monovalent examples in that an additional bond is by substitution of a hydrogen atom, examples of such radicals are - (CH 2) -, -CH (CH 3) -, -C (CH 3) 2 -, -CH (CH 3) - CH 2 -, -C 6 H 4 -, -CH (Ph) -CH 2 -, -C (CF 3) 2 -, - (CH 2) 0 -C 6 H 4 - (CH 2) G -, - (CH 2) 0 -C S H 4 -C 6 H 4 - (CH 2 ) 0 -, - (CH 2 0) p, (CH 2 CH 2 0) o, - (CH 2) o -0 x -C 6 H 4 -S0 2 - C 6 H 4 -O x - (CH 2 ) 0 -, where x is 0 or 1, and Ph, o and p have the meaning above mentioned.

It is preferable that the radical R 4 is a monovalent, from aliphatic carbon-carbon -Mehrfachbindungen free, SiC-bonded, optionally substituted

Hydrocarbon radical having 1 to 18 carbon atoms, particularly preferably a monovalent, from aliphatic carbon-carbon -Mehrfachbindungen free, SiC-bonded hydrocarbon radical having 1 to 6

Carbon atoms, especially the methyl or phenyl radical.

The radical R 5 may be, any groups amenable to an addition reaction (hydrosilylation) with a SiH functional compound. If radical R 5 is an SiC-bonded, substituted

These hydrocarbon radicals are as substituents

Preferably halogen atoms, cyano radicals and -OR 6, wherein R 6 has the abovementioned meaning. It is preferable that the radical R 5 alkenyl and alkynyl groups having 2 to 16 carbon atoms, such as vinyl, allyl, methallyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl , cyclopentadienyl, cyclohexenyl, vinylcyclohexylethyl, divinylcyclohexylethyl, norbornenyl, vinylphenyl or styryl radicals, wherein the vinyl, allyl and hexenyl radicals are particularly preferably used.

The molecular weight of the component (A) can vary within wide limits, for instance between 10 2 and 10 e g / mol. Thus, it may, the constituent (A), for example, a relatively low molecular weight alkenyl-functional oligosiloxane such as 1,2-divinyltetramethyldisiloxane, but may also be a pendant or terminal Si-bonded vinyl groups, highly polymeric polydimethylsiloxane, for example with a molecular weight of 10 5 g / mol (determined by NMR number average). The structure of the component (A) forming molecules is not fixed; in particular, the structure of a high molecular weight, ie oligomeric or polymeric siloxane may be linear, cyclic, branched or resinous, network-like. Linear and cyclic polysiloxanes are preferably composed of units of the formula R 4 3 SIOI / 2, R 5 R R composed SIOI 2/2, R 5 4 SIOI / 2 and R 4 2 Si0 2/2, where R 4 and R 5 have the above- have the meaning given. Branched and network-like polysiloxanes contain trifunctional and / or tetrafunctional units in addition, those of the formulas R 4 Si0 3/2, R 5, Si0 3/2 and Si0 / 2 is preferred. Of course, mixtures of different criteria of the component (A) sufficient siloxanes may be used.

Particularly preferred as component (A) is the use of vinyl-functional, substantially linear

Polydiorganosiloxanes having a viscosity of from 0.01 to 500,000 Pa »s, particularly preferably from 0.1 to 100,000 Pa 's, each at 25 ° C.

The organosilicon compound (B) all hydrogen-functional organosilicon compounds can be used, which have also been used in addition compositions.

Organopolysiloxanes (B) having Si-bonded hydrogen atoms are preferably linear, cyclic or branched organopolysiloxanes comprising units of the general formula (III)

R H d SiO (4 _ c _ d), used 4 c / 2 (III) wherein

R 4 has the abovementioned meaning,

c 0,1 2 or 3 and

d is 0, 1 or 2,

with the proviso that the sum of c + d is less than or equal to 3 and that there are at least two Si-bonded hydrogen atoms per molecule.

Preferably, the organopolysiloxane used in the invention contains (B) Si-bonded hydrogen in the range from 0.04 to 1.7 weight percent, based on the total weight of the organopolysiloxane (B).

The molecular weight of the component (B) can also vary within wide limits, for instance between 10 2 and 10 6 g / mol. Thus, it may, the constituent (B), for example, a relatively low molecular weight SiH-functional oligosiloxane, such as tetramethyldisiloxane, however, exhibiting also a along the chain or terminally SiH groups verfügendes high polymer polydimethylsiloxane or a SiH group-silicone resin.

The structure of the component (B) forming molecules is not fixed; in particular, the structure of a high molecular weight, ie oligomeric or polymeric SiH-containing siloxane may be linear, cyclic, branched or resinous, network-like. Linear and cyclic polysiloxanes (B) are preferably composed R 3 SIOI / 2, HR 4 2 Si0 1/2, HR 4 Si0 2/2 and R 2 Si0 2/2 units of the formula wherein R 4 has the meaning given above , Branched and network-like polysiloxanes additionally contain trifunctional and / or tetrafunctional units, those of the formulas R 4 Si0 3/2, hsi0 are 3/2 and Si0 / 2 is preferred, wherein R 4 has the meaning given above.

Of course, mixtures of different criteria of the component (B) sufficient siloxanes may be used. In particular, the component (B) forming molecules also aliphatically unsaturated groups in addition to the obligatory SiH groups optionally also contain. Particularly preferred is the use of low molecular weight SiH-functional compounds such as tetrakis (dimethylsiloxy) silane and tetramethylcyclotetrasiloxane, and also relatively high molecular weight, SiH containing siloxanes such as poly (hydrogen methyl) siloxane and poly (dimethylhydrogenmethyl) siloxane having a viscosity at 25 ° C from 10 to 10,000 mPa 's, or analogous SiH-containing compounds in which some of the methyl groups is replaced by 3, 3, 3 -Trifluorpropyl- or phenyl groups.

Component (B) is preferably in such an amount present in the novel curable silicone compositions, the molar ratio of SiH groups to aliphatically unsaturated groups of (A) from 0.1 to 20, more preferably between 1.0 and 5.0, lies.

The components employed in this invention (A) and (B) are commercial products or by methods customary in chemistry can be produced.

Silicone compositions of the invention may instead of organopolysiloxanes of component (A) and (B)

have multiple bonds and Si-bonded hydrogen atoms, containing - (C), the same aliphatic carbon-carbon. The invention can

Silicone compositions of all three components (A), (B) and

(C).

If siloxanes are used (C) are preferably those comprising units of the general formulas (IV), (V) and (VI)

R 4 g R 3 Si0 5 -g / 2 (V)

R h hsi0 3 _ h / 2 (I) wherein and R 5 have the meaning given above

f is 0, 1, 2 or 3, g is 0, 1 or 2 and

h is O 1 or 2, with the proviso that each molecule at least 2 radicals R 5 and at least 2 Si-bonded hydrogen atoms are present.

Examples of organopolysiloxanes (C) are those prepared from S0 4 / R 4 3 SIOI / 2 -, R 2 R 5 SIOI / 2 - and R 2 HSiOi / 2 - units, so-called MP resins, wherein these resins additionally RSi0 3 / 2 - and R may contain from 2 SiO units, and linear organopolysiloxanes consisting essentially of R 4 2 R 5 SIOI / 2 -, R 4 2 SiO and R 4 HSiO units with R 4 and R 5 is as defined above.

The organopolysiloxanes (C) preferably have an average viscosity of 0.01 to 500,000 Pa 's, particularly preferably from 0.1 to 100,000 Pa »s at 25 ° C, respectively.

Organopolysiloxanes (C) are prepared by methods customary in the chemistry.

As hydrosilylation catalyst (D) all of the prior art known catalysts can be used. Component (D) may be a platinum group metal such as platinum, rhodium, ruthenium, palladium, osmium or iridium, an organometallic compound or a combination thereof. Examples of component (D) are compounds such as hexachloroplatinic (IV) acid, platinum dichloride, platinum acetylacetonate and complexes of the said compounds which are encapsulated in a matrix or core-shell-like structure. Among the platinum complexes of low molecular weight organopolysiloxanes of the 1, 3 include -Diethenyl- 1,1,3,3 - tetramethyldisiloxane complexes with platinum. Other examples are Platinphosphitkomplexe, Platinphosphinkomplexe or Alkylplatinkomplexe. These compounds can be encapsulated in a resin matrix. The concentration of component (D) is for catalyzing the hydrosilylation reaction of components (A) and (B) upon exposure sufficient to produce the required here in the described process heat. The amount of component (D) may be between 0.1 and 1000 parts per million (ppm), 0.5 and 100 ppm or 1 and 25 ppm of platinum group metal, depending on the total weight of the components. The cure rate may be low when the part of the platinum group metal is less than 1 ppm. The use of more than 100 ppm of platinum group metal is uneconomical or may reduce the stability of the adhesive formulation.

In another embodiment, curable silicone compositions of the invention can also be peroxide cured. In this case, the

Silicone composition at least of the components (A) and (H). Here, preferably between 0.1 and 20 wt .-% component (H) in the inventive

Silicone compositions. As crosslinking agents in accordance with the component, all the prior art and typical peroxides may be used (H). Examples of the component (H) are dialkyl peroxides such as 2, 5-dimethyl-2, 5 -di (tert-butylperoxy) hexane, 1, 1-di-

(tert-butylperoxy) cyclohexane, l, l-di- (tert-butylperoxy) - 3, 3, 5 -trimethylcyclohexane, a-Hydroxyperoxy-a 1

hydroxydicyclohexylperoxid, 3, 6-Dicyclohexyliden-l, 2,4,5-tetroxane, di-tert-butyl peroxide, tert-butyl tert-triptylperoxid and tert-butyl-triethyl-5-methyl peroxide, diaralkyl peroxides such as dicumyl peroxide, Alkylaralkylperoxide as tert-butyl cumyl peroxide and a, a '-di (tert-butylperoxy) -m / p-diisopropylbenzene, Alkylacylperoxide such as t-butyl perbenzoate, and diacyl peroxides such as dibenzoyl peroxide, bis (2-methylbenzoyl), bis (4 -methylbenzoylperoxid) and bis- (2, 4-dichlorobenzoyl). the use of vinyl specific peroxides whose most important representatives are dialkyl and diaralkyl is preferred. Particularly preferred is the use of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and dicumyl peroxide. There can be used single or mixtures of different peroxides (H). The content of the silicone compositions according to the invention of component

(H) is preferably between 0.1 and 5.0 wt -.%, Particularly preferably between 0.5 and 1.5 wt .-%. Thus, according to the invention, crosslinkable Siliconkzusammensetzungen the, characterized in that the crosslinking agent (H) is contained from 0.1 to 5.0% by weight and is an organic peroxide or a mixture of organic peroxides are preferred. In a further embodiment, cross-linkable silicone compositions of the invention may also by adding component attempts (X) to condensation

Silicone compositions are networked.

Kondensatiuosnvernetztende silicone compositions have long been known in the art. A more detailed description can be found for example in EP0787766A1.

All according to the invention described above peroxide, addition and kondensationsvernetzdenden Siliconzlusammensetzungen can optionally reinforcing fillers, as component (E), such as fumed or precipitated silicas whose BET surface areas of at least 50 m 2 / g as well as carbon blacks and activated carbons such as furnace black and acetylene soot, wherein pyrogenic and precipitated silicas with BET surface areas of at least 50 m 2 / g are preferred. The silica fillers may have hydrophilic character or have been hydrophobicized by known processes. The content of the crosslinkable composition according to the invention actively reinforcing filler (E) is in the range of 0 to 70 wt .-%, preferably at 0 to 50 -.%.

Particularly preferred are the erfindugnsgemäßen crosslinkable silicone compositions are characterized in that the filler (E) is surface-treated. The

Surface treatment is achieved by the known prior art process for hydrophobicizing finely divided fillers. The hydrophobization may for example be effected either prior to incorporation into the polyorganosiloxane in the presence of a polyorganosiloxane according to the in-situ method. Both methods can also be carried out continuously in both batch process as well. Hydrophobizing agents are preferably used are organosilicon compounds which are permanently physisorbed to the filler capable of reacting with the filler to form covalent bonds or the like. Examples of hydrophobic agents are alkylchlorosilanes how

Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, octylmethyldichlorosilane, octadecylmethyldichlorosilane, octyldimethylchlorosilane, octadecyldimethylchlorosilane and tert. -

butyldimethylchlorosilane; Alkylalkoxysilanes such as

Dirnethyldimethoxysilan, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane;

trimethylsilanol; cyclic diorgano (poly) siloxanes, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane; linear diorganopolysiloxanes such as dimethylpolysiloxanes, and trimethylsiloxy-terminated dimethylpolysiloxanes having silanol or alkoxy end groups; Disilazanes how

Hexaalkyldisilazanes, especially hexamethyldisilazane

divinyltetramethyldisilazane,

Bis (trifluoropropyl) tetramethyldisilazane; cyclic dimethylsilazanes as hexamethylcyclotrisilazane. It may also be mixtures of the above mentioned

Water repellents are used. To the

accelerating hydrophobicization is carried out if necessary also the addition of catalytically active additives, such as amines, metal hydroxides and water.

The hydrophobization, for example, in one step using one or a mixture of more hydrophobicizing agents, but also by using one or more hydrophobicizing agents in several steps take place.

Preferred fillers (e) have due to a

Surface treating a carbon content of at least 0.01 to a maximum of 20 wt .-%, preferably between 0.1 and 10 wt .-%, more preferably between 0.5 to 5 wt .-% on. Particularly preferred curable silicone compositions which are characterized in that the filler (E) is a surface-treated silica comprising from 0.01 to 2% by weight of Si-bonded, aliphatically unsaturated groups. For example, it is at these to Si-bonded vinyl groups. In the inventive silicone composition of the component (E) is preferably also preferably used as a single or as a mixture of several finely divided fillers.

The silicone compositions of the invention may optionally further additives as constituents (F) in a proportion of up to 70 wt .-%, preferably from 0.0001 to 40 wt .-% contained. These additives (F) can, for example, inert fillers, resin-like polyorganosiloxanes other than the siloxanes (A), (B), (C), (E) and (X) are different, fungicides, fragrances, rheological additives, inhibitors, and stabilizers for the targeted setting of the processing time, temperature and crosslinking rate, corrosion inhibitors,

its oxidation inhibitors, light stabilizers, flame retardants, and agents for influencing the electrical properties of dispersing agents, solvents, adhesion promoters, pigments, dyes, plasticizers, organic polymers, heat stabilizers, etc.. These include additives such as quartz flour, diatomaceous earth, clays, chalk, lithopone, graphite, metal oxides, metal carbonates, sulfates, metal salts of carboxylic acids, metal dusts, fibers such as glass fibers, synthetic fibers, plastic powder, Metallst ube, dyes, pigments, etc.

These fillers can also be thermally conductive or electrically conductive. Examples of thermally conductive fillers are aluminum; alumina; barium titanate; beryllium oxide; boron nitride; Diamond; Graphite; magnesium oxide; particulate metal such as copper, gold, nickel or silver; silicon carbide; tungsten carbide; Zinc oxide and a combination thereof. Thermally conductive fillers are known in the art and are commercially available. For example, CB-A20S and Al-43-Me are aluminum oxide fillers of different particle sizes that are commercially available from Showa-Denko, and AA-04, AA-2, and AA1 8 are aluminum oxide fillers commercially from Sumitomo Chemical Company are available. Silver fillers are commercially available from Metalor Technologies USA Corp. of Attleboro, Massachusetts, USA. Boron nitride fillers are commercially available from Advanced Ceramics Corporation, Cleveland, Ohio, USA. It can be used with different particle sizes and different particle size distribution, a combination of fillers.

Inhibitors and stabilizers are used for controlled adjustment of the processing time, temperature and crosslinking rate of the invention

Silicone compositions. These inhibitors and stabilizers are known in the art for a long time. Examples of customary inhibitors are acetylenic alcohols such as 1-ethynyl-l-cyclohexanol, 2-methyl-3-butyn-2-ol and 3.5- dimethyl-l-hexyne-3-ol, 3-methyl-1-dodecyn-3 - ol,

Polymethylvinylcyclosiloxanes as 1,3,5,7

Tetravinyltetramethyltetracyclosiloxan low molecular weight silicone oils having methylvinyl-SiO ^ groups and / or F ^ vinylSiO] ^ -. Groups. as Divinyltetramethydisiloxan

Tetravinyldimethyldisiloxane, Trialkylcyanurate, alkyl maleates, such as Diallylmaleate, Dirnethylmaleat and diethyl maleate, fumarates such as diallyl fumarate and Diethylfurmarat, organic hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide and pinane hydroperoxide, organic peroxides, organic sulfoxides, organic amines. Diamines and amides, phosphanes and phosphites, nitrites, triazoles, Diaziridines and oximes. The effect of these inhibitor additives (F) depends on their chemical structure, so that the concentration must be determined individually. Inhibitors and inhibitor mixtures are added to the total weight of the mixture preferably in an amount ranging from 0.00001% to 5%, preferably from 0.00005 to 2% and more preferably 0.0001 to 1

The silicone composition may optionally contain a solvent (G) in addition. However, it is important to ensure that the solvent (G) has no adverse effects on the overall system. Suitable solvents (G) are known in the art and are commercially available. The solvent (G) an organic solvent having 3 to 20 carbon atoms may be, for example. Examples of the solvent (G) include aliphatic hydrocarbons such as nonane, decalin, and dodecane; aromatic hydrocarbons such as mesitylene, xylene and toluene; Esters such as ethyl acetate and butyrolactone; Ethers such as n-butyl ether and Polyethylenglycolmonomethylester; Ketones such as methyl isobutyl ketone and methyl pentyl ketone; Silicone fluid, such as linear, branched and cyclic polydimethylsiloxanes, and combinations of these solvents. The optimum concentration of a particular solvent (G) in the silicone composition can be readily determined by routine experimentation. Depending on the weight of the compound, the amount of the solvent (G) can be between 0 and 95% or between 1 and 95%.

The curable silicone compositions of the invention have the advantage that they readily available starting materials and thus can be economically produced in a simple process using. The crosslinkable silicone compositions according to the invention have the further advantage that they also have as one-component formulation at 25 ° C and ambient pressure a good storage stability and crosslink rapidly only at elevated temperature. the invention

Silicone compositions have the advantage that they result in two-component formulation by mixing the two components a crosslinkable silicone composition whose workability is retained over a long period of time are made at 25 ° C and ambient pressure, thus exhibit extremely long pot life, and crosslinked quickly only at elevated temperature.

Silicone rubbers of the invention are produced by crosslinking the silicone compositions according to the invention by means of the prior art known methods. Manufacturable silicone rubbers for medical devices are, for example, face masks, valves, tubes, catheters, lining materials, bandages, prostheses,

Dressing materials. The medical devices thus produced have a permanent suppression of the colonization of their surfaces by bacteria and thus a substantially reduced risk of infection to the patient during their use.

Examples:

In the following examples, all parts and percentages are, unless indicated otherwise, by weight. Unless indicated otherwise, the examples below are at a pressure of the surrounding atmosphere, ie at about lOOOhPa, and at room temperature, ie at about 20 ° C, or at a temperature which upon combining the reactants at room temperature without additional heating or cooling adjusts performed. Hereinafter, all viscosity data relate to a temperature of 25 ° C. The following examples illustrate the invention without being limiting.

It uses the following abbreviations:

Cat. platinum catalyst

Example Ex.

No. No.

PDMS polydimethylsiloxane

LSR Liquid Silicone Rubber

HTV High Temperature Cure

Wt.% By weight, w / w

M unit monofunctional siloxane radical, R 3 SiO? / 2

D unit difunctional siloxane radical, R 2 Si0 2/2

T unit trifunctional siloxane radical, R 3 Si0 3/2

Q unit tetrafunctional siloxane, Si0 4/2

wherein R represents an organic residue. Example 1 Synthesis of Compound (X):

One possible synthetic introduction of functional groups which allow a connection to the network PDMS, is the widespread in silicone chemistry equilibration reaction of suitable precursors. This type of connectivity exemplifies a way of the compound (X) to produce and is not intended to be limiting the scope of the application because the Darstellungsweg shows no influence on the effectiveness.

Step 1:

Preparation of a, ω-bernsteinsäureanhydridfunktionellen silicone by hydrosilylation of 2-

Allylsuccinic and a, ω-Si-H-terminated Polidimethylsiloxans having an average chain length of 50 D units: lower noble metal catalysis (platinum group metals, preferred are platinum compounds) reacting the H- carried terminated silicone polymer with 2-

Allylbersteinsäureanhydrid preferably at about 90-110 ° C. The synthesis is carried out under use of equimolar based on the functional groups (Si-H and allyl). An over or under income for the individual reactants is also possible.

Level 2:

Functionalization for the connection to silicone elastomers: It is reacted the product of step 1 with a Si-vinyl-functional polymer with the aid of the equilibration reaction, wherein the vinyl-functional polymer can carry both warp and terminal vinyl groups. The molar ratio of the two reactants may be between 1: 1 are selected and preferably a ratio of between 1:20 to 5:: 100 to 100 1, and more preferably a ratio of between 1:10 and 2: is selected. 1 Equilibration itself can be carried out by all the prior art known methods such as, for example, acid or base catalyzed equilibration, or using phosphazenes. For this example, 0.45 moles of α, ω- bernsteinsäureanhydridfunktionellen equilibrated silicone with 4.5 mol divinyldisiloxane using a phosphazene having the average molecular formula PNC1. 2 After heating the mixture to 100 ° C to 120 ° C 400 ppm Äquilbrierungskatalysator (based on the total weight of the reactants) are added in two installments of 200 ppm. After stirring for two hours, the catalyst is quenched by addition of divinyltetramethyldisilazane and volatile

Components are removed by applying an oil pump vacuum.

Example 2 Synthesis of the compound (X):

Step 1: Preparation of an α, ω- functional silicone by hydrosilylation of Acrylsäuretrimethylsilylester

(Propensäuretrimethylisliylester) and an α, ω-SiH-terminated polydimethylsiloxane having an average chain length of 50 D units: lower noble metal catalysis (Pt metals) the reaction of the H-terminated silicone polymer having Acrylsäuretrimethylsilylester preferably at about 90-110 ° C , The synthesis is carried out under use of equimolar based on the functional groups (Si-H and vinyl). An over or under income for the individual reactants is also possible.

Step 2: Functionalization for linking to silicone elastomers analogously to Example 1, wherein the ratio Carbonsäureestergruppen: vinyl groups = 1: 5.

Example 3 Synthesis of Compound (X):

Starting from Undecensäure- triisopropylsxlylester the compound (X) is prepared analogously to Example 1, wherein in step 2, the ratio Carbonsäureestergruppen: vinyl groups = 1: 2.

Example 4 (Comparative Example): silicone base composition 1 (LSR-silicone): Commercially available LSR 3003/40 mixture ELASTOSIL ® A / B. If the crosslinking of the material by compression at 165 ° C for 10 min.

Example 5:

Compound (X) and additional Si-H crosslinker is added to the commercially available LSR 3003/40 mixture ELASTOSIL ® A / B of Example 4. FIG. By introducing the vinyl groups from compound (X) a balance of the functional groups is needed, which is why a linear Si-H Kammvernetzer with a Si-H content of 4.8 mmol of Si-H per gram is added, where additionally added (X) (molar calculation) corresponding to the amount of Si-H in about the amount of vinyl groups of compound. If the crosslinking of the material by compression at 165 ° C for 10 min.

In Table 1, various compounds (X) may be varied at different addition amounts and the results are shown. Example 6 (Comparative Example): silicone base composition 2 (HTV-silicone): Commercially available peroxide crosslinking HTV mixture ELASTOSIL ® 401/60 C6. If the crosslinking of the material by compression at 165 ° C for 10 min, then the material is annealed at 200 ° C for 4 hours.

Example 7: To the commercially available peroxide-crosslinking HTV mixture ELASTOSIL ® R 401/60 C6 compound (X) is compounded. If the crosslinking of the material by compression at 165 ° C for 10 min, then the material is annealed at 200 ° C for 4 hours. In Table 1, various compounds (X) may be varied at different addition amounts and the results are shown.

Example 8 (Comparative Example): silicone base composition 3 (RTV-2 silicone): Commercially available addition-crosslinking RTV 2 mixture SILPURAN. If the crosslinking of the material by heating to 50 ° C for 1 h.

Example 9: To the commercially available addition-crosslinking RTV 2 mixture SILPURAN ® 2420 A / B is added to compound (X). By introducing the vinyl groups from compound (X) a compensation of the f nktionellen groups is required, which is why HD-Cyclen (mainly HD5 and HD6) are added, with the addition of added amount of Si-H in about the amount of vinyl groups of compound (X) (molar calculation). the crosslinking takes place by heating the material at 50 ° C for 1 hour. In Table 1, various compounds 1 can be varied at different addition amounts and the results are shown.

test method

By the covalent binding of the acid or Säureestergruppen to the PDMS matrix are test methods based on the diffusion of active substances suitable for the characterization of the surface (agar diffusion test or inhibition zone test). Due to the diverse

Applications antimicrobial equipped products exist does not have a national or international standard for the testing of products. However, the behavior of the crosslinked silicone rubber is to be as realistic as possible tested, so the efficacy tests to colonize the surface based on the Japanese standard JI SZ 2801: were conducted 2000th In this case, bacteria are applied in a nutrient solution to the material to be examined and incubated. After the inoculation of the samples, a thin film is pressed on the inoculum, thus the activity of the surface may be tested so that the bacterial suspension is distributed in a thin layer as possible on the test specimen and. The specific action is based on the difference in bacteria counts between a with compound (X) additive-containing sample and the zero sample, which consists of the same base material (without additive (ie without compound X)). The efficacy of antimicrobial surfaces is defined by the microbial reduction achieved within the contact time and given in log steps. A log-stage corresponds to the reduction of the germs at a power of ten (loglO). The specified number of bacteria refers to the evaluation of the test by counting.

Table 1

inventively

Example 52: Synthesis of Compound (X)

Step 1:

Producing a warp constant,

bernsteinsäureanhydridfunktionellen silicone by

Hydrosilylation of 1, 1, 1, 3, 5, 5, 5 -Heptamethylsilan with

Allylsuccinic, preferably at about 90-110 ° C. The synthesis is carried out under use of equimolar based on the functional Si-H groups and allyl. An over- or

Deficiency of the individual reactants is also possible. After the reaction, purification, for example, by

carried distilling the reaction product.

Level 2:

Functionalization for the connection to silicone elastomers: It is the product of step 1 with a 1, 1, 3, 3 - tetramethyl - 1, 3 -divinyldisiloxan implemented using the equilibration reaction. The molar ratio 1, 1, 3, 3 - tetramethyl - 1, -divinyldisiloxan 3 and the reaction product of step 1 is at least 2, preferably at least 3. The

Temperature of the solution must not exceed 138 ° C. Pentamethyl - - 1-vinyldisiloxane, which are removed via the top of the column during the reaction from the mixture, in order to shift the equilibrium in the direction of divinyl functionalized species during equilibration products Hexamethyldisxloxan and 1, 1, 2, 2, 2 are formed. The

Reaction product exists at the end of the reaction of, preferably at least 90% Divinylfunktionalisierten monomers: 3- (3- (1,1,3,5, 5-pentamethyl-1, 5 -divinyltrisiloxan-3 - yl) propyl) dihydrofuran 2, 5- dion. Fortifying

anhydride functionalized D group, in the

equilibration take place, but this is irrelevant to the application. Purification by

Distillation is carried out in a preferred embodiment. is as equilibration of the previous

Examples with the average catalyst used

Molecular formula PNC1 2 used.

Example 53: Synthesis of Compound (X)

Introduction of D-units in the product of Example 52 by equilibration with an a, ω-vinyl-functional

Polydimethylsiloxane. The chain length of the inserted

Polydimethylsiloxane is chosen such that statistically the desired number of D groups in compound (X) is incorporated. In Example 53 the product of Example 52 in a ratio of 1: 4 with an a, ω-vinyl-functional

Polydimethylsiloxane equilibrated with an average chain length of 200 units. Result of this reaction is an inventive a, ω-vinyl-functional, with one or more pendant Propyldihydrofuran-2-5-dione groups modified polydimethylsiloxane.

Claims

claims
1. A crosslinkable silicone composition comprising at least one silicone compound (X) of the general formula (I)
Formula (I]
in which is a hydrogen, a monovalent, optionally heteroatom-containing radical such as alkyl, aryl, arylalkyl, alkylaryl, SiR 7 3 -, polydimethylsiloxane, identical or different, represent a hydrogen, a monovalent, optionally heteroatom-containing radicals such as alkyl, aryl -, arylalkyl, alkylaryl, R 8 COOR 1, identical or different, represent a hydrogen, a monovalent, optionally heteroatom-containing radical such as alkenyl, alkenylaryl, alkyl, aryl, arylalkyl, alkylaryl, -OSiR 7 3, a monovalent, optionally heteroatom-containing radical such as alkenyl, alkenylaryl, alkyl, aryl, arylalkyl, alkylaryl, -OSiR 7 3, a bivalent alkyl radical, a number between 1 and 30 m n is a number between 0 and 6000, mean at least one R 3, with the proviso that, per molecule of the compound (X) 5 an aliphatically unsaturated double bond or a hydrogen atom, and with the proviso that the silicone compound (X) is used in amounts such that the silicone composition from 0.005 mmol / g and 2 mmol / g of carboxylic acid groups or carboxylic acids to 10 or hydrolyzable Carbonsäureester
Carboxylic contains.
2. Crosslinkable silicone composition according to claim 1, characterized in that the radicals R 1 are selected from methyl, ethyl, phenyl, silyl, and Polydimethylsiloxanresten
15 as well as anhydrides or lactones from further present in the same molecule, carboxyl or hydroxyl groups.
3. Crosslinkable silicone composition according to claim 1 or 2, characterized in that the radicals R 2 selected from hydrogen, methyl, ethyl, phenyl, silyl, and
! 0 Polydimethylsiloxanresten and anhydrides or lactones from other, existing in the same molecule carboxyl or hydroxyl groups.
4. Crosslinkable silicone composition according to claim 1 to 3, characterized in that it addition- a peroxide, or
5 condensation-curing silicone composition!.
5. silicone rubber produced by crosslinking the
Silicon composition according to claims 1 to. 4
EP20130814093 2013-12-17 2013-12-17 Cross-linkable silicone composition Withdrawn EP3083856A1 (en)

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EP3114172A4 (en) * 2014-03-06 2017-10-25 Henkel AG & Co. KGaA A single crystal alumina filled die attach paste
WO2018157941A1 (en) * 2017-03-03 2018-09-07 Wacker Chemie Ag Stretched silicon membranes

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US4495340A (en) * 1983-12-23 1985-01-22 Dow Corning Corporation Curable masses producing carboxyfunctional silicone coatings
DE3447457A1 (en) * 1984-12-27 1986-07-03 Wacker Chemie Gmbh Linkable organopolysiloxanes process for their manufacture and use of these organopolysiloxanes
DE19603628A1 (en) 1996-02-01 1997-08-07 Wacker Chemie Gmbh At room temperature vulcanizing, condensation-curing silicone rubbers
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JP3562578B2 (en) * 2000-10-04 2004-09-08 信越化学工業株式会社 The curable composition
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JP2017502133A (en) 2017-01-19 application

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