WO2008065039A1 - Siloxane-urea copolymers - Google Patents

Siloxane-urea copolymers Download PDF

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Publication number
WO2008065039A1
WO2008065039A1 PCT/EP2007/062695 EP2007062695W WO2008065039A1 WO 2008065039 A1 WO2008065039 A1 WO 2008065039A1 EP 2007062695 W EP2007062695 W EP 2007062695W WO 2008065039 A1 WO2008065039 A1 WO 2008065039A1
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formula
different
optionally
sime
radical
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PCT/EP2007/062695
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German (de)
French (fr)
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Wolfgang Ziche
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Wacker Chemie Ag
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D183/00—Coating 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
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

  • the invention relates to organopolysiloxane-urea copolymers, processes for preparing the organopolysiloxane-urea copolymers, compositions containing the organopolysiloxane-urea copolymers and their preparation.
  • these copolymers can be thermoplastic elastomers.
  • such copolymers are plastic above the softening point, while having elastic properties below.
  • they can be used, for example, as a structural polymer for components such as gaskets.
  • a disadvantage of the use of such copolymers as structural polymer is that deformation can occur due to temperature increase and pressure, as in the case of all thermoplastic elastomers, ie the compression set is large, since hydrogen bonds can constantly dissolve and re-bond even below the softening point , Thus, the range of application is limited to applications in which no elevated temperatures or forces act on the thermoplastic elastomer.
  • the invention relates to copolymers of the general formula
  • X may be identical or different and is an alkylene radical optionally substituted by fluorine, chlorine, C 1 -C 6 -alkyl or C 1 -C 6 -alkyl ester having 1 to 10 000 carbon atoms, in which non-adjacent methylene units are represented by groups -O-, - COO, -OCO- or -OCOO- may be replaced, or an optionally substituted arylene radical having 6 to 22 carbon atoms, Y may be the same or different and a divalent hydrocarbon radical having 1 to 30 carbon atoms, in the non-adjacent methylene units by Groups -O- may be replaced, or the radical is - (CH 2 ) 3 -NH- SiR 2 - (CH 2 ) 3 -NH-,
  • Z may be identical or different and is a bivalent hydrocarbon radical optionally substituted by fluorine or chlorine and having from 1 to 30 carbon atoms,
  • D may be the same or different and represents hydrogen or a monovalent, optionally substituted hydrocarbon radical
  • E may be the same or different and represents an oxygen atom or an amino group -ND-
  • R can be identical or different and denotes a monovalent hydrocarbon radical with 1 to 20 carbon atoms which is optionally substituted by fluorine or chlorine,
  • R 'in the case of R''is a hydrogen atom is a radical HND-Y-Si (OR 1) 0 R2 0 - (0-SiR 2) n -O-Si (OR 1) o R 2 _ o -Y-ND -, HNR 4 -G-NR 4 - or HE-XE- and in the case of R '' is equal to -CO-NH- (Z-NH-CO-NHJh-Z-NCO the meaning of OCN- ⁇ Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1) 0 R2 0 - (0-SiR 2) n "0- Si (OR 1 J 0 R 2 - O -Y-ND-, OCN-iZ-NH-CO-NHJ h -Z-NH-CO-NR ⁇ G-NR 4 - or OCN- ⁇ Z-NH-CO-NHJ h -Z-NH-CO- EXE-, n
  • the copolymer of formula (I) has at least one unit with h different 0 and the individual blocks (A), (B) and (C) may be randomly distributed in the polymer.
  • organopolysiloxanes is intended to encompass both polymeric, oligomeric and dimeric siloxanes.
  • divalent radicals Z are alkylene radicals, such as the methylene, ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene, tert. Butylene, n-pentylene, iso-pentylene, neo-pentylene, tert.
  • Pentylene radical hexylene radicals, such as the n-hexylene radical, heptylene radicals, such as the n-heptylene radical, octylene radicals, such as the n-octylene radical and isooctylene radicals, such as the 2,2,4-trimethylpentylene radical, nonylene radicals, such as n -Nonyl radical, decyl radicals, such as the n-decylene radical, dodecylene radicals, such as the n-dodecylene radical; Alkenylene radicals, such as the vinylene and allylene radicals; Cycloalkylene radicals, such as cyclopentylene, cyclohexylene, cycloheptylene radicals and methylcyclohexylene radicals; Arylene radicals, such as the phenylene and the naphthylene radical; Alkarylene radicals, such as o-, m
  • Radical Z is preferably alkylene groups having 1 to 24 carbon atoms, more preferably hexylene,
  • Examples of the bivalent radicals G are the examples listed for Z.
  • Radicals G are preferably alkylene radicals having 1 to 6 carbon atoms, arylene radicals, such as the o-, m- or p-phenylene radical, and aralkylene radicals, such as the phenylene radical, with the radical -CH 2 CH 2 - being particularly preferred ,
  • Z ⁇ examples are all examples given for Z.
  • it is at rest Z ⁇ alkylene groups having 1 to 24 carbon atoms, more preferably alkylene groups having 1 or 3 carbon atoms.
  • radicals Y are preferably alkylene radicals having 1 to 30 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O-, or arylene radicals having 6 to 22 carbon atoms.
  • Particularly preferred radical Y is alkylene groups having 1 to 3 carbon atoms, in particular the methylene or propylene radical.
  • radical X examples are the butylene radical, ethylene radical, hexylene radical, - (CH 2 ) 3 - (O-CH (CH 3 ) -CH 2 ) 2 - 3 ooo-O- (CH 2 ) 3 -, -CH ( CH 3) -CH 2 - (O-CH (CH 3) -CH 2) 2 - 3O oo-, - (CH 2) 3 - (0-CH 2 -CH 2) 2 _ 300 -O- (CH 2 ) 3 - and -CH 2 -CH 2 - (OCH 2 -CH 2 ) 2-300- •
  • the radicals X are preferably polyether radicals, particularly preferably polypropylene glycol radicals, in particular those having 2 to 600 carbon atoms.
  • radical R examples include alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • -Pentyl hexyl, such as the n-hexyl, heptyl, such as the n-heptyl, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2, 2, 4-trimethylpentyl, nonyl, such as the n Nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical; Alkenyl radicals, such as the vinyl and allyl radicals; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl and the naphthyl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals, xy
  • Radical R is preferably a hydrocarbon radical having 1 to 6 carbon atoms, more preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl radical.
  • Radicals R 1 are preferably linear or branched alkyl radicals having 1 to 12 carbon atoms and alkoxyalkyl radicals such as 2-methoxyethyl, 2-ethoxyethyl and 2- (2'-methoxyethyl) ethyl, particularly preferably alkyl radicals 1 to 12 carbon atoms, in particular the methyl and ethyl radical.
  • radical R 4 are the radicals specified for R, hydrogen atom and the radicals - (CH 2 ) 4 Si (OCH 3 ) 3 ,
  • Radical R 4 is preferably hydrogen and the abovementioned silyl-substituted alkyl radicals, more preferably hydrogen and the radicals - (CH 2 ) 3 Si (OCH 3 ) 3 ,
  • hydrocarbon radicals D are the radicals given above for R.
  • the radical D is preferably an alkyl radical or hydrogen atom, particularly preferably an alkyl radical having 1 to 12 carbon atoms or hydrogen atom, in particular hydrogen atom.
  • the radical E is preferably an oxygen atom.
  • A preferably has the meaning of an integer from 1 to 1000, particularly preferably from 5 to 1000, in particular from 5 to 100.
  • B preferably has the meaning of an integer from 1 to 1000, particularly preferably from 5 to 1000, in particular from 5 to 100.
  • c has the meaning of 0 or an integer of 1 to 100, more preferably of 0 or an integer of 1 to 10, especially 0.
  • H has the meaning of an integer from 1 to 4, particularly preferably from 1 to 2, in particular 1.
  • radicals R ' in the case where R "is hydrogen, are radicals which result from the unreacted end groups from the educts used, such as H 2 N- (CH 2 ) 3-Si (CH 3 ) 2 - (O-Si (CH 3 ) 2 ) 40 -O-Si (CH 3 ) 2 - (CH 2 ) 3 -NH-, H 2 N-CH 2 -CH 2 -N- (CH 2 ) 3 Si ( OCH 3 ) 3 ,
  • radicals R ' in the event that R "is equal to -CO-NH- (Z-NH-CO-NHJh-Z-NCO, radicals which arise from the unreacted end groups from the starting materials used, such as OCN- ⁇ (CH 2 ) 6 -NH-CO-HNj 2 - (CH 2 ) 3 -Si (CH 3 ) 2 - (O-Si (CH 3 ) 2 ) 4 o-O-Si (CH 3 ) 2 - (CH 2) 3 -NH-, OCN- (C 6 H 1O -CH 2 -C 6 H 10 -NH-CO-HNH-CH 2 -CH 2 -N- (CH 2) 3 Si (OCH 3) 3 ,
  • the radical R ' is in the case of R''is a hydrogen atom preferably a radical HND-Y-Si (OR 1) 0 R 2 - 0 - (0-SiR 2) n -O- Si (OR 1 J 0 R 2 - O -Y-ND- or HNR 4 -G-NR 4 - and in the case of R ", equal -CO-NH- (Z-NH-CO-NHJh-Z-NCO, preferably at OCN- (Z-) NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1 J 0 R 2 - O - (0-SiR 2) n -0-Si (OR 1 J 0 R 2 - o -Y ND or OCN- ⁇ Z-NH-CO-NH ⁇ h -Z-NH-CO-NR 4 -G-NR 4 -.
  • radicals R are hydrogen atom, -CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NCO, -CO-NH-C 6 H 1 O -CH 2 -C 6 H 10 -NCO and -CO-NH-C 6 H 3 (CH 3 ) -NCO, with hydrogen being preferred.
  • N is preferably an integer from 10 to 4000, more preferably from 30 to 1000.
  • Copolymers of the invention comprising units (C) can give a harder material compared to copolymers according to the invention which contain no unit (C), since there are more hydrogen bonds in them.
  • Polyether units as units (C) can be used, e.g. in US 20060014916 A can be used to keep the processing temperatures of the material below the decomposition temperatures of the material, if necessary.
  • the properties such as, for example, peel and peel strength, printability, tensile and tear propagation resistance or water vapor permeability, can be set in a targeted manner.
  • Copolymers of the formula (I) with c are preferably 0, since thus exclusively siloxane chains are present and thus the polymers have advantages such as, for example, high transparency and UV stability with simultaneously low surface energies.
  • copolymers of the formula (I) according to the invention are H [NH (CH 2) 3SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH2) 3-NH-CO-NH- (CH 2) 6 -NH-CO-NH- (CH 2) 6 -NH-CO -NH-CH 2 CH 2 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH-CO] 10 -NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O 35SiMe 2 (CH 2 ) 3-NH 2 ,
  • copolymers of the formula (I) according to the invention have a content of units A of the formula (II) of preferably greater than 70% by weight, particularly preferably greater than 80% by weight, in each case based on the total weight of the copolymer.
  • novel copolymers of the formula (I) are preferably rubber-elastic solids at room temperature with tensile strengths of preferably between about 0.5 and 20 MPa and elongation at break of between about 50 and 1000%. They soften at temperatures between preferably 60 and 240 0 C and thereby lose their rubber-elastic properties.
  • the hydrolyzable radical -OR 1 can react to form OH groups, which in turn can condense with further OR 1 or OH groups to form siloxane bonds.
  • copolymers according to the invention also have the advantage that they have very good mechanical properties without having to add fillers.
  • copolymers according to the invention are distinguished by excellent physical properties, as are known from polyorganosiloxanes, such as, for example, lower
  • copolymers according to the invention are the high thermal and oxidative stability, good resistance to swelling and decomposition by hydrocarbons containing solvents.
  • copolymers according to the invention can be prepared analogously to any process which is already known to the person skilled in the art and is carried out, for example, for the synthesis of (prep) polymers for polyurethanes.
  • X, Y, Z, D, E, G, R, R 1 , R 4 , and o have one of the meanings mentioned above and h 'is an integer of at least 1.
  • Examples of the compounds of the formula (V) used in accordance with the invention are CCCO-aminopropyldimethylsilyl-terminated polydimethylsiloxanes, CC, CO-aminopropyldimethoxysilyl-terminated polydimethylsiloxanes, CC, CO-aminomethyldimethylsilyl-terminated polydimethylsiloxanes and CC, CO-aminomethyldimethoxysilyl-terminated polydimethylsiloxanes.
  • Preferred compounds of the formula (VI) which can be used in the process according to the invention are 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyldimethylmethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, N, N'-bis (3-trimethoxysilylpropyl) ethylenediamine, N, N'-bis- (3-triethoxysilylpropyl) - ethylenediamine, N, N'-bis- (3-dimethoxymethylsilylpropyl) ethylenediamine and N, N'-bis (3-diethoxymethylsilylpropyl) ethylenediamine, N-trimethoxysilylmethyl
  • isocyanates of the formula (IX) used in accordance with the invention are hexylene diisocyanate, 4,4'-methylenedicyclohexyl-1-diisocyanate, 4,4'-methylenediphenylene diisocyanate, 1,3-diazotidine-2,4-dione bis (4,4 '). -methylenedicyclohexyl) diisocyanate, 1, 3-diazetidine-2,4-dione bis (4,4'-methylenediphenyl) diisocyanate,
  • Tetramethylenexylylene diisocyanate and isophorone diisocyanate, hexylene diisocyanate, 4,4'-methylenedicyclohexylene diisocyanate, 4,4'-methylenediphenylene diisocyanate, tetramethylenexylylene diisocyanate, cyanate and isophorone diisocyanate are preferred as well as Hexylendiisocy- anat, 4, 4 '-Methylendicyclohexylendiisocyanat and isophorone diisocyanate are particularly preferred.
  • Examples of the isocyanates of the formula (VII) used according to the invention are OCN-Z-NH-CO-NH-Z-NCO, OCN-Z-NH-CO-NH-Z-NH-CO-NH-Z-NCO, with Z is hexylene, 4, 4 '-methylenedicyclohexylene, 4, 4' -methylenediphenylene, tetramethylenxylylene and isophorone lenrest, wherein OCN-Z-NH-CO-NH-Z-NCO with Z is hexylene, 4, 4 'Methylenedicyclohexylen-, 4, 4' -Methylendiphenylen-, Tetramethylenxylylen- and Isophoronylenrest preferred and OCN-Z-NH-CO-NH-Z-NCO with Z equal to 4, 4 '-Methylendicyclohexylen- and isophoronylene are particularly preferred.
  • the isocyanates of the formula (VII) used according to the invention can be prepared by reacting diisocyanates of the formula (IX) and water, preferably in the presence of catalysts, such as, for example, N, N-dimethylethanolamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N', N'-pentamethyldiethylenetriamine, N, N'-trimethylaminoethylethanolamine, triethylenediamine, dibutyltin dilaurate, tin (II ) octoate and synergistic mixtures of triethylenediamine and dibutyltin dilaurate are prepared or formed in situ in carrying out the method according to the invention.
  • the catalysts used to prepare the diisocyanates of the formula (VII) do not interfere with the reaction according to the invention of (a) with (b) and optionally (c), (d) and (e).
  • the isocyanates of formulas (VII) and / or (IX) may each be wholly or partly in the form of the corresponding blocked diisocyanates, but this is not preferred. These may be, in particular, thermally unstable reaction products of isocyanates with, for example, phenols, ketoximes, lonestern and nitrogen-containing heterocycles, which are known in the art. In the reaction of the blocked isocyanate with the other educts then the necessary temperature for deblocking must be achieved, the then freed blocking molecules remain in the reaction mixture.
  • Examples of the compounds of the formula (VIII) used according to the invention are compounds known from polyurethane chemistry, such as diols, e.g. Ethylene glycol, 1,4-butanediol, polyethylene glycols, polypropylene glycols and polyester polyols, diamines, e.g.
  • the compounds of the formula (VIII) are preferably 1,4-butanediol, polyethylene glycols, polypropylene glycols, 2-methyl-1,5-pentanediamine and amino-terminated polyethers (ATPE), 1,4-butanediol, polypropylene glycols, Methyl-1,5-pentanediamine are particularly preferred.
  • the stoichiometry of the reactants for the preparation of the copolymers according to the invention is preferably selected such that the molar ratio of the isocyanate groups from the compounds of the formulas (VII) and (IX) to the sum of the isocyanate-reactive EH and NH groups from the compounds of the formulas (V), (VI) and (VIII) is in the range of preferably 0.7 to 1.3, particularly preferably 0.95 to 1.05, in particular 1. At a ratio of the isocyanate groups to the reactive
  • R " -CO-NH- (Z-NH-CO-NH-NH-Z-NCO and the resulting R 'radicals as defined above at the other end of the polymer chains.
  • the process according to the invention can be carried out in the presence of catalysts (f).
  • the catalysts which may be used may be all known catalysts which comprise the addition of the isocyanate groups of the compounds of the general formulas (VII) and (IX) to the active groups of the compounds of the formulas (V), (VI) and ( VIII) promote, are used.
  • catalysts (f) are diorganotin compounds such as stannous octoate, dibutyltin dilaurate and dibutyltin diacectate, bismuth compounds such as bismuth (2-ethylhexanoate), bismuth neodecanoate and bismuth tetramethylheptanedionate, and zinc compounds such as zinc acetylacetonate, zinc 2-ethylhexanoate and zinc neodecanoate.
  • diorganotin compounds such as stannous octoate, dibutyltin dilaurate and dibutyltin diacectate
  • bismuth compounds such as bismuth (2-ethylhexanoate), bismuth neodecanoate and bismuth tetramethylheptanedionate
  • zinc compounds such as zinc acetylacetonate, zinc 2-ethylhexanoate and zinc n
  • Examples of commercially available catalysts are Borchi® Kat 22, Borchi® Kat VP 0243 and Borchi® Kat VP 0244 from Borchers GmbH, Germany, the BICAT® grades from The Shepherd Chemical Company, USA and K-Kat® K-348 from KING INDUSTRIES, INC., USA.
  • catalysts are used in the process according to the invention, these are amounts of preferably 0.0001 to 1 part by weight, particularly preferably 0.001 to 0.1 part by weight, in each case based on 100 parts by weight of the total mixture.
  • the process according to the invention can be carried out in the presence of solvents (g), with orga- nische solvents, in particular non-protic, polar solvents, are preferred.
  • solvents are used in the process according to the invention, these are amounts of preferably 10 to 200 parts by weight, more preferably 10 to 100 parts by weight, in each case based on 100 parts by weight of the total mixture.
  • the reaction according to the invention can be carried out in solution or in substance, a reaction in substance being preferred.
  • temperatures of from 0 to 100 ° C. are preferred and from 20 to 80 ° C. are particularly preferred.
  • temperatures above the softening point of the copolymer produced of the formula (I) are preferred.
  • the process according to the invention can be carried out by methods known to the person skilled in the art, for example by means of extruders, kneaders, roll mills, dynamic or static mixers.
  • the process according to the invention is carried out, in particular in the presence of organyloxysilyl groups, preferably with the exclusion of moisture.
  • siloxane-urea copolymers prepared according to the invention can now be freed of any starting materials still present or of any solvents or catalysts used, if appropriate, by any desired methods known hitherto. by distillation or extraction.
  • the components used in the process according to the invention are commercially available products or can be prepared by methods customary in chemistry.
  • the components used in the process according to the invention may each be a type of such a component as well as a mixture of at least two types of a respective component.
  • the process according to the invention has the advantage that it is simple to carry out and many possible copolymers with great variability can be prepared.
  • the process according to the invention has the advantage that copolymers can be prepared in a well-defined manner.
  • the copolymers according to the invention or those produced according to the invention can be used everywhere where organopolysiloxane-urea copolymers have hitherto been used.
  • copolymers of the formula (I) according to the invention or prepared according to the invention can be processed by the customary processing methods for polymers or thermoplastic elastomers, for example by means of extrusion, injection molding, blow molding, vacuum thermoforming. Processing as a solution or emulsion or suspension is also possible.
  • Preferred applications of the copolymers of the formula (I) according to the invention or inventively prepared are uses as a base material for thermoplastic elastomers, such as cable sheaths, hoses, gaskets, keyboard mats, for membranes, such as selectively gas-permeable membranes, paintable and recoatable components for the automotive industry, film for Laminated safety glass, as additives in polymer blends, such as impact modifiers or flame retardants, or as a material for the modification of fibers or for coating applications, for example in anti-adhesive coatings, fabric-compatible coatings, flame-retardant coatings or as a coating material for wood, paper or cardboard, such as as a release coating for adhesive tapes and labels.
  • thermoplastic elastomers such as cable sheaths, hoses, gaskets, keyboard mats
  • membranes such as selectively gas-permeable membranes, paintable and recoatable components for the automotive industry
  • film for Laminated safety glass as additives in
  • Preferred applications are furthermore coatings for textile fibers or textile fabrics, as a coating material for natural materials, such as leather and furs.
  • Further possible applications include sealants and adhesives, such as, for example, hot melt adhesives or adhesives to be applied as a solution, primers for improving the adhesion of sealants and adhesives on various substrates, additives for polymer processing, such as extrusion aids for thermoplastic processing, Cleaning, cleaning or care preparations, anti-fouling coatings, cosmetics, body care preparations, paint additives, PSA coatings, detergent additives and textile processing, defoamer formulations, modifiers for resins or bitumen modification, as mold release agents, as biocompatible materials in medical applications, such as contact lenses, as material for membranes and as material for photoactive systems, for example for lithographic processes, optical data backup or optical data transmission.
  • sealants and adhesives such as, for example, hot melt adhesives or adhesives to be applied as a solution
  • copolymers of the formula (I) according to the invention or those prepared according to the invention are suitable for use in crosslinkable compositions, such as room-temperature crosslinkable compositions.
  • Another object of the present invention are crosslinkable compositions containing inventive or inventively prepared copolymers of the formula (I).
  • condensation reaction implies that, if appropriate, a hydrolysis step of hydrolyzable radicals takes place before the condensation reaction.
  • crosslinkable compositions according to the invention are preferably one-component compositions.
  • the constituents used in each case can be mixed with one another in any desired and hitherto known manner. This mixing preferably takes place at room temperature or at a temperature which occurs when the components are added together at room temperature without additional heating or cooling, and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa. If desired, however, this mixing can take place even at higher or lower pressures, for example at low pressures to avoid gas inclusions.
  • the preparation of the compositions according to the invention and their storage are preferably carried out under substantially anhydrous conditions in order to avoid premature reaction of the compositions.
  • the component (i) used according to the invention is preferably copolymers of the formula (I) which have at least two radicals -OR 1 , where R 1 has the meaning given above.
  • crosslinkers (ii) are preferably organyloxysilanes and also their partial hydrolysates, such as tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-butyltrimethoxysilane, n-octyltrimethoxysilane, i-octyltrimethoxysilane, vinyltrimethoxysilane and Vi - nyltriethoxysilane and their Generalhydrolysate, with methyl and vinyltrimethoxysilane are particularly preferred.
  • crosslinkable compositions according to the invention contain crosslinkers (ii), these are amounts of preferably 0.05 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based in each case on 100 parts by weight of crosslinkable composition.
  • condensation catalysts (iii) are butyl titanates and organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, and also the reaction products thereof with the alkoxysilanes which are mentioned as crosslinkers or adhesion promoters.
  • NEN dialkyltin oxide in the mentioned as crosslinkers or adhesion promoters alkoxysilanes, with di-n-butyltin dilaurate and dibutyltin oxide in tetraethoxysilane is preferred and di-n-butyltin dilaurate is particularly preferred.
  • crosslinkable compositions according to the invention comprise catalyst (iii), these are amounts of preferably 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • Filler (iv) is preferably pyrogenic kiesiklaren or carbon blacks or mixtures thereof, with carbon black having a BET surface area of at least 30 m 2 / g is particularly preferred. If the compositions according to the invention comprise fillers (iv), these are amounts of preferably 1 to 50 parts by weight, preferably 2 to 30 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • adhesion promoter (s) optionally used it is possible to use all adhesion promoters which have hitherto been used in compositions which can be crosslinked by condensation.
  • adhesion promoters (v) are silanes with hydrolyzable groups and SiC-bonded vinyl, acryloxy, methacryloxy, epoxy, acid anhydride, acid, ester or ether groups and their partial and mixed hydrolysates.
  • compositions according to the invention comprise adhesion promoters (v), these are amounts of preferably 0.01 to 5 parts by weight, preferably 0.5 to 4 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • component (vi) are amounts of preferably 0.01 to 30 parts by weight, particularly preferably 0.05 to 25 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • crosslinkable compositions according to the invention can contain crosslinkable polymers (vii), such as organopolysiloxanes having reactive end groups.
  • crosslinkable siloxanes are CCCO-dihydroxypolydimethylsiloxanes and OC, CO-bis (dimethoxymethylsilyl) -terminated polydimethylsiloxanes.
  • the component (vii) optionally used in the crosslinkable compositions according to the invention is preferably polydiorganosiloxanes having at least one OH group or a hydrolyzable group at the chain ends, more preferably polydimethylsiloxanes having at least one OH group or a hydrolyzable group at the chain ends , in particular ⁇ , ⁇ -dihydroxypolydimethylsiloxanes or ⁇ , ⁇ -bis (di-methoxymethylsilyl) terminated polydimethylsiloxanes having a viscosity of 100 to 500,000 mPas.
  • the crosslinkable compositions according to the invention preferably contain component (vii).
  • This component is preferably used to adjust the processing properties, such as viscosity or pot life. If component (vii) is used, these are amounts of preferably 1 to 50 parts by weight, more preferably 2 to 25 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • the individual constituents of the crosslinkable compositions according to the invention may each be one type of such constituent as well as a mixture of at least two different types of such constituents.
  • compositions according to the invention contain no further constituents apart from component (i), if appropriate (ii), (iii), (iv), (v), (vi) and (vii).
  • the preparation of the crosslinkable compositions according to the invention can be carried out by simple mixing.
  • Vulcanizates of the compositions according to the invention can be obtained by optionally necessary hydrolysis of hydrolyzable radicals and subsequent condensation of the resulting silanol groups.
  • the hydrolysis can be carried out by atmospheric moisture or by steam, water baths or aqueous solutions in contact with the copolymer of the invention according to the general formula (I).
  • the usual water content of the air is preferably sufficient.
  • the crosslinking of the compositions of the invention is preferably carried out at room temperature. If desired, it can also be used at higher or lower Ren temperatures as room temperature, such as at -5 to 15 ° C or at 30 to 50 0 C, for example, by means of the normal water content of the air excess concentrations of water are performed.
  • the crosslinking is carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
  • the vulcanizates of the copolymers according to the invention have, after moisture crosslinking, a lower dependence of the mechanical properties on the temperature.
  • the vulcanizates of the copolymers according to the invention no longer become plastic when the temperature increases, so they can no longer flow and are thus more dimensionally stable.
  • the vulcanizates according to the invention generally have better mechanical properties over a wider temperature range, so that they can be used in more diverse fields of application.
  • crosslinkable compositions of the invention are preferably used as hot melt adhesive, adhesive, PSA (Pressure Sensitive Adhesive), sealant, coating for example paper, textile, fibers or silicate surfaces, impregnating agent, paint, Component used in composites, additive for polymers, molding and component for medical purposes as well as for use in automotive or laminated glass.
  • PSA Pressure Sensitive Adhesive
  • sealant coating for example paper, textile, fibers or silicate surfaces
  • impregnating agent paint
  • Component used in composites additive for polymers, molding and component for medical purposes as well as for use in automotive or laminated glass.
  • compositions of the invention have the advantage that they possess all of the abovementioned advantages of the copolymers according to the invention used.
  • compositions of the invention have the advantage that they have very good mechanical properties.
  • compositions according to the invention are the high thermal and oxidative stability, good resistance to swelling and decomposition by solvents containing hydrocarbons.
  • compositions of the invention have the advantage that the properties, such as peel and peel strength, printability, tensile and tear propagation resistance or water vapor permeability, can be adjusted in a targeted manner.
  • the shaped bodies according to the invention have the advantage that they have a lower dependence of the mechanical properties on the temperature, in particular at higher temperatures.
  • the shaped bodies according to the invention furthermore have the advantage that they have a very good adhesion to substrates.
  • all viscosity data refer to a temperature of 25 ° C. Unless indicated otherwise, the following examples are at a pressure of the surrounding atmosphere, that is about 1000 hPa, and at room temperature, ie at about 23 ° C, or at a temperature that occurs when combining the reactants at room temperature without additional heating or cooling, and carried out at a relative humidity of about 50%. Furthermore, all parts and percentages are by weight unless otherwise specified.
  • the Shore A hardness is determined according to DIN (German Industrial Standard) 53505 (March 2000 edition).
  • the compression set (DVR) was determined according to ISO 815 at 70 0 C.
  • Example 1 17.1 g of isophorone diisocyanate are heated to 70 ° C. for 2 hours with 0.7 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran. For this purpose, 99.3 g of a CC, CO-aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are added. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 82 Shore A, tensile strength 7.8 MPa, elongation at break 461%, stress at 100% elongation 4.07 MPa. The DVR is 88%. Comparative Example 1
  • 20.0 g of 4, 4 '-Methylendicyclohexylendiisocyanat be with 0.7 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran for 2 hours at 70 0 C heated.
  • 99.3 g of a CC, C0-amino-propyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are added.
  • the viscous solution was poured into PTFE molds and the solvent removed by evaporation.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 81 Shore A, tensile strength 8.4 MPa, elongation at break 301%, stress at 100% elongation 5.49 MPa.
  • the DVR is 90%.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 55 Shore A, tensile strength 5.3 MPa, elongation at break 450%, stress at 100% elongation 1.6 MPa. The DVR is 98%.
  • 1700.0 g of an ⁇ , ⁇ -aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are vigorously stirred with 300 g of water and then allowed to stand for 14 days and separated from the water.
  • the polydimethylsiloxane then contains 3032 ppm of water.
  • 100 g of the hydrous polydimethylsiloxane were dissolved in 340 ml of tetrahydrofuran (THF) and admixed with 11.5 g of isophorone diisocyanate and 10 mg of di-butyltin dilaurate. Subsequently, the mixture was heated to 70 0 C for 1 hour. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
  • THF tetrahydrofuran
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 61 Shore A, tensile strength 6.1 MPa, elongation at break 557%, stress at 100% elongation 2.25 MPa.
  • Example 4 4.4 g of isophorone diisocyanate are heated to 70 ° C. with 0.18 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran for 2 hours.
  • the viscous solution was poured into PTFE molds and the solvent removed by evaporation.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 31 Shore A, tensile strength 3.4 MPa, elongation at break 601%, stress at 100% elongation 0.81 MPa.
  • the DVR is 51%.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 15 Shore A, tensile strength 1.2 MPa, elongation at break 650%, stress at 100% elongation 0.45 MPa.
  • the DVR is 97%.
  • the temperature of the extruder was 170 ° C at this point. The remaining sectors were kept at 180 ° C. At the end of the extruder emerged a crystal clear colorless thermoplastic extrudate strand which was comminuted in a subsequent granulator. The granules thus obtained were pressed in a press at 180 0 C to a 2 mm thick plate and punched therefrom mold S2 according to DIN 53504. The following mechanical properties were determined: hardness 66 Shore A, tensile strength 6.8 MPa, elongation at break 543%, stress at 100% elongation 2.3 MPa.

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Abstract

The invention relates to organopolysiloxane-urea copolymers, a process for preparing the organopolysiloxane-urea copolymers, compositions containing the organopolysiloxane-urea copolymers and their production.

Description

Siloxan-Harnstoff-CopolymereSiloxane-urea copolymers
Die Erfindung betrifft Organopolysiloxan-Harnstoff-Copolymere, Verfahren zur Herstellung der Organopolysiloxan-Harnstoff- Copolymere, Zusammensetzungen enthaltend die Organopolysiloxan- Harnstoff-Copolymere sowie deren Herstellung.The invention relates to organopolysiloxane-urea copolymers, processes for preparing the organopolysiloxane-urea copolymers, compositions containing the organopolysiloxane-urea copolymers and their preparation.
Organopolysiloxan-Polyharnstoff-Blockcopolymere sind bekannt und werden durch Copolymerisation von mit Aminoalkylgruppen terminierten Siloxanen und Diisocyanaten hergestellt.Organopolysiloxane-polyurea block copolymers are known and are prepared by copolymerization of aminoalkyl terminated siloxanes and diisocyanates.
Durch die Ausbildung von Wasserstoffbrücken zwischen den Harnstoffgruppen, den Hartblöcken, können diese Copolymere thermoplastische Elastomere sein. Somit sind derartige Copolymere o- berhalb des Erweichungspunktes plastisch, während sie darunter elastische Eigenschaften haben. Damit können sie beispielsweise als strukturelles Polymer für Bauteile, wie Dichtungen, verwendet werden. Nachteilig für die Verwendung derartiger Copolymere als strukturelles Polymer ist jedoch, dass durch Temperaturer- höhung und Druckeinwirkung wie bei allen thermoplastischen E- lastomeren Verformung eintreten kann, d.h dass der Druckverformungsrest groß ist, da sich Wasserstoffbrücken auch unterhalb des Erweichungspunktes ständig lösen und neu knüpfen können. Damit ist der Einsatzbereich limitiert auf Anwendungen, bei de- nen keine erhöhten Temperaturen bzw. Kräfte auf das thermoplastische Elastomer einwirken.By forming hydrogen bonds between the urea groups, the hard blocks, these copolymers can be thermoplastic elastomers. Thus, such copolymers are plastic above the softening point, while having elastic properties below. Thus, they can be used, for example, as a structural polymer for components such as gaskets. However, a disadvantage of the use of such copolymers as structural polymer is that deformation can occur due to temperature increase and pressure, as in the case of all thermoplastic elastomers, ie the compression set is large, since hydrogen bonds can constantly dissolve and re-bond even below the softening point , Thus, the range of application is limited to applications in which no elevated temperatures or forces act on the thermoplastic elastomer.
Bekannt sind Verfahren zur in situ-Hydrolyse von Polyisocyana- ten (DE 1 020 327B) zur Ausbildung von Harnstoffgruppen enthaltenden Polyisocyanaten .Methods for the in situ hydrolysis of polyisocyanates (DE 1 020 327B) for the formation of polyisocyanates containing urea groups are known.
Gegenstand der Erfindung sind Copolymere der allgemeinen FormelThe invention relates to copolymers of the general formula
R'- [(A)a(B)b(C)c] -R" (I), worinR'- [(A) a (B) b (C) c ] -R "(I), wherein
(A) gleich oder verschieden sein kann und eine Einheit der For- mel (II)(A) may be the same or different and a unit of the formula (II)
- [CO-NH- { Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR1J0Ra-O- (0-SiR2) n-O- Si(OR1J0R2-O-Y-ND]-,- [CO-NH- {Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1 J 0 Ra- O - ( O -SiR 2 ) nO-Si (OR 1 J 0 R 2 - O -Y-ND] -,
(B) gleich oder verschieden sein kann und eine Einheit der Formel (III)(B) may be the same or different and a unit of the formula (III)
- [CO-NH- {Z-NH-CO-NH}h-Z-NH-CO-NR4-G-NR4] -- [CO-NH- {Z-NH-CO-NH} h -Z-NH-CO-NR 4 -G-NR 4 ] -
undand
(C) gleich oder verschieden sein kann und eine Einheit der Formel (IV)(C) may be the same or different and a unit of the formula (IV)
- [CO-NH- { Z-NH-CO-NHJh-Z-NH-CO-E-X-E] -- [CO-NH- {Z-NH-CO-NHJ h -Z-NH-CO-EXE] -
darstellen, wobeirepresent, wherein
X gleich oder verschieden sein kann und einen gegebenenfalls durch Fluor, Chlor, d-C6-Alkyl- oder Ci-C6-Alkylester sub- stituierten Alkylenrest mit 1 bis 10000 Kohlenstoffatomen bedeutet, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -0-, -COO-, -OCO- oder -OCOO- ersetzt sein können, oder einen gegebenenfalls substituierten Ary- lenrest mit 6 bis 22 Kohlenstoffatomen bedeutet, Y gleich oder verschieden sein kann und einen zweiwertigen Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können, oder den Rest - (CH2) 3-NH- SiR2-(CH2)3-NH- darstellt,X may be identical or different and is an alkylene radical optionally substituted by fluorine, chlorine, C 1 -C 6 -alkyl or C 1 -C 6 -alkyl ester having 1 to 10 000 carbon atoms, in which non-adjacent methylene units are represented by groups -O-, - COO, -OCO- or -OCOO- may be replaced, or an optionally substituted arylene radical having 6 to 22 carbon atoms, Y may be the same or different and a divalent hydrocarbon radical having 1 to 30 carbon atoms, in the non-adjacent methylene units by Groups -O- may be replaced, or the radical is - (CH 2 ) 3 -NH- SiR 2 - (CH 2 ) 3 -NH-,
Z gleich oder verschieden sein kann und einen zweiwertigen, gegebenenfalls durch Fluor oder Chlor substituierten Koh- lenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen bedeutet,Z may be identical or different and is a bivalent hydrocarbon radical optionally substituted by fluorine or chlorine and having from 1 to 30 carbon atoms,
D gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest darstellt, E gleich oder verschieden sein kann und ein Sauerstoffatom oder eine Aminogruppe -ND- darstellt,D may be the same or different and represents hydrogen or a monovalent, optionally substituted hydrocarbon radical, E may be the same or different and represents an oxygen atom or an amino group -ND-,
R gleich oder verschieden sein kann und einen einwertigen, gegebenenfalls durch Fluor oder Chlor substituierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen bedeu- tet,R can be identical or different and denotes a monovalent hydrocarbon radical with 1 to 20 carbon atoms which is optionally substituted by fluorine or chlorine,
R1 gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls durch Fluor, Chlor oder Organyloxygruppen substituierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, -(C=O)-R oder -N=CR2 darstellt, R4 gleich oder verschieden sein kann und einen Rest der Formel -Z λ-SiRp (OR1) 3-p mit Zλ gleich einer für Z oben angegebenen Bedeutung und p gleich 0, 1 oder 2, Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest bedeutet, G gleich oder verschieden sein kann und eine für Z angegebene Bedeutung hat, R" Wasserstoffatom oder eine Einheit -CO-NH- { Z-NH-CO-NH}h-Z-R 1 may be identical or different and is hydrogen or a monovalent, optionally substituted by fluorine, chlorine or organyloxy groups hydrocarbon radical having 1 to 20 carbon atoms, - (C = O) -R or -N = CR 2 , R 4 be the same or different can and a radical of the formula -Z λ -SiR p (OR 1 ) 3-p with Z λ is equal to a meaning given above for Z and p is 0, 1 or 2, hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, G is the same or is different and has the meaning given for Z, R "is hydrogen or a unit -CO-NH- {Z-NH-CO-NH} h -Z-
NCO bedeutet,NCO means
R' im Fall von R' ' gleich Wasserstoffatom einen Rest HND-Y-Si (OR1) 0R2-0- (0-SiR2) n-O-Si (OR1) oR2_o-Y-ND-, HNR4-G-NR4- oder HE-X-E- bedeutet und im Fall von R'' gleich -CO-NH-(Z-NH-CO-NHJh-Z-NCO die Bedeutung von OCN- { Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR1) 0R2-0- (0-SiR2) n"0- Si (OR1J0R2-O-Y-ND-, OCN-iZ-NH-CO-NHJh-Z-NH-CO-NR^G-NR4- oder OCN- { Z-NH-CO-NHJh-Z-NH-CO-E-X-E- hat, n gleich oder verschieden sein kann und eine ganze Zahl von 1 bis 4000 ist, o gleich oder verschieden sein kann und 0, 1 oder 2 ist, a eine ganze Zahl von mindestens 1 ist, b 0 oder eine ganze Zahl von mindestens 1 ist, c 0 oder eine ganze Zahl von mindestens 1 ist, h 0 oder eine ganze Zahl von mindestens 1 ist,R 'in the case of R''is a hydrogen atom is a radical HND-Y-Si (OR 1) 0 R2 0 - (0-SiR 2) n -O-Si (OR 1) o R 2 _ o -Y-ND -, HNR 4 -G-NR 4 - or HE-XE- and in the case of R '' is equal to -CO-NH- (Z-NH-CO-NHJh-Z-NCO the meaning of OCN- {Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1) 0 R2 0 - (0-SiR 2) n "0- Si (OR 1 J 0 R 2 - O -Y-ND-, OCN-iZ-NH-CO-NHJ h -Z-NH-CO-NR ^ G-NR 4 - or OCN- {Z-NH-CO-NHJ h -Z-NH-CO- EXE-, n may be the same or different and is an integer from 1 to 4000, o may be the same or different and is 0, 1 or 2, a is an integer of at least 1, b is 0 or an integer of is at least 1, c is 0 or an integer of at least 1, h is 0 or an integer of at least 1,
mit der Maßgabe, dass das Copolymer der Formel (I) mindestens eine Einheit mit h verschieden 0 aufweist und die einzelnen Blöcke (A) , (B) und (C) im Polymer statistisch verteilt sein können.with the proviso that the copolymer of formula (I) has at least one unit with h different 0 and the individual blocks (A), (B) and (C) may be randomly distributed in the polymer.
Im Rahmen der vorliegenden Erfindung sollen von dem Begriff Or- ganopolysiloxane sowohl polymere, oligomere wie auch dimere Si- loxane mitumfasst werden.In the context of the present invention, the term organopolysiloxanes is intended to encompass both polymeric, oligomeric and dimeric siloxanes.
Beispiele für zweiwertige Reste Z sind Alkylenreste, wie der Methylen-, Ethylen-, n-Propylen-, iso-Propylen-, n-Butylen-, iso-Butylen-, tert . -Butylen-, n-Pentylen-, iso-Pentylen-, neo- Pentylen-, tert . -Pentylenrest, Hexylenreste, wie der n-Hexylen- rest, Heptylenreste, wie der n-Heptylenrest, Octylenreste, wie der n-Octylenrest und iso-Octylenreste, wie der 2,2,4-Trime- thylpentylenrest, Nonylenreste, wie der n-Nonylenrest, Decy- lenreste, wie der n-Decylenrest, Dodecylenreste, wie der n-Do- decylenrest ; Alkenylenreste, wie der Vinylen- und der Allylen- rest; Cycloalkylenreste, wie Cyclopentylen-, Cyclohexylen-, Cy- cloheptylenreste und Methylcyclohexylenreste; Arylenreste, wie der Phenylen- und der Naphthylenrest ; Alkarylenreste, wie o-, m-, p-Tolylenreste, Xylylenreste und Ethylphenylenreste; Aral- kylenreste, wie der Benzylenrest, der CC- und der ß-Phenylethy- lenrest sowie der 4, 4' -Methylendiphenylenrest .Examples of divalent radicals Z are alkylene radicals, such as the methylene, ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene, tert. Butylene, n-pentylene, iso-pentylene, neo-pentylene, tert. Pentylene radical, hexylene radicals, such as the n-hexylene radical, heptylene radicals, such as the n-heptylene radical, octylene radicals, such as the n-octylene radical and isooctylene radicals, such as the 2,2,4-trimethylpentylene radical, nonylene radicals, such as n -Nonyl radical, decyl radicals, such as the n-decylene radical, dodecylene radicals, such as the n-dodecylene radical; Alkenylene radicals, such as the vinylene and allylene radicals; Cycloalkylene radicals, such as cyclopentylene, cyclohexylene, cycloheptylene radicals and methylcyclohexylene radicals; Arylene radicals, such as the phenylene and the naphthylene radical; Alkarylene radicals, such as o-, m-, p-tolylene radicals, xylylene radicals and ethylphenylene radicals; Aral kylenreste, such as the benzylene radical, the CC and the ß-Phenylethy- lenrest and the 4, 4 '-Methylendiphenylenrest.
Bevorzugt handelt es sich bei Rest Z um Alkylengruppen mit 1 bis 24 Kohlenstoffatomen, besonders bevorzugt um Hexylen-,Radical Z is preferably alkylene groups having 1 to 24 carbon atoms, more preferably hexylene,
4 , 4 ' -Methylen-biscyclohexylen- und 3-Methylen-3, 5, 5-trimethyl- cyclohexylenrest .4, 4 '-Methylen-biscyclohexylen- and 3-methylene-3, 5, 5-trimethylcyclohexylene.
Beispiele für die zweiwertigen Reste G sind die für Z aufge- führten Beispiele. Bevorzugt handelt es sich bei Rest G um Al- kylenreste mit 1 bis 6 Kohlenstoffatomen, Arylenreste, wie der o- , m-, oder p-Phenylenrest und Aralkylenreste wie der Phe- nethylenrest, wobei Rest -CH2CH2- besonders bevorzugt ist.Examples of the bivalent radicals G are the examples listed for Z. Radicals G are preferably alkylene radicals having 1 to 6 carbon atoms, arylene radicals, such as the o-, m- or p-phenylene radical, and aralkylene radicals, such as the phenylene radical, with the radical -CH 2 CH 2 - being particularly preferred ,
Beispiele für Zλ sind alle für Z angegebenen Beispiele. Bevorzugt handelt es sich bei Rest Zλ um Alkylengruppen mit 1 bis 24 Kohlenstoffatomen, besonders bevorzugt um Alkylengruppen mit 1 oder 3 Kohlenstoffatomen .Examples of Z λ are all examples given for Z. Preferably it is at rest Z λ alkylene groups having 1 to 24 carbon atoms, more preferably alkylene groups having 1 or 3 carbon atoms.
Beispiele für Y sind alle für Z angegebenen Beispiele. Bei Rest Y handelt es sich bevorzugt um Alkylenreste mit 1 bis 30 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können, oder um Arylenreste mit 6 bis 22 Kohlenstoffatomen . Besonders bevorzugt han- delt es sich bei Rest Y um Alkylengruppen mit 1 bis 3 Kohlenstoffatomen, insbesondere um den Methylen- oder Propylenrest .Examples of Y are all examples given for Z. The radicals Y are preferably alkylene radicals having 1 to 30 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O-, or arylene radicals having 6 to 22 carbon atoms. Particularly preferred radical Y is alkylene groups having 1 to 3 carbon atoms, in particular the methylene or propylene radical.
Beispiele für Rest X sind der Butylenrest, Ethylenrest, Hexy- lenrest, - (CH2) 3- (O-CH (CH3) -CH2) 2_3ooo-0- (CH2) 3-, -CH (CH3) -CH2- (O- CH(CH3) -CH2) 2-3Ooo-, - (CH2) 3- (0-CH2-CH2) 2_300-O- (CH2) 3- und -CH2-CH2- (OCH2-CH2) 2-300- • Bei Rest X handelt es sich bevorzugt um Polyetherreste, besonders bevorzugt um Polypropylenglykolreste, insbesondere um solche mit 2 bis 600 Kohlenstoffatomen .Examples of radical X are the butylene radical, ethylene radical, hexylene radical, - (CH 2 ) 3 - (O-CH (CH 3 ) -CH 2 ) 2 - 3 ooo-O- (CH 2 ) 3 -, -CH ( CH 3) -CH 2 - (O-CH (CH 3) -CH 2) 2 - 3O oo-, - (CH 2) 3 - (0-CH 2 -CH 2) 2 _ 300 -O- (CH 2 ) 3 - and -CH 2 -CH 2 - (OCH 2 -CH 2 ) 2-300- • The radicals X are preferably polyether radicals, particularly preferably polypropylene glycol radicals, in particular those having 2 to 600 carbon atoms.
Beispiele für Rest R sind Alkylreste, wie der Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, tert . -Butyl-, n- Pentyl-, iso-Pentyl-, neo-Pentyl-, tert . -Pentylrest, Hexylres- te, wie der n-Hexylrest, Heptylreste, wie der n-Heptylrest, Oc- tylreste, wie der n-Octylrest und iso-Octylreste, wie der 2, 2, 4-Trimethylpentylrest, Nonylreste, wie der n-Nonylrest, De- cylreste, wie der n-Decylrest, Dodecylreste, wie der n-Dodecyl- rest; Alkenylreste, wie der Vinyl- und der Allylrest; Cycloal- kylreste, wie Cyclopentyl-, Cyclohexyl-, Cycloheptylreste und Methylcyclohexylreste; Arylreste, wie der Phenyl- und der Naphthylrest ; Alkarylreste, wie o-, m-, p-Tolylreste, Xylyl- reste und Ethylphenylreste; Aralkylreste, wie der Benzylrest, der CC- und der ß-Phenylethylrest .Examples of radical R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentyl, hexyl, such as the n-hexyl, heptyl, such as the n-heptyl, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2, 2, 4-trimethylpentyl, nonyl, such as the n Nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical; Alkenyl radicals, such as the vinyl and allyl radicals; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl and the naphthyl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; Aralkyl radicals, such as the benzyl radical, the CC and the ß-phenylethyl radical.
Bevorzugt handelt es sich bei Rest R um einen Kohlenwasser- Stoffrest mit 1 bis 6 Kohlenstoffatomen, besonders bevorzugt um einen Alkylrest mit 1 bis 4 Kohlenstoffatomen, insbesondere um den Methylrest.Radical R is preferably a hydrocarbon radical having 1 to 6 carbon atoms, more preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl radical.
Beispiele für Rest R1 sind die für Rest R angegebene Beispiele sowie Alkoxyalkylreste .Examples of radical R 1 are the examples given for radical R and alkoxyalkyl radicals.
Bevorzugt handelt es sich bei Rest R1 um lineare oder verzweigte Alkylreste mit 1 bis 12 Kohlenstoffatomen und Alkoxyalkylreste wie der 2-Methoxyethyl-, 2-Ethoxyethyl- und 2- (2' Methoxy- ethyl) ethylrest, besonders bevorzugt um Alkylreste mit 1 bis 12 Kohlenstoffatomen, insbesondere um den Methyl- und Ethylrest. Beispiele für Rest R4 sind die für R angegebenen Reste, Wasserstoffatom sowie die Reste - (CH2) 4Si (OCH3) 3,Radicals R 1 are preferably linear or branched alkyl radicals having 1 to 12 carbon atoms and alkoxyalkyl radicals such as 2-methoxyethyl, 2-ethoxyethyl and 2- (2'-methoxyethyl) ethyl, particularly preferably alkyl radicals 1 to 12 carbon atoms, in particular the methyl and ethyl radical. Examples of radical R 4 are the radicals specified for R, hydrogen atom and the radicals - (CH 2 ) 4 Si (OCH 3 ) 3 ,
- (CH2CH (CH3) CH2) Si (OCH3) 3, - (CH2CH (CH3) CH2) Si (OCH2CH3) 3,- (CH 2 CH (CH 3 ) CH 2 ) Si (OCH 3 ) 3 , - (CH 2 CH (CH 3 ) CH 2 ) Si (OCH 2 CH 3 ) 3 ,
- (CH2CH (CH3) CH2) SiCH3 (OCH3) 2, - (CH2CH (CH3) CH2) SiCH3 (OCH2CH3) 3, - (CH2) 3Si (OCH3) 3, - (CH2) 3Si (OCH2CH3) 3, - (CH2) 3SiCH3 (OCH3) 2,- (CH 2 CH (CH 3 ) CH 2 ) SiCH 3 (OCH 3 ) 2 , - (CH 2 CH (CH 3 ) CH 2 ) SiCH 3 (OCH 2 CH 3 ) 3 , - (CH 2 ) 3 Si ( OCH 3 ) 3 , - (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , - (CH 2 ) 3 SiCH 3 (OCH 3 ) 2 ,
- (CH2) 3SiCH3 (OCH2CH3)2, -CH2Si (OCH3) 3, -CH2Si (OCH2CH3) 3, -CH2SiCH3 (OCH3) 2, -CH2SiCH3 (OCH3) 2, - (CH2) 3SiCH3 (OCH2CH2OCH3) 2 und -C6H4- (CH2) 2SiCH3 (OCH2CH3) 2.- (CH 2 ) 3 SiCH 3 (OCH 2 CH 3 ) 2 , -CH 2 Si (OCH 3 ) 3 , -CH 2 Si (OCH 2 CH 3 ) 3 , -CH 2 SiCH 3 (OCH 3 ) 2 , - CH 2 SiCH 3 (OCH 3 ) 2 , - (CH 2 ) 3 SiCH 3 (OCH 2 CH 2 OCH 3 ) 2 and -C 6 H 4 - (CH 2 ) 2 SiCH 3 (OCH 2 CH 3 ) 2 .
Bevorzugt handelt es sich bei Rest R4 um Wasserstoffatom und die zuvor angegebenen silylsubstituierten Alkylreste, besonders bevorzugt um Wasserstoffatom und die Reste - (CH2) 3Si (OCH3) 3,Radical R 4 is preferably hydrogen and the abovementioned silyl-substituted alkyl radicals, more preferably hydrogen and the radicals - (CH 2 ) 3 Si (OCH 3 ) 3 ,
- (CH2) 3Si (OCH2CH3) 3, - (CH2) 3SiCH3 (OCH3) 2, - (CH2) 3SiCH3 (OCH2CH3) 2, -CH2Si(OCH3)3, -CH2Si(OCH2CH3)3, -CH2SiCH3 (OCH3) 2 sowie -CH2SiCH3 (OCH3) 2.- (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 , - (CH 2 ) 3 SiCH 3 (OCH 3 ) 2 , - (CH 2 ) 3 SiCH 3 (OCH 2 CH 3 ) 2 , -CH 2 Si ( OCH 3 ) 3 , -CH 2 Si (OCH 2 CH 3 ) 3 , -CH 2 SiCH 3 (OCH 3 ) 2 and -CH 2 SiCH 3 (OCH 3 ) 2 .
Beispiele für Kohlenwasserstoffreste D sind die für R oben angegebenen Reste.Examples of hydrocarbon radicals D are the radicals given above for R.
Bei Rest D handelt es sich bevorzugt um einen Alkylrest oder Wasserstoffatom, besonders bevorzugt um einen Alkylrest mit 1 bis 12 Kohlenstoffatomen oder Wasserstoffatom, insbesondere um Wasserstoffatom.The radical D is preferably an alkyl radical or hydrogen atom, particularly preferably an alkyl radical having 1 to 12 carbon atoms or hydrogen atom, in particular hydrogen atom.
Bei Rest E handelt es sich bevorzugt um Sauerstoffatom.The radical E is preferably an oxygen atom.
Bevorzugt hat a die Bedeutung einer ganzen Zahl von 1 bis 1000, besonders bevorzugt von 5 bis 1000, insbesondere 5 bis 100.A preferably has the meaning of an integer from 1 to 1000, particularly preferably from 5 to 1000, in particular from 5 to 100.
Bevorzugt hat b die Bedeutung einer ganzen Zahl von 1 bis 1000, besonders bevorzugt von 5 bis 1000, insbesondere 5 bis 100. Bevorzugt hat c die Bedeutung von 0 oder einer ganzen Zahl von 1 bis 100, besonders bevorzugt von 0 oder einer ganzen Zahl von 1 bis 10, insbesondere 0.B preferably has the meaning of an integer from 1 to 1000, particularly preferably from 5 to 1000, in particular from 5 to 100. Preferably c has the meaning of 0 or an integer of 1 to 100, more preferably of 0 or an integer of 1 to 10, especially 0.
Bevorzugt hat h die Bedeutung von einer ganzen Zahl von 1 bis 4, besonders bevorzugt von 1 bis 2, insbesondere 1.H has the meaning of an integer from 1 to 4, particularly preferably from 1 to 2, in particular 1.
Beispiele für Reste R' sind, für den Fall dass R' ' gleich Wasserstoffatom ist, Reste, die sich von den nicht umgesetzten Endgruppen aus den eingesetzten Edukten ergeben, wie H2N- (CH2) 3-Si (CH3) 2- (O-Si (CH3) 2) 40-O-Si (CH3) 2- (CH2) 3-NH-, H2N-CH2-CH2-N- (CH2) 3Si (OCH3) 3,Examples of radicals R ', in the case where R "is hydrogen, are radicals which result from the unreacted end groups from the educts used, such as H 2 N- (CH 2 ) 3-Si (CH 3 ) 2 - (O-Si (CH 3 ) 2 ) 40 -O-Si (CH 3 ) 2 - (CH 2 ) 3 -NH-, H 2 N-CH 2 -CH 2 -N- (CH 2 ) 3 Si ( OCH 3 ) 3 ,
und HO-(CH2CH(CH3)O)5O-.and HO- (CH 2 CH (CH 3 ) O) 5 O-.
Beispiele für Reste R' sind, für den Fall dass R' ' gleich -CO-NH-(Z-NH-CO-NHJh-Z-NCO ist, Reste, die sich von den nicht umgesetzten Endgruppen aus den eingesetzten Edukten ergeben, wie OCN-{ (CH2) 6-NH-CO-HNj2- (CH2) 3-Si (CH3) 2- (O-Si (CH3) 2) 4o-0-Si (CH3) 2- (CH2) 3-NH-, OCN-(C6H1O-CH2-C6H10-NH-CO-HNh-CH2-CH2-N- (CH2) 3Si(OCH3) 3,Examples of radicals R ', in the event that R "is equal to -CO-NH- (Z-NH-CO-NHJh-Z-NCO, radicals which arise from the unreacted end groups from the starting materials used, such as OCN- {(CH 2 ) 6 -NH-CO-HNj 2 - (CH 2 ) 3 -Si (CH 3 ) 2 - (O-Si (CH 3 ) 2 ) 4 o-O-Si (CH 3 ) 2 - (CH 2) 3 -NH-, OCN- (C 6 H 1O -CH 2 -C 6 H 10 -NH-CO-HNH-CH 2 -CH 2 -N- (CH 2) 3 Si (OCH 3) 3 ,
und OCN-C6H3 ( CH3 ) -NH-CO-NH-C6H3 ( CH3 ) -NH-CO-O- ( CH2CH ( CH3 ) O ) 50 - .and OCN-C 6 H 3 (CH 3) -NH-CO-NH-C 6 H 3 (CH 3) -NH-CO-O- (CH 2 CH (CH 3) O) 50 -.
Bei Rest R' handelt es sich im Fall von R' ' gleich Wasserstoffatom bevorzugt um einen Rest HND-Y-Si (OR1) 0R2-0- (0-SiR2) n-O- Si (OR1J0R2-O-Y-ND- oder HNR4-G-NR4- und im Fall von R'' gleich -CO-NH-(Z-NH-CO-NHJh-Z-NCO bevorzugt um OCN-(Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR1J0R2-O- (0-SiR2) n-0-Si (OR1J0R2- o-Y-ND- oder OCN- { Z-NH-CO-NH}h-Z-NH-CO-NR4-G-NR4- . Beispiele für Reste R'' sind Wasserstoffatom, -CO-NH- (CH2) 6-NH- CO-NH- (CH2) 6-NCO, -CO-NH-C6H1O-CH2-C6H10-NCO und -CO-NH-C6H3(CH3)- NCO, wobei Wasserstoffatom bevorzugt ist.The radical R 'is in the case of R''is a hydrogen atom preferably a radical HND-Y-Si (OR 1) 0 R 2 - 0 - (0-SiR 2) n -O- Si (OR 1 J 0 R 2 - O -Y-ND- or HNR 4 -G-NR 4 - and in the case of R ", equal -CO-NH- (Z-NH-CO-NHJh-Z-NCO, preferably at OCN- (Z-) NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1 J 0 R 2 - O - (0-SiR 2) n -0-Si (OR 1 J 0 R 2 - o -Y ND or OCN- {Z-NH-CO-NH} h -Z-NH-CO-NR 4 -G-NR 4 -. Examples of radicals R "are hydrogen atom, -CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NCO, -CO-NH-C 6 H 1 O -CH 2 -C 6 H 10 -NCO and -CO-NH-C 6 H 3 (CH 3 ) -NCO, with hydrogen being preferred.
Bevorzugt ist n eine ganze Zahl von 10 bis 4000, besonders bevorzugt 30 bis 1000.N is preferably an integer from 10 to 4000, more preferably from 30 to 1000.
Index p ist bevorzugt 0.Index p is preferably 0.
Index o ist bevorzugt 0.Index o is preferably 0.
Erfindungsgemäße Copolymere enthaltend Einheiten (C) können ein härteres Material ergeben im Vergleich zu erfindungsgemäßen Co- polymeren, die keine Einheit (C) enthalten, da in ihnen mehr Wasserstoffbrücken vorliegen. Polyetherbausteine als Einheiten (C) können, wie z.B. in US 20060014916 A beschrieben, verwendet werden um die Verarbeitungstemperaturen des Materials unterhalb der Zersetzungstemperaturen des Materials zu halten, falls dies nötig ist.Copolymers of the invention comprising units (C) can give a harder material compared to copolymers according to the invention which contain no unit (C), since there are more hydrogen bonds in them. Polyether units as units (C) can be used, e.g. in US 20060014916 A can be used to keep the processing temperatures of the material below the decomposition temperatures of the material, if necessary.
Je nach der Anzahl der Einheiten (C) in den erfindungsgemäßen Copolymeren können die Eigenschaften, wie beispielsweise Schäl- und Ablösefestigkeit, Bedruckbarkeit, Zug- und Durchreißfestigkeit oder Wasserdampfdurchlässigkeit, gezielt eingestellt wer- den.Depending on the number of units (C) in the copolymers according to the invention, the properties, such as, for example, peel and peel strength, printability, tensile and tear propagation resistance or water vapor permeability, can be set in a targeted manner.
Bevorzugt sind Copolymere der Formel (I) mit c gleich 0, da somit ausschließlich Siloxanketten vorliegen und dadurch die Polymere Vorteile, wie beispielsweise hohe Transparenz und UV- Stabilität bei gleichzeitig niedrigen Oberflächenenergien, aufweisen .Copolymers of the formula (I) with c are preferably 0, since thus exclusively siloxane chains are present and thus the polymers have advantages such as, for example, high transparency and UV stability with simultaneously low surface energies.
Beispiele für erfindungsgemäße Copolymere der Formel (I) sind H [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH-CO-NH-CH2CH2-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH-CO] 10- NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2,Examples of copolymers of the formula (I) according to the invention are H [NH (CH 2) 3SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH2) 3-NH-CO-NH- (CH 2) 6 -NH-CO-NH- (CH 2) 6 -NH-CO -NH-CH 2 CH 2 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH-CO] 10 -NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O 35SiMe 2 (CH 2 ) 3-NH 2 ,
H [NH (CH2) 3Si (OMe) 20 (SiMe2O) 35Si (OMe) 2 (CH2) 3-NH-CO-NH- (CH2) 6-NH-CO- NH- (CH2) 6-NH-CO-NH-CH2CH2-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH- CO] 10-NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2,H [NH (CH 2 ) 3 Si (OMe) 2 O (SiMe 2 O) 35 Si (OMe) 2 (CH 2 ) 3 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- ( CH 2 ) 6 -NH-CO-NH-CH 2 CH 2 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH-CO] 1 O-NH (CH 2 ) 3SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3-NH 2 ,
H [ [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH-CO- ] 5- [NH-CH2CH2-NH-CO-NH- (CH2) 6-NH-CO] 5] I0-NH-CH2CH2- NH2,H [[NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6- NH-CO-] 5- [NH-CH 2 CH 2 -NH-CO-NH- (CH 2) 6 -NH-CO] 5] I0 -NH-CH 2 CH 2 - NH 2,
H [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH-CO-NH-CH2CH2-NH-CO-NH-- (CH2) 6-NH-CO-NH (CH2) 6-NH-CO-O- (CH2CH2O) 5-CO-NH- (CH2) 6-NH-CO] I0-NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3 -NH2,H [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH -CO-NH-CH 2 CH 2 -NH-CO-NH-- (CH 2 ) 6 -NH-CO-NH (CH 2 ) 6 -NH-CO-O- (CH 2 CH 2 O) 5-CO -NH- (CH 2 ) 6 -NH-CO] 10 -NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 -NH 2 ,
H [NH-CH2-SiMe2O (SiMe2O) 35SiMe2-CH2-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6- NH-CO-NH-CH2CH2-NH-CO-NH-- (CH2) 6-NH-CO-NH (CH2) 6-NH-CO-NH- (CH2CH2O) 5-CH2CH2-NH-CO-NH- (CH2) 6-NH-CO] I0-CH2-SiMe2O (SiMe2O) 35 SiMe2-CH2-NH2,H [NH-CH 2 -SiMe 2 O (SiMe 2 O) 35 SiMe 2 -CH 2 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH-CO- NH-CH 2 CH 2 -NH-CO-NH-- (CH 2 ) 6 -NH-CO-NH (CH 2 ) 6 -NH-CO-NH- (CH 2 CH 2 O) 5-CH 2 CH 2 -NH-CO-NH- (CH 2 ) 6 -NH-CO] 10 -CH 2 -SiMe 2 O (SiMe 2 O) 35 SiMe 2 -CH 2 -NH 2 ,
H [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH-CO-NH-CI0H20-NH-CO-NH- CI0H20-NH-CO-NH-CH2CH2-NH-CO-NH-CI0H20-NH-CO-NH-CI0H20-NH-CO] i0- NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2,H [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 -NH-CO-NH-C 10 H 20 -NH-CO-NH-C 10 H 20 -NH-CO -NH-CH 2 CH 2 -NH-CO-NH-C 10 H 20 -NH-CO-NH-C 10 H 20 -NH-CO] i0 -NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 -NH 2 ,
OCN-C7H6-NH-CO-NH-C7H6-NH-CO- [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3- NH-CO-NH-C7H6-NH-CO-NH-C7H6-NH-CO-NH-CH2CH2-NH-CO-NH-C7H6-NH-CO- NH-C7H6-NH-CO] I0-NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH-CO-NH-C7H6- NH-CO-NH-C7H6-NCO und OCN-C7H6-NH-CO-NH-C7H6-NH-CO- [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3- NH-CO-NH-C7H6-NH-CO-NH-C7H6-NH-CO-NH-CH2CH2-NH-CO-NH-C7H6-NH-CO- NH-C7H6-NH-CO] !0-NH-CH2CH2-NH-CO-NH-C7H6-NH-CO-NH-C7H6-NCO.OCN-C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO- [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH 2 ) 3 - NH-CO-NH- C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO-NH-CH 2 CH 2 -NH-CO-NH-C 7 H 6 -NH-CO-NH-C 7 H 6 -NH -CO] I0 -NH (CH 2) 3SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH2) 3-NH-CO-NH-C 7 H 6 - NH-CO-NH-C 7 H 6 -NCO and OCN-C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO- [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH 2 ) 3 - NH-CO-NH- C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO-NH-CH 2 CH 2 -NH-CO-NH-C 7 H 6 -NH-CO-NH-C 7 H 6 -NH -CO] ! 0 -NH-CH 2 CH 2 -NH-CO-NH-C 7 H 6 -NH-CO-NH-C 7 H 6 -NCO.
H [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH-CO-NH-CH2CH2-N{ (CH2) 3-Si (OMe) 3 } -CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH-CO] 10-NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2,H [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH -CO-NH-CH 2 CH 2 -N {(CH 2 ) 3 -Si (OMe) 3 } -CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH-CO ] 1 0-NH (CH 2) 3SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH 2) 3 NH 2,
H [NH (CH2) 3Si (OMe) 20 (SiMe2O) 35Si (OMe) 2 (CH2) 3-NH-CO-NH- (CH2) 6-NH-CO- NH- (CH2) 6-NH-CO-NH-CH2CH2-N{ (CH2) 3-SiMe (OMe) 2 } -CO-NH- (CH2) 6-NH-CO- NH- (CH2) 6-NH-CO] 10-NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2,H [NH (CH 2 ) 3 Si (OMe) 2 O (SiMe 2 O) 35 Si (OMe) 2 (CH 2 ) 3 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- ( CH 2 ) 6 -NH-CO-NH-CH 2 CH 2 -N {(CH 2 ) 3 -SiMe (OMe) 2 } -CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6-NH-CO] 1 O-NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3-NH 2 ,
H [ [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH-CO- ] 5- [NH-CH2CH2-N{ (CH2) 3-Si (OEt ) 3 } -CO-NH- (CH2) 6-NH- CO] 5] io-NH-CH2CH2-N{ (CH2) 3-Si (OEt)3)H,H [[NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6- NH-CO-] 5- [NH-CH 2 CH 2 -N {(CH 2 ) 3 -Si (OEt) 3} -CO-NH- (CH 2 ) 6 -NH-CO] 5 ] io-NH- CH 2 CH 2 -N {(CH 2 ) 3 -Si (OEt) 3 ) H,
H [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6-NH-CO-NH-CH2CH2-N{ (CH2) 3-Si (OMe) 3 } -CO-NH-- (CH2) 6-NH-CO- NH (CH2) 6-NH-CO-O- (CH2CH2O) 5-CO-NH- (CH2) 6-NH-CO] I0-NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2,H [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH -CO-NH-CH 2 CH 2 -N {(CH 2 ) 3 -Si (OMe) 3} -CO-NH-- (CH 2 ) 6 -NH-CO-NH (CH 2 ) 6 -NH-CO -O- (CH 2 CH 2 O) 5-CO-NH- (CH 2 ) 6 -NH-CO] 10 -NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 - NH 2 ,
H [NH-CH2-SiMe2O (SiMe2O) 35SiMe2-CH2-NH-CO-NH- (CH2) 6-NH-CO-NH- (CH2) 6- NH-CO-NH-CH2CH2-N{ (CH2) 3-Si (OMe) 3 } -CO-NH- (CH2) 6-NH-CO-NH (CH2) 6-NH- CO-NH- (CH2CH2O) 5-CH2CH2-NH-CO-NH- (CH2) 6-NH-CO] I0-CH2-SiMe2O (SiMe2O)3SSiMe2-CH2-NH2,H [NH-CH 2 -SiMe 2 O (SiMe 2 O) 35 SiMe 2 -CH 2 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH-CO- NH-CH 2 CH 2 -N {(CH 2 ) 3 -Si (OMe) 3 } -CO-NH- (CH 2 ) 6 -NH-CO-NH (CH 2 ) 6 -NH-CO-NH- CH 2 CH 2 O) 5-CH 2 CH 2 -NH-CO-NH- (CH 2 ) 6 -NH-CO] 10 -CH 2 -SiMe 2 O (SiMe 2 O) 3S SiMe 2 -CH 2 -NH 2 ,
H [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) S-NH-CO-NH-CI0H20-NH-CO-NH- Ci0H20-NH-CO-NH-CH2CH2-N(CH2-SiMe (OEt)2I-CO-NH-Ci0H20-NH-CO-NH- Ci0H20-NH-CO] I0-NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2,H [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) S -NH-CO-NH-C 10 H 20 -NH-CO-NH-Ci 0 H 20 -NH-CO -NH-CH 2 CH 2 -N (CH 2 -SiMe (OEt) 2 I-CO-NH-Ci 0 H 20 -NH-CO-NH-Ci 0 H 20 -NH-CO] I0 -NH (CH 2 ) 3SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH 2 ) 3-NH 2 ,
OCN-C7H6-NH-CO-NH-C7H6-NH-CO- [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3- NH-CO-NH-C7H6-NH-CO-NH-C7H6-NH-CO-NH-CH2CH2-N{ (CH2) 3-Si (OMe)3J-CO- NH-C7H6-NH-CO-NH-C7H6-NH-CO] I0-NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3- NH-CO-NH-C7H6-NH-CO-NH-C7H6-NCO und OCN-C7H6-NH-CO-NH-C7H6-NH-CO- [NH (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3- NH-CO-NH-C7H6-NH-CO-NH-C7H6-NH-CO-NH-CH2CH2-N{ (CH2) 3-Si (OMe)3J-CO- NH-C7H6-NH-CO-NH-C7H6-NH-CO] IO-NH-CH2CH2-N{ (CH2) 3-Si (OMe) 3} -CO-NH- C7H6-NH-CO-NH-C7H6-NCO, wobei Me gleich Methylrest und Et gleich Ethylrest bedeutet.OCN-C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO- [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH 2 ) 3 - NH-CO-NH- C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO-NH-CH 2 CH 2 -N {(CH 2 ) 3 -Si (OMe) 3 J-CO-NH-C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO] 10 -NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3 - NH-CO-NH-C 7 H 6 - NH-CO-NH-C 7 H 6 -NCO and OCN-C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO- [NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH 2 ) 3 - NH-CO-NH- C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO-NH-CH 2 CH 2 -N {(CH 2 ) 3 -Si (OMe) 3 J-CO-NH-C 7 H 6 -NH-CO-NH-C 7 H 6 -NH-CO] IO -NH-CH 2 CH 2 -N {(CH 2 ) 3 -Si (OMe) 3 } -CO-NH- C 7 H 6 -NH -CO-NH-C 7 H 6 -NCO, where Me is methyl and Et is ethyl.
Die erfindungsgemäßen Copolymere der Formel (I) haben einen Gehalt an Einheiten A der Formel (II) von bevorzugt größer 70 Gew.-%, besonders bevorzugt größer 80 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Copolymers.The copolymers of the formula (I) according to the invention have a content of units A of the formula (II) of preferably greater than 70% by weight, particularly preferably greater than 80% by weight, in each case based on the total weight of the copolymer.
Die erfindungsgemäßen Copolymere der Formel (I) sind bei Raumtemperatur bevorzugt gummielastische Festkörper mit Zugfestig- keiten zwischen vorzugsweise etwa 0,5 und 20 MPa sowie Reißdehnungen zwischen bevorzugt etwa 50 bis 1000 %. Sie erweichen bei Temperaturen zwischen bevorzugt 60 und 2400C und verlieren dabei ihre gummielastischen Eigenschaften. Durch Einwirkung von Feuchtigkeit können, falls vorhanden, die hydrolysierbaren Res- te -OR1 zu OH-Gruppen reagieren, die ihrerseits wiederum mit weiteren OR1- oder OH-Gruppen unter Bildung von Siloxanbindun- gen kondensieren können.The novel copolymers of the formula (I) are preferably rubber-elastic solids at room temperature with tensile strengths of preferably between about 0.5 and 20 MPa and elongation at break of between about 50 and 1000%. They soften at temperatures between preferably 60 and 240 0 C and thereby lose their rubber-elastic properties. By the action of moisture, if present, the hydrolyzable radical -OR 1 can react to form OH groups, which in turn can condense with further OR 1 or OH groups to form siloxane bonds.
Die erfindungsgemäßen Copolymere haben weiterhin den Vorteil, dass sie sehr gute mechanische Eigenschaften aufweisen, ohne dass Füllstoffe zugegeben werden müssen.The copolymers according to the invention also have the advantage that they have very good mechanical properties without having to add fillers.
Weiterhin zeichnen sich die erfindungsgemäßen Copolymere durch hervorragende physikalische Eigenschaften aus, wie sie von Po- lyorganosiloxanen bekannt sind, wie beispielsweise niedrigeFurthermore, the copolymers according to the invention are distinguished by excellent physical properties, as are known from polyorganosiloxanes, such as, for example, lower
Glasübergangstemperaturen, Transparenz, gute Beständigkeit gegenüber UV-Licht, geringe Oberflächenenergien, niedrige Hydro- phobizität, gute dielektrische Eigenschaften und hohe Permeabilität gegenüber Gasen.Glass transition temperatures, transparency, good resistance to UV light, low surface energies, low hydro- phobicity, good dielectric properties and high permeability to gases.
Weitere Vorteile der erfindungsgemäßen Copolymere sind die hohe thermische und oxidative Beständigkeit, gute Beständigkeiten gegenüber Quellung und Zersetzung durch Kohlenwasserstoffe enthaltende Lösemitteln.Further advantages of the copolymers according to the invention are the high thermal and oxidative stability, good resistance to swelling and decomposition by hydrocarbons containing solvents.
Ferner haben die erfindungsgemäßen Copolymere den Vorteil, dass sie einen deutlich verbesserten Druckverformungsrest haben.Furthermore, the copolymers of the invention have the advantage that they have a significantly improved compression set.
Die Herstellung der erfindungsgemäßen Copolymere kann analog beliebiger Verfahren erfolgen, die dem Fachmann bereits bekannt sind und beispielsweise zur Synthese von (Prä) polymeren für Po- lyurethane eingesetzt werden, erfolgen.The copolymers according to the invention can be prepared analogously to any process which is already known to the person skilled in the art and is carried out, for example, for the synthesis of (prep) polymers for polyurethanes.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Copolymere der Formel (I) durch Umsetzung vonAnother object of the present invention is a process for the preparation of the copolymers of the formula (I) according to the invention by reacting
(a) mindestens einem Polymer der Formel(a) at least one polymer of the formula
H-ND-Y-Si (OR1) 0R2-0- (0-SiR2) n-O-Si (OR1) OR2-O-Y-ND-H (V) ,H-ND-Y-Si (OR 1) 0R2-0- (0-SiR 2) n -O-Si (OR 1) 2 O R - O -Y-ND-H (V)
(b) mindestens einem Diisocyanat der Formel(B) at least one diisocyanate of the formula
OCN- { Z-NH-CO-NH}h. Z-NCO (VII),OCN- {Z-NH-CO-NH} h . Z-NCO (VII),
(c) gegebenenfalls einer Verbindung der Formel(c) optionally a compound of the formula
H-NR4-G-NR4-H (VI),H-NR 4 -G-NR 4 -H (VI),
(d) gegebenenfalls Verbindungen der Formel H-E-X-E-H (VIII)(d) optionally compounds of the formula HEXEH (VIII)
undand
(e) gegebenenfalls Diisocyanaten der Formel OCN-Z-NCO (IX) ,(e) optionally diisocyanates of the formula OCN-Z-NCO (IX),
wobei X, Y, Z, D, E, G, R, R1, R4, und o eine der oben genannten Bedeutungen aufweisen und h' eine ganze Zahl von mindestens 1 ist.wherein X, Y, Z, D, E, G, R, R 1 , R 4 , and o have one of the meanings mentioned above and h 'is an integer of at least 1.
Beispiele der erfindungsgemäß eingesetzten Verbindungen der Formel (V) sind CCCO-aminopropyldimethylsilylterminierte Polydi- methylsiloxane, CC,CO-aminopropyldimethoxysilylterminierte Polydi- methylsiloxane, CC,CO-aminomethyldimethylsilylterminierte Polydi- methylsiloxane und CC,CO-aminomethyldimethoxysilylterminierte Po- lydimethylsiloxane .Examples of the compounds of the formula (V) used in accordance with the invention are CCCO-aminopropyldimethylsilyl-terminated polydimethylsiloxanes, CC, CO-aminopropyldimethoxysilyl-terminated polydimethylsiloxanes, CC, CO-aminomethyldimethylsilyl-terminated polydimethylsiloxanes and CC, CO-aminomethyldimethoxysilyl-terminated polydimethylsiloxanes.
Bevorzugt handelt es sich bei den Verbindungen der Formel (V) um H2N (CH2) 3SiMe2O (SiMe2O) I2-I8SiMe2 (CH2) 3-NH2,It is preferable that in the compounds of formula (V) to H 2 N (CH 2) 3SiMe 2 O (SiMe 2 O) I2 - I8 SiMe 2 (CH 2) 3 NH 2,
H2N (CH2) 3Si (OMe) 20 (SiMe2O) I2-I8Si (OMe) 2 (CH2) 3-NH2,H 2 N (CH 2) 3 Si (OMe) 2 0 (SiMe 2 O) I2 - I8 Si (OMe) 2 (CH 2) 3 NH 2,
H2N (CH2) SiMe2O (SiMe2O) I2-I8SiMe2 (CH2) -NH2,H 2 N (CH 2) SiMe 2 O (SiMe 2 O) I2 - I8 SiMe 2 (CH 2) -NH 2,
H2N (CH2) Si (OMe) 20 (SiMe2O) I2-I8Si (OMe) 2 (CH2) -NH2, H2N (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2,H 2 N (CH 2) Si (OMe) 2 0 (SiMe 2 O) I2 - I8 Si (OMe) 2 (CH 2) -NH 2, H 2 N (CH 2) 3SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH 2 ) 3 -NH 2 ,
H2N (CH2) 3Si (OMe) 20 (SiMe2O) 35Si (OMe) 2 (CH2) 3-NH2,H 2 N (CH 2 ) 3 Si (OMe) 2 O (SiMe 2 O) 35 Si (OMe) 2 (CH 2 ) 3 NH 2 ,
H2N (CH2) SiMe2O (SiMe2O) 35SiMe2 (CH2) -NH2,H 2 N (CH 2 ) SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) -NH 2 ,
H2N (CH2) Si (OMe) 20 (SiMe2O) 35Si (OMe) 2 (CH2) -NH2,H 2 N (CH 2 ) Si (OMe) 2 O (SiMe 2 O) 35 Si (OMe) 2 (CH 2 ) -NH 2 ,
H2N (CH2) 3SiMe2O (SiMe2O) 130-160SiMe2 (CH2) 3-NH2, H2N (CH2) 3Si (OMe) 20 (SiMe2O) i3o-i6oSi (OMe) 2 (CH2) 3-NH2,H 2 N (CH 2) 3SiMe 2 O (SiMe 2 O) 1 30- 1 60SiMe 2 (CH 2) 3 NH 2, H 2 N (CH 2) 3 Si (OMe) 2 0 (SiMe 2 O) i 3 o-i6oSi (OMe) 2 (CH 2 ) 3-NH 2 ,
H2N (CH2) SiMe2O (SiMe2O) 130-160SiMe2 (CH2) -NH2 undH 2 N (CH 2 ) SiMe 2 O (SiMe 2 O) 1 30- 1 60SiMe 2 (CH 2 ) -NH 2 and
H2N (CH2) Si (OMe) 20 (SiMe2O) i3o-i6oSi (OMe) 2 (CH2) -NH2, wobeiH 2 N (CH 2 ) Si (OMe) 2 O (SiMe 2 O) i 3 o-i6oSi (OMe) 2 (CH 2 ) -NH 2 where
H2N (CH2) 3SiMe2O (SiMe2O) I2-I8SiMe2 (CH2) 3-NH2, H2N (CH2) SiMe2O (SiMe2O) I2-I8SiMe2 (CH2) -NH2, H2N (CH2) 3SiMe2O (SiMe2O) 35SiMe2 (CH2) 3-NH2, H2N (CH2) SiMe2O (SiMe2O) 35SiMe2 (CH2) -NH2, H2N (CH2) 3SiMe2O (SiMe2O) 130-160SiMe2 (CH2) 3-NH2 und H2N (CH2) SiMe2O (SiMe2O) i3o-iβoSiMe2 (CH2) -NH2, besonders bevorzugt sind, wobei Me gleich Methylrest bedeutet.H 2 N (CH 2) 3SiMe 2 O (SiMe 2 O) I2 - I8 SiMe 2 (CH 2) 3 NH 2, H 2 N (CH 2 ) SiMe 2 O (SiMe 2 O) I 2 -I 8 SiMe 2 (CH 2 ) -NH 2 , H 2 N (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) 3-NH 2 , H 2 N (CH 2 ) SiMe 2 O (SiMe 2 O) 35 SiMe 2 (CH 2 ) -NH 2 , H 2 N (CH 2 ) 3 SiMe 2 O (SiMe 2 O) 130-160 SiMe 2 (CH 2 ) 3-NH 2 and H 2 N (CH 2 ) SiMe 2 O (SiMe 2 O) i 3 o-iβoSiMe 2 (CH 2 ) -NH 2 , where Me is methyl.
Bevorzugte Verbindungen der Formel (VI) , die im erfindungsgemäßen Verfahren eingesetzt werden können, sind 3- (2-Amino- ethyl) aminopropyltrimethoxysilan, 3- (2-Aminoethyl) aminopropyl- triethoxysilan, 3- (2-Aminoethyl) aminopropylmethyldimethoxysi- lan, 3- (2-Aminoethyl) aminopropyldimethylmethoxysilan, 3- (2-Ami- noethyl) aminopropylmethyldiethoxysilan, N, N' -Bis- (3-trimethoxy- silylpropyl) -ethylendiamin, N, N' -Bis- (3-triethoxysilylpropyl) - ethylendiamin, N, N' -Bis- (3-dimethoxymethylsilylpropyl) ethylendiamin und N, N' -Bis- (3-diethoxymethylsilylpropyl) ethylendiamin, N-Trimethoxysilylmethylethylendiamin, N-Triethoxysilylmethyl- ethylendiamin, N-Dimethoxymethylsilylmethylethylendiamin, N-Di- ethoxymethylsilylmethylethylendiamin und N-Methoxydimethylsi- lylmethylethylendiamin, wobei 3- (2-Aminoethyl) aminopropyltrimethoxysilan, 3- (2-Aminoethyl) aminopropyltriethoxysilan, 3- (2- Aminoethyl) aminopropylmethyldimethoxysilan, 3- (2-Aminoethyl) - aminopropyldimethylmethoxysilan und 3- (2-Aminoethyl) aminopropylmethyldiethoxysilan besonders bevorzugt sind.Preferred compounds of the formula (VI) which can be used in the process according to the invention are 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyldimethylmethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, N, N'-bis (3-trimethoxysilylpropyl) ethylenediamine, N, N'-bis- (3-triethoxysilylpropyl) - ethylenediamine, N, N'-bis- (3-dimethoxymethylsilylpropyl) ethylenediamine and N, N'-bis (3-diethoxymethylsilylpropyl) ethylenediamine, N-trimethoxysilylmethylethylenediamine, N-triethoxysilylmethylethylenediamine, N-dimethoxymethylsilylmethylethylenediamine, N-diethoxymethylsilylmethylethylenediamine and N-methoxydimethylsilylmethylethylenediamine, whereby 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyldimethylmethoxysilane and 3- (2-aminoethyl) aminopropylmethyldiethoxysilane are particularly preferred.
Beispiele für die erfindungsgemäß eingesetzten Isocyanate der Formel (IX) sind Hexylendiisocyanat, 4, 4' -Methylendicyclohexy- lendiisocyanat, 4, 4' -Methylendiphenylendiisocyanat, 1,3-Diaze- tidine-2, 4-dion-bis (4,4' -methylendicyclohexyl) diisocyanat, 1, 3- Diazetidine-2 , 4-dion-bis (4,4' -methylendiphenyl) diisocyanat,Examples of the isocyanates of the formula (IX) used in accordance with the invention are hexylene diisocyanate, 4,4'-methylenedicyclohexyl-1-diisocyanate, 4,4'-methylenediphenylene diisocyanate, 1,3-diazotidine-2,4-dione bis (4,4 '). -methylenedicyclohexyl) diisocyanate, 1, 3-diazetidine-2,4-dione bis (4,4'-methylenediphenyl) diisocyanate,
Tetramethylenxylylendiisocyanat und Isophorondiisocyanat, wobei Hexylendiisocyanat, 4,4' -Methylendicyclohexylendiisocyanat, 4,4' -Methylendiphenylendiisocyanat, Tetramethylenxylylendiiso- cyanat und Isophorondiisocyanat bevorzugt sowie Hexylendiisocy- anat, 4, 4' -Methylendicyclohexylendiisocyanat und Isophorondiisocyanat besonders bevorzugt sind.Tetramethylenexylylene diisocyanate and isophorone diisocyanate, hexylene diisocyanate, 4,4'-methylenedicyclohexylene diisocyanate, 4,4'-methylenediphenylene diisocyanate, tetramethylenexylylene diisocyanate, cyanate and isophorone diisocyanate are preferred as well as Hexylendiisocy- anat, 4, 4 '-Methylendicyclohexylendiisocyanat and isophorone diisocyanate are particularly preferred.
Beispiele für die erfindungsgemäß eingesetzten Isocyanate der Formel (VII) sind OCN-Z-NH-CO-NH-Z-NCO, OCN-Z-NH-CO-NH-Z-NH-CO- NH-Z-NCO, mit Z gleich Hexylen-, 4, 4' -Methylendicyclohexylen-, 4, 4' -Methylendiphenylen-, Tetramethylenxylylen- und Isophorony- lenrest, wobei OCN-Z-NH-CO-NH-Z-NCO mit Z gleich Hexylen-, 4, 4' -Methylendicyclohexylen-, 4, 4' -Methylendiphenylen-, Tetramethylenxylylen- und Isophoronylenrest bevorzugt sowie OCN-Z- NH-CO-NH-Z-NCO mit Z gleich 4, 4' -Methylendicyclohexylen- und Isophoronylen besonders bevorzugt sind.Examples of the isocyanates of the formula (VII) used according to the invention are OCN-Z-NH-CO-NH-Z-NCO, OCN-Z-NH-CO-NH-Z-NH-CO-NH-Z-NCO, with Z is hexylene, 4, 4 '-methylenedicyclohexylene, 4, 4' -methylenediphenylene, tetramethylenxylylene and isophorone lenrest, wherein OCN-Z-NH-CO-NH-Z-NCO with Z is hexylene, 4, 4 'Methylenedicyclohexylen-, 4, 4' -Methylendiphenylen-, Tetramethylenxylylen- and Isophoronylenrest preferred and OCN-Z-NH-CO-NH-Z-NCO with Z equal to 4, 4 '-Methylendicyclohexylen- and isophoronylene are particularly preferred.
Die erfindungsgemäß eingesetzten Isocyanate der Formel (VII) können durch Umsetzung von Diisocyanaten der Formel (IX) und Wasser bevorzugt in Anwesenheit von Katalysatoren, wie z.B. N, N-dimethylethanolamin, Bis (2-dimethylaminoethyl) ether, N, N, N' ,N' ,N' ' -Pentamethyl-diethylen-triamin, N, N' -trimethyl- aminoethylethanolamin, Triethylenediamin, Dibutylzinndilaurat, Zinn ( II ) octoat sowie synergistische Mischungen aus Triethylenediamin und Dibutylzinndilaurat hergestellt werden oder in situ bei Durchführung des erfindungsgemäßen Verfahrens entstehen. Die zur Herstellung der Diisocyanate der Formel (VII) gegebe- nenfalls verwendeten Katalysatoren stören die erfindungsgemäße Umsetzung von (a) mit (b) und gegebenenfalls (c) , (d) und (e) nicht .The isocyanates of the formula (VII) used according to the invention can be prepared by reacting diisocyanates of the formula (IX) and water, preferably in the presence of catalysts, such as, for example, N, N-dimethylethanolamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N', N'-pentamethyldiethylenetriamine, N, N'-trimethylaminoethylethanolamine, triethylenediamine, dibutyltin dilaurate, tin (II ) octoate and synergistic mixtures of triethylenediamine and dibutyltin dilaurate are prepared or formed in situ in carrying out the method according to the invention. The catalysts used to prepare the diisocyanates of the formula (VII) do not interfere with the reaction according to the invention of (a) with (b) and optionally (c), (d) and (e).
Die Isocyanate der Formeln (VII) und/oder (IX) können jeweils ganz oder zum Teil in Form der entsprechenden blockierten Diisocyanate vorliegen, was jedoch nicht bevorzugt ist. Es kann sich dabei insbesondere um thermisch instabile Umsetzungsprodukte von Isocyanaten mit zum Beispiel Phenolen, Ketoximen, Ma- lonestern und stickstoffhaltigen Heterocyclen handeln, die dem Fachmann bekannt sind. Bei der Umsetzung der blockierten Isocy- anate mit den anderen Edukten muss dann die nötige Temperatur zur Entblockierung erreicht werden, wobei die dann freigeworde- ne Blockierungsmoleküle im Reaktionsgemisch verbleiben.The isocyanates of formulas (VII) and / or (IX) may each be wholly or partly in the form of the corresponding blocked diisocyanates, but this is not preferred. These may be, in particular, thermally unstable reaction products of isocyanates with, for example, phenols, ketoximes, lonestern and nitrogen-containing heterocycles, which are known in the art. In the reaction of the blocked isocyanate with the other educts then the necessary temperature for deblocking must be achieved, the then freed blocking molecules remain in the reaction mixture.
Beispiele der erfindungsgemäß eingesetzten Verbindungen der Formel (VIII) sind aus der Polyurethanchemie bekannte Verbindungen wie Diole, wie z.B. Ethylenglycol, 1, 4-Butandiol, Polyethy- lenglycole, Polypropylenglycole und Polyesterpolyole, Diamine, wie z.B. Ethylendiamin, 2-Methyl-l, 5-pentandiamin, 5-Amino-3- (aminomethyl) -1, 3, 3-trimethylcyclohexan, Bis (4-amino-3-methyl- phenyl) methan, Isomerengemisch des Diaminodiethylmethylbenzols, Bis (4-amino-3-chlorphenyl) methan und 2-Methylpropyl-4-chlor- 3, 5-diaminobenzoat, und aminoterminierte Polyether (ATPE) .Examples of the compounds of the formula (VIII) used according to the invention are compounds known from polyurethane chemistry, such as diols, e.g. Ethylene glycol, 1,4-butanediol, polyethylene glycols, polypropylene glycols and polyester polyols, diamines, e.g. Ethylenediamine, 2-methyl-l, 5-pentanediamine, 5-amino-3- (aminomethyl) -1,3,3-trimethylcyclohexane, bis (4-amino-3-methylphenyl) methane, mixture of isomers of diaminodiethylmethylbenzene, bis ( 4-amino-3-chlorophenyl) methane and 2-methylpropyl-4-chloro-3,5-diaminobenzoate, and amino-terminated polyethers (ATPE).
Bevorzugt handelt es sich bei den Verbindungen der Formel (VIII) um 1 , 4-Butandiol , Polyethylenglycole, Polypropylenglycole, 2-Methyl-l, 5-pentandiamin und aminoterminierte Polyether (ATPE), wobei 1, 4-Butandiol, Polypropylenglycole, 2-Methyl-1, 5- pentandiamin besonders bevorzugt sind.The compounds of the formula (VIII) are preferably 1,4-butanediol, polyethylene glycols, polypropylene glycols, 2-methyl-1,5-pentanediamine and amino-terminated polyethers (ATPE), 1,4-butanediol, polypropylene glycols, Methyl-1,5-pentanediamine are particularly preferred.
Die Stöchiometrie der Reaktanden zur Herstellung der erfindungsgemäßen Copolymere wird vorzugsweise derart gewählt, dass das molare Verhältnis der Isocyanatgruppen aus den Verbindungen der Formeln (VII) und (IX) zur Summe der mit den Isocyanatgruppen reaktiven EH- und NH-Gruppen aus den Verbindungen der Formeln (V), (VI) und (VIII) im Bereich von bevorzugt 0,7 bis 1,3, besonders bevorzugt 0,95 bis 1,05, insbesondere bei 1, liegt. Bei einem Verhältnis der Isocyanatgruppen zu den reaktivenThe stoichiometry of the reactants for the preparation of the copolymers according to the invention is preferably selected such that the molar ratio of the isocyanate groups from the compounds of the formulas (VII) and (IX) to the sum of the isocyanate-reactive EH and NH groups from the compounds of the formulas (V), (VI) and (VIII) is in the range of preferably 0.7 to 1.3, particularly preferably 0.95 to 1.05, in particular 1. At a ratio of the isocyanate groups to the reactive
Gruppen von größer 1, also einem Überschuss an Isocyanatgruppen, ergeben sich erfindungsgemäße Polymere der Formel (I) mit R''= -CO-NH-(Z-NH-CO-NHJh-Z-NCO und den sich daraus ergebenden Resten R' wie oben definiert am anderen Ende der Polymerketten. Bei einem Verhältnis kleiner 1, also einem Unterschuss an Iso- cyanatgruppen, ergeben sich erfindungsgemäße Polymere der Formel (I) mit R' ' =H und den sich daraus ergebenden Resten R' wie oben definiert am anderen Ende der Polymerketten.Groups of greater than 1, ie an excess of isocyanate groups, give polymers of the formula (I) according to the invention with R "= -CO-NH- (Z-NH-CO-NH-NH-Z-NCO and the resulting R 'radicals as defined above at the other end of the polymer chains. At a ratio of less than 1, ie a lower amount of isocyanate groups, polymers of the formula (I) according to the invention with R "= H and the resulting radicals R 'as defined above are formed at the other end of the polymer chains.
Falls erwünscht, kann das erfindungsgemäße Verfahren in Anwesenheit von Katalysatoren (f) durchgeführt werden. Bei den gegebenenfalls eingesetzten Katalysatoren kann es sich um alle bisher bekannten Katalysatoren, welche die Addition der Isocya- natgruppen der Verbindungen der allgemeinen Formeln (VII) und (IX) an die aktiven Gruppen der Verbindungen der Formeln (V), (VI) und (VIII) fördern, eingesetzt werden.If desired, the process according to the invention can be carried out in the presence of catalysts (f). The catalysts which may be used may be all known catalysts which comprise the addition of the isocyanate groups of the compounds of the general formulas (VII) and (IX) to the active groups of the compounds of the formulas (V), (VI) and ( VIII) promote, are used.
Beispiele für Katalysatoren (f) sind Diorganozinnverbindungen, wie Zinn (II) octoat, Dibutylzinndilaurat und Dibutylzinndiace- tat, Bismutverbindungen, wie Bismut- (2-ethylhexanoat) , Bismut- neodecanoat und Bismuttetramethylheptandionat, sowie Zinkverbindungen, wie Zinkacetylacetonat, Zink-2-ethylhexanoat und Zinkneodecanoat . Beispiele für kommerziell erhältliche Katalysatoren sind Borchi® Kat 22, Borchi® Kat VP 0243 und Borchi® Kat VP 0244 der Borchers GmbH, Deutschland, die BICAT®-Typen der The Shepherd Chemical Company, USA und K-Kat® K-348 der KING INDUSTRIES, INC., USA.Examples of catalysts (f) are diorganotin compounds such as stannous octoate, dibutyltin dilaurate and dibutyltin diacectate, bismuth compounds such as bismuth (2-ethylhexanoate), bismuth neodecanoate and bismuth tetramethylheptanedionate, and zinc compounds such as zinc acetylacetonate, zinc 2-ethylhexanoate and zinc neodecanoate. Examples of commercially available catalysts are Borchi® Kat 22, Borchi® Kat VP 0243 and Borchi® Kat VP 0244 from Borchers GmbH, Germany, the BICAT® grades from The Shepherd Chemical Company, USA and K-Kat® K-348 from KING INDUSTRIES, INC., USA.
Falls im erfindungsgemäßen Verfahren Katalysatoren eingesetzt werden, handelt es sich um Mengen von vorzugsweise 0,0001 bis 1 Gewichtsteile, besonders bevorzugt 0,001 bis 0,1 Gewichtsteile, jeweils bezogen auf 100 Gewichtsteile der Gesamtmischung.If catalysts are used in the process according to the invention, these are amounts of preferably 0.0001 to 1 part by weight, particularly preferably 0.001 to 0.1 part by weight, in each case based on 100 parts by weight of the total mixture.
Falls erwünscht, kann das erfindungsgemäße Verfahren in Anwesenheit von Lösungsmitteln (g) durchgeführt werden, wobei orga- nische Lösungsmittel, insbesondere nicht-protische, polare Lösungsmittel, bevorzugt sind.If desired, the process according to the invention can be carried out in the presence of solvents (g), with orga- nische solvents, in particular non-protic, polar solvents, are preferred.
Beispiele für die im erfindungsgemäßen Verfahren gegebenenfalls eingesetzten Lösungsmittel (g) sind Tetrahydrofuran, Dimethyl- formamid, N-Methylpyrrolidon und Methylethylketon, wobei Tetrahydrofuran und N-Methylpyrrolidon bevorzugt und Tetrahydrofuran besonders bevorzugt sind.Examples of the solvents (g) optionally used in the process according to the invention are tetrahydrofuran, dimethylformamide, N-methylpyrrolidone and methyl ethyl ketone, with tetrahydrofuran and N-methylpyrrolidone being preferred and tetrahydrofuran being particularly preferred.
Falls im erfindungsgemäßen Verfahren Lösungsmittel eingesetzt wird, handelt es sich um Mengen von vorzugsweise 10 bis 200 Gewichtsteile, besonders bevorzugt 10 bis 100 Gewichtsteile, jeweils bezogen auf 100 Gewichtsteile Gesamtmischung.If solvents are used in the process according to the invention, these are amounts of preferably 10 to 200 parts by weight, more preferably 10 to 100 parts by weight, in each case based on 100 parts by weight of the total mixture.
Die erfindungsgemäße Umsetzung kann in Lösung oder in Substanz erfolgen, wobei eine Umsetzung in Substanz bevorzugt ist.The reaction according to the invention can be carried out in solution or in substance, a reaction in substance being preferred.
Falls die erfindungsgemäße Umsetzung in Lösung erfolgt, sind Temperaturen von 0 bis 1000C bevorzugt und von 20 bis 800C be- sonders bevorzugt.If the reaction according to the invention takes place in solution, temperatures of from 0 to 100 ° C. are preferred and from 20 to 80 ° C. are particularly preferred.
Falls die erfindungsgemäße Umsetzung in Substanz erfolgt, sind Temperaturen oberhalb des Erweichungspunkts des hergestellten Copolymers der Formel (I) bevorzugt.If the reaction according to the invention takes place in substance, temperatures above the softening point of the copolymer produced of the formula (I) are preferred.
Das erfindungsgemäße Verfahren kann diskontinuierlich oder kontinuierlich durchgeführt werden. Im Falle einer diskontinuierlichen Arbeitsweise wird das Verfahren bevorzugt bei einem Druck der umgebenden Atmosphäre, also zwischen 900 und 1100 hPa, durchgeführt. Bei kontinuierlicher Herstellung, z.B. in einem Doppelschneckenextruder, wird bei einem Druck von bevorzugt bis zu 15 MPa in einigen Abschnitten des Extruders und zur Entgasung bei Drücken von bevorzugt 0,1 bis 1100 hPa gearbeitet. Bevorzugt erfolgt die Herstellung kontinuierlich.The process according to the invention can be carried out batchwise or continuously. In the case of a discontinuous procedure, the process is preferably carried out at a pressure of the surrounding atmosphere, ie between 900 and 1100 hPa. In continuous production, for example in a twin-screw extruder, at a pressure of preferably up to 15 MPa in some sections of the extruder and the Degassing at pressures of preferably 0.1 to 1100 hPa worked. Preferably, the preparation is carried out continuously.
Das erfindungsgemäße Verfahren kann mit Methoden erfolgen, die dem Fachmann bekannt sind, wie beispielsweise mittels Extrudern, Knetern, Walzenstühlen, dynamischem oder statischen Mischern .The process according to the invention can be carried out by methods known to the person skilled in the art, for example by means of extruders, kneaders, roll mills, dynamic or static mixers.
Das erfindungsgemäße Verfahren wird, insbesondere bei Anwesen- heit von Organyloxysilylgruppen, bevorzugt unter Ausschluss von Feuchtigkeit durchgeführt.The process according to the invention is carried out, in particular in the presence of organyloxysilyl groups, preferably with the exclusion of moisture.
Die erfindungsgemäß hergestellten Siloxan-Harnstoff-Copolymere können nun nach beliebigen, bisher bekannten Verfahren von ge- gebenenfalls noch vorhandenen Edukten bzw. gegebenenfalls eingesetzten Lösungsmitteln bzw. Katalysatoren befreit werden, wie z.B. durch Destillation oder Extraktion.The siloxane-urea copolymers prepared according to the invention can now be freed of any starting materials still present or of any solvents or catalysts used, if appropriate, by any desired methods known hitherto. by distillation or extraction.
Die im erfindungsgemäßen Verfahren eingesetzten Komponenten sind handelsübliche Produkte bzw. können nach in der Chemie gängigen Methoden hergestellt werden.The components used in the process according to the invention are commercially available products or can be prepared by methods customary in chemistry.
Bei den im erfindungsgemäßen Verfahren eingesetzten Komponenten kann es sich jeweils um eine Art einer solchen Komponente wie auch um ein Gemisch aus mindestens zwei Arten einer jeweiligen Komponente handeln.The components used in the process according to the invention may each be a type of such a component as well as a mixture of at least two types of a respective component.
Das erfindungsgemäße Verfahren hat den Vorteil, dass es einfach in der Durchführung ist und viele mögliche Copolymere mit gro- ßer Variabilität hergestellt werden können.The process according to the invention has the advantage that it is simple to carry out and many possible copolymers with great variability can be prepared.
Des Weiteren hat das erfindungsgemäße Verfahren den Vorteil, dass Copolymere wohldefiniert hergestellt werden können. Die erfindungsgemäßen bzw. erfindungsgemäß hergestellten Copo- lymere können überall dort eingesetzt werden, wo auch bisher Organopolysiloxan-Harnstoff-Copolymere eingesetzt wurden.Furthermore, the process according to the invention has the advantage that copolymers can be prepared in a well-defined manner. The copolymers according to the invention or those produced according to the invention can be used everywhere where organopolysiloxane-urea copolymers have hitherto been used.
Die erfindungsgemäßen bzw. erfindungsgemäß hergestellten Copo- lymere der Formel (I) können mit den üblichen Verarbeitungsmethoden für Polymere bzw. thermoplastische Elastomere verarbeitet werden, beispielsweise mittels Extrusion, Spritzguss, Blas- Verformung, Vakuumtiefziehen. Eine Verarbeitung als Lösung oder Emulsion bzw. Suspension ist ebenfalls möglich.The copolymers of the formula (I) according to the invention or prepared according to the invention can be processed by the customary processing methods for polymers or thermoplastic elastomers, for example by means of extrusion, injection molding, blow molding, vacuum thermoforming. Processing as a solution or emulsion or suspension is also possible.
Bevorzugte Anwendungen der erfindungsgemäßen bzw. erfindungsgemäß hergestellten Copolymere der Formel (I) sind Verwendungen als Basisstoff für thermoplastische Elastomere, wie beispielsweise Kabelumhüllungen, Schläuche, Dichtungen, Tastaturmatten, für Membranen, wie selektiv gasdurchlässige Membranen, überstreichbare und überlackierbare Bauteile für die Automobilindustrie, Folie für laminiertes Sicherheitsglas, als Zusatzstof- fe in Polymerblends, etwa als Schlagzähverbesserer oder Flammschutzmittel, oder als Material für die Modifizierung von Fasern oder für Beschichtungsanwendungen, beispielsweise in Anti- haftbeschichtungen, gewebeverträglichen Überzügen, flammgehemmten Überzügen oder als Beschichtungsmaterial für Holz, Papier oder Pappe, etwa als Trenn-Beschichtung für Klebebänder und E- tiketten. Bevorzugte Anwendungen sind weiterhin Beschichtungen für Textilfasern oder textile Gewebe, als Beschichtungsmaterial für Naturstoffe, wie z.B. Leder und Pelze. Weitere Anwendungsmöglichkeiten sind Dicht- und Klebstoffe, wie z.B. Schmelzkle- ber oder als Lösung zu applizierende Klebstoffe, Primer zur Verbesserung der Haftung von Dicht- und Klebstoffen auf verschiedenen Untergründen, Additive für die Polymerverarbeitung, wie etwa als Extrusionshilfsmittel für Thermoplastverarbeitung, Putz-, Reinigungs- oder Pflegemittel, anti-fouling Überzüge, Kosmetika, Körperpflegemittel, Lackadditive, PSA- Beschichtungen, Hilfsstoff in Waschmitteln und Textilbearbei- tung, Material für Entschäumerformulierungen, zum Modifizieren von Harzen oder zur Bitumenmodifizierung, als Formentrennmittel, als biokompatibles Material in medizinischen Anwendungen, wie Kontaktlinsen, als Material für Membranen und als Material für photoaktive Systeme, beispielsweise für lithographische Verfahren, optische Datensicherung oder optische Datenübertra- gung.Preferred applications of the copolymers of the formula (I) according to the invention or inventively prepared are uses as a base material for thermoplastic elastomers, such as cable sheaths, hoses, gaskets, keyboard mats, for membranes, such as selectively gas-permeable membranes, paintable and recoatable components for the automotive industry, film for Laminated safety glass, as additives in polymer blends, such as impact modifiers or flame retardants, or as a material for the modification of fibers or for coating applications, for example in anti-adhesive coatings, fabric-compatible coatings, flame-retardant coatings or as a coating material for wood, paper or cardboard, such as as a release coating for adhesive tapes and labels. Preferred applications are furthermore coatings for textile fibers or textile fabrics, as a coating material for natural materials, such as leather and furs. Further possible applications include sealants and adhesives, such as, for example, hot melt adhesives or adhesives to be applied as a solution, primers for improving the adhesion of sealants and adhesives on various substrates, additives for polymer processing, such as extrusion aids for thermoplastic processing, Cleaning, cleaning or care preparations, anti-fouling coatings, cosmetics, body care preparations, paint additives, PSA coatings, detergent additives and textile processing, defoamer formulations, modifiers for resins or bitumen modification, as mold release agents, as biocompatible materials in medical applications, such as contact lenses, as material for membranes and as material for photoactive systems, for example for lithographic processes, optical data backup or optical data transmission.
Insbesondere eignen sich die erfindungsgemäßen bzw. erfindungsgemäß hergestellten Copolymere der Formel (I) zur Verwendung in vernetzbaren Zusammensetzungen, wie etwa bei Raumtemperatur vernetzbaren Zusammensetzungen.In particular, the copolymers of the formula (I) according to the invention or those prepared according to the invention are suitable for use in crosslinkable compositions, such as room-temperature crosslinkable compositions.
Ein weiterer Gegenstand der vorliegenden Erfindung sind vernetzbare Massen enthaltend erfindungsgemäße bzw. erfindungsgemäß hergestellte Copolymere der Formel (I) .Another object of the present invention are crosslinkable compositions containing inventive or inventively prepared copolymers of the formula (I).
Bevorzugt handelt es sich bei den erfindungsgemäßen vernetzbaren Massen um durch Kondensationsreaktion vernetzbare Massen.The crosslinkable compositions of the invention are preferably compositions crosslinkable by condensation reaction.
Im Rahmen der vorliegenden Erfindung impliziert die Bezeichnung „Kondensationsreaktion", dass vor der Kondensationsreaktion gegebenenfalls ein Hydrolyseschritt hydrolysierbarer Reste stattfindet .In the context of the present invention, the term "condensation reaction" implies that, if appropriate, a hydrolysis step of hydrolyzable radicals takes place before the condensation reaction.
Im Rahmen der vorliegenden Erfindung sollen unter der Bezeich- nung „kondensationsfähige Reste" auch solche Reste verstanden werden, aus denen in einem gegebenenfalls vorangehenden Hydrolyseschritt kondensationsfähige Gruppen erzeugt werden. Bei den erfindungsgemäßen durch Kondensationsreaktion vernetzbare Massen handelt es sich bevorzugt um solche enthaltend (i) Copolymer der Formel (I), welche kondensationsfähige Reste aufweisen, gegebenenfalls (ii) Vernetzer, gegebenenfalls (iii) Katalysator, gegebenenfalls (iv) Füllstoff, gegebenenfalls (v) Haftvermittler, gegebenenfalls (vi) weitere Stoffe ausgewählt aus der Gruppe enthaltend Weichmacher, Stabilisatoren, Antioxidantien, Flammschutzmittel, Lichtschutzmittel und Pigmente, und gegebenenfalls (vii) vernetzbare Polymere, die unterschiedlich sind zu (i) .In the context of the present invention, the term "condensable radicals" should also be understood as meaning those radicals from which condensable groups are generated in an optionally preceding hydrolysis step. The condensation reaction crosslinkable compositions of the invention are preferably those containing (i) copolymer of formula (I) which have condensable radicals, optionally (ii) crosslinker, optionally (iii) catalyst, optionally (iv) filler, optionally (v ) Adhesion promoters, optionally (vi) further substances selected from the group comprising plasticizers, stabilizers, antioxidants, flame retardants, light stabilizers and pigments, and optionally (vii) crosslinkable polymers which are different from (i).
Bei diesen erfindungsgemäßen vernetzbaren Massen handelt es sich bevorzugt um Einkomponentenmassen. Zur Bereitung dieser Einkomponentenmassen können die jeweils eingesetzten Bestandteile auf beliebige und bisher bekannte Weise miteinander vermischt werden. Dieses Vermischen erfolgt bevorzugt bei Raumtem- peratur bzw. bei einer Temperatur, die sich beim Zusammengeben der Bestandteile bei Raumtemperatur ohne zusätzliche Heizung oder Kühlung einstellt, und dem Druck der umgebenden Atmosphäre, also etwa 900 bis 1100 hPa. Falls erwünscht, kann dieses Vermischen aber auch bei höheren oder niedrigen Drücken erfol- gen, beispielsweise bei niedrigen Drücken zur Vermeidung von Gaseinschlüssen. Die Herstellung der erfindungsgemäßen Massen und deren Lagerung erfolgen vorzugsweise unter im Wesentlichen wasserfreien Bedingungen, um ein vorzeitiges Reagieren der Massen zu vermeiden.These crosslinkable compositions according to the invention are preferably one-component compositions. In order to prepare these one-component compositions, the constituents used in each case can be mixed with one another in any desired and hitherto known manner. This mixing preferably takes place at room temperature or at a temperature which occurs when the components are added together at room temperature without additional heating or cooling, and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa. If desired, however, this mixing can take place even at higher or lower pressures, for example at low pressures to avoid gas inclusions. The preparation of the compositions according to the invention and their storage are preferably carried out under substantially anhydrous conditions in order to avoid premature reaction of the compositions.
Bei der erfindungsgemäß eingsetzten Komponente (i) handelt es sich bevorzugt um Copolymere der Formel (I), welche mindestens zwei Reste -OR1 aufweisen, wobei R1 die oben dafür angegebene Bedeutung hat .The component (i) used according to the invention is preferably copolymers of the formula (I) which have at least two radicals -OR 1 , where R 1 has the meaning given above.
Als gegebenenfalls eingesetzte Vernetzer (ii) können alle Vernetzer eingesetzt werden, die auch bisher in durch Kondensation vernetzbaren Massen eingesetzt worden sind. Bevorzugt handelt es sich bei Vernetzer (ii) um Organyloxysilane sowie deren Teilhydrolysate, wie beispielsweise Tetraethoxysilan, Tetra- isopropoxysilan, Tetra-n-propoxysilan, Methyltrimethoxysilan, Methyltriethoxysilan, n-Butyltrimethoxysilan, n-Octyltrimeth- oxysilan, i-Octyltrimethoxysilan, Vinyltrimethoxysilan und Vi- nyltriethoxysilan sowie deren Teilhydrolysate, wobei Methyl- und Vinyltrimethoxysilan besonders bevorzugt sind.As crosslinkers (ii) optionally used, it is possible to use all crosslinkers which have hitherto been used in compositions which can be crosslinked by condensation. Crosslinkers (ii) are preferably organyloxysilanes and also their partial hydrolysates, such as tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-butyltrimethoxysilane, n-octyltrimethoxysilane, i-octyltrimethoxysilane, vinyltrimethoxysilane and Vi - nyltriethoxysilane and their Teilhydrolysate, with methyl and vinyltrimethoxysilane are particularly preferred.
Falls die erfindungsgemäßen vernetzbaren Massen Vernetzer (ii) enthalten, handelt es sich um Mengen von vorzugsweise 0,05 bis 10 Gewichtsteilen, besonders bevorzugt 0,2 bis 5 Gewichtteilen, jeweils bezogen auf 100 Gewichtsteile vernetzbare Masse.If the crosslinkable compositions according to the invention contain crosslinkers (ii), these are amounts of preferably 0.05 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based in each case on 100 parts by weight of crosslinkable composition.
Als gegebenenfalls eingesetzte Katalysatoren (iii) können alle dem Fachmann bekannten Kondensationskatalysatoren verwendet werden .As optionally used catalysts (iii), it is possible to use all condensation catalysts known to the person skilled in the art.
Beispiele für Kondensationskatalysatoren (iii) sind Butyltita- nate und organische Zinnverbindungen, wie Di-n-butylzinndilau- rat und Di-n-butylzinndiacetat sowie dessen Umsetzungsprodukte mit den als Vernetzer bzw. Haftvermittler genannten Alkoxysila- nen, Dialkylzinnoxidlösungen in den als Vernetzer bzw. Haftvermittler genannten Alkoxysilanen, wobei Di-n-butylzinndilaurat und Dibutylzinnoxid in Tetraethoxysilan bevorzugt und Di-n-butylzinndilaurat besonders bevorzugt ist.Examples of condensation catalysts (iii) are butyl titanates and organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, and also the reaction products thereof with the alkoxysilanes which are mentioned as crosslinkers or adhesion promoters. NEN, dialkyltin oxide in the mentioned as crosslinkers or adhesion promoters alkoxysilanes, with di-n-butyltin dilaurate and dibutyltin oxide in tetraethoxysilane is preferred and di-n-butyltin dilaurate is particularly preferred.
Falls die erfindungsgemäßen vernetzbaren Massen Katalysator (iii) enthalten, handelt es sich um Mengen von vorzugsweise 0,01 bis 3 Gewichtsteilen, bevorzugt 0,05 bis 2 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile vernetzbare Masse.If the crosslinkable compositions according to the invention comprise catalyst (iii), these are amounts of preferably 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
Als gegebenenfalls eingesetzte Füllstoffe (iv) können alle Füllstoffe eingesetzt werden, die auch bisher in vernetzbaren Massen eingesetzt worden sind. Beispiele für Füllstoffe sind verstärkende Füllstoffe, also Füllstoffe mit einer BET-Ober- fläche von mindestens 30 m2/g, wie beispielsweise Ruße, pyrogen hergestellte Kieselsäure, gefällte Kieselsäure und Silicium- Aluminium-Mischoxide, wobei die genannten Füllstoffe hydropho- biert sein können, sowie nicht verstärkenden Füllstoffe, also Füllstoffe mit einer BET-Oberflache von weniger als 30 m2/g, wie beispielsweise Pulver aus Quarz, Cristobalit, Diatomeenerde, Calciumsilikat, Zirkoniumsilikat, Montmorillonite, wie Ben- tonite, Zeolithe einschließlich der Molekularsiebe, wie Natriumaluminiumsilikat, Metalloxide, wie Aluminium- oder Zinkoxid bzw. deren Mischoxide, Metallhydroxide, wie Aluminiumhydroxid, Bariumsulfat, Calciumcarbonat, Gips, Siliciumnitrid, Silicium- carbid, Bornitrid, Glas-, Kohle- und Kunststoffpulver und Glas- und Kunststoffhohlkugeln .As optional fillers (iv) all fillers can be used, which have also been used in crosslinkable compositions. Examples of fillers are reinforcing fillers, ie fillers having a BET surface area of at least 30 m 2 / g, such as, for example, carbon blacks, fumed silica, precipitated silica and silicon-aluminum mixed oxides, where the fillers mentioned may be hydrophobic , as well as non-reinforcing fillers, ie fillers having a BET surface area of less than 30 m 2 / g, such as powder of quartz, cristobalite, diatomaceous earth, calcium silicate, zirconium silicate, montmorillonites, such as Benmentite, zeolites including molecular sieves such as sodium aluminosilicate , Metal oxides such as aluminum or zinc oxide or their mixed oxides, metal hydroxides such as aluminum hydroxide, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass, carbon and plastic powder and glass and plastic hollow spheres.
Bevorzugt handelt es sich bei Füllstoff (iv) um pyrogene Kie- seisäuren oder Ruße oder deren Gemische, wobei Ruß mit einer BET-Oberflache von mindestens 30 m2/g besonders bevorzugt ist. Falls die erfindungsgemäßen Massen Füllstoffe (iv) enthalten, handelt es sich um Mengen von vorzugsweise 1 bis 50 Gewichtsteilen, bevorzugt 2 bis 30 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile vernetzbare Masse.Filler (iv) is preferably pyrogenic kiesisäuren or carbon blacks or mixtures thereof, with carbon black having a BET surface area of at least 30 m 2 / g is particularly preferred. If the compositions according to the invention comprise fillers (iv), these are amounts of preferably 1 to 50 parts by weight, preferably 2 to 30 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
Als gegebenenfalls eingesetzte Haftvermittler (v) können alle Haftvermittler eingesetzt werden, die auch bisher in durch Kondensation vernetzbaren Massen eingesetzt worden sind. Beispiele für Haftvermittler (v) sind Silane mit hydrolysierbaren Gruppen und SiC-gebundenen Vinyl-, Acryloxy-, Methacryloxy-, Epoxy-, Säureanhydrid-, Säure-, Ester- oder Ethergruppen sowie deren Teil- und Mischhydrolysate .As adhesion promoter (s) optionally used, it is possible to use all adhesion promoters which have hitherto been used in compositions which can be crosslinked by condensation. Examples of adhesion promoters (v) are silanes with hydrolyzable groups and SiC-bonded vinyl, acryloxy, methacryloxy, epoxy, acid anhydride, acid, ester or ether groups and their partial and mixed hydrolysates.
Bevorzugt wird als Haftvermittler (v) 3-Aminopropyltriethoxy- silan, 3- (2-Aminoethyl) aminopropyltrimethoxysilan, 3-Amino- propyltrimethoxysilan und 3- (2-Aminoethyl) aminopropyltriethoxy- silan eingesetzt, wobei 3-Aminopropyltriethoxysilan besonders bevorzugt ist.Preferred adhesion promoters (v) used are 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3- (2-aminoethyl) aminopropyltriethoxysilane, with 3-aminopropyltriethoxysilane being particularly preferred.
Falls die erfindungsgemäßen Massen Haftvermittler (v) enthalten, handelt es sich um Mengen von vorzugsweise 0,01 bis 5 Gewichtsteilen, bevorzugt 0,5 bis 4 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile vernetzbare Masse.If the compositions according to the invention comprise adhesion promoters (v), these are amounts of preferably 0.01 to 5 parts by weight, preferably 0.5 to 4 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
Beispiele für weitere Stoffe (vi) sind Weichmacher, wie tri- methylsilylterminierte Polydimethylsiloxane und Kohlenwasserstoffe mit etwa 16 bis 30 Kohlenstoffatomen, Stabilisatoren, wie 2-Etylhexylphosphat, Octylphosphonsäure, Polyether, Antio- xidantien, Flammschutzmittel, wie Phosphorsäureester, Licht- Schutzmittel und Pigmente, wie Titandioxid, Eisenoxide.Examples of further substances (vi) are plasticizers, such as trimethylsilyl-terminated polydimethylsiloxanes and hydrocarbons having about 16 to 30 carbon atoms, stabilizers, such as 2-ethylhexyl phosphate, octylphosphonic acid, polyethers, antioxidants, flame retardants, such as phosphoric acid esters, light stabilizers and pigments, such as titanium dioxide, iron oxides.
Bevorzugt handelt es sich bei den gegebenenfalls eingesetzten weiteren Stoffen (vi) um Weichmacher, wie trimethylsilyltermi- nierte Polydimethylsiloxane und Kohlenwasserstoffe mit etwa 16 bis 30 Kohlenstoffatomen, Stabilisatoren, wie 2-Etylhexylphos- phat, Octylphosphonsäure, Polyether, Flammschutzmittel, wie Phosphorsäureester und Pigmente, wie Titandioxid, Eisenoxide, wobei Stabilisatoren und Pigmente besonders bevorzugt sind.The optionally used further substances (vi) are preferably plasticizers, such as trimethylsilyltermi. ned polydimethylsiloxanes and hydrocarbons having about 16 to 30 carbon atoms, stabilizers such as 2-Etylhexylphos- phat, octylphosphonic acid, polyethers, flame retardants such as phosphoric acid esters and pigments such as titanium dioxide, iron oxides, with stabilizers and pigments are particularly preferred.
Falls Bestandteil (vi) eingesetzt wird, handelt es sich um Mengen von bevorzugt 0,01 bis 30 Gewichtsteilen, besonders bevorzugt 0,05 bis 25 Gewichtsteilen, jeweils bezogen auf 100 Ge- wichtsteile vernetzbare Masse.If component (vi) is used, these are amounts of preferably 0.01 to 30 parts by weight, particularly preferably 0.05 to 25 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
Gegebenenfalls können die erfindungsgemäßen vernetzbaren Massen vernetzbare Polymere (vii) , wie Organopolysiloxane mit reaktiven Endgruppen, enthalten. Beispiele für solche vernetzbaren Siloxane sind CCCO-Dihydroxypolydimethylsiloxane und OC,CO-bis (di- methoxymethylsilyl) terminierte Polydimethylsiloxane .Optionally, the crosslinkable compositions according to the invention can contain crosslinkable polymers (vii), such as organopolysiloxanes having reactive end groups. Examples of such crosslinkable siloxanes are CCCO-dihydroxypolydimethylsiloxanes and OC, CO-bis (dimethoxymethylsilyl) -terminated polydimethylsiloxanes.
Bevorzugt handelt es sich bei der gegebenenfalls in den erfindungsgemäßen vernetzbaren Massen eingesetzten Komponente (vii) um Polydiorganosiloxane mit mindestens einer OH-Gruppe oder einer hydrolysierbaren Gruppe an den Kettenenden, besonders bevorzugt um Polydimethylsiloxane mit mindestens einer OH-Gruppe oder einer hydrolysierbaren Gruppe an den Kettenenden, insbesondere um α, ω-Dihydroxypolydimethylsiloxane oder α,ω-bis(di- methoxymethylsilyl) terminierte Polydimethylsiloxane mit einer Viskosität von 100 bis 500 000 mPas .The component (vii) optionally used in the crosslinkable compositions according to the invention is preferably polydiorganosiloxanes having at least one OH group or a hydrolyzable group at the chain ends, more preferably polydimethylsiloxanes having at least one OH group or a hydrolyzable group at the chain ends , in particular α, ω-dihydroxypolydimethylsiloxanes or α, ω-bis (di-methoxymethylsilyl) terminated polydimethylsiloxanes having a viscosity of 100 to 500,000 mPas.
Bevorzugt enthalten die erfindungsgemäßen vernetzbaren Massen Komponente (vii) . Dieser Bestandteil wird bevorzugt zur Ein- Stellung der Verarbeitungseigenschaften, wie beispielsweise Viskosität oder Topfzeit, eingesetzt. Falls Komponente (vii) eingesetzt wird, handelt es sich um Mengen von bevorzugt 1 bis 50 Gewichtsteilen, besonders bevorzugt 2 bis 25 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile vernetzbare Masse.The crosslinkable compositions according to the invention preferably contain component (vii). This component is preferably used to adjust the processing properties, such as viscosity or pot life. If component (vii) is used, these are amounts of preferably 1 to 50 parts by weight, more preferably 2 to 25 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
Bei den einzelnen Bestandteilen der erfindungsgemäßen vernetzbaren Massen kann es sich jeweils um eine Art eines solchen Bestandteils wie auch um ein Gemisch aus mindestens zwei verschiedenen Arten derartiger Bestandteile handeln.The individual constituents of the crosslinkable compositions according to the invention may each be one type of such constituent as well as a mixture of at least two different types of such constituents.
Insbesondere enthalten die erfindungsgemäßen Massen außer der Komponente (i) , gegebenenfalls (ii) , (iii) , (iv) , (v) , (vi) und (vii) keine weiteren Bestandteile.In particular, the compositions according to the invention contain no further constituents apart from component (i), if appropriate (ii), (iii), (iv), (v), (vi) and (vii).
Die Herstellung der erfindungsgemäßen vernetzbaren Massen kann durch einfaches Vermischen erfolgen.The preparation of the crosslinkable compositions according to the invention can be carried out by simple mixing.
Die Herstellung der erfindungsgemäßen vernetzbaren Massen kann mit den für die Herstellung von Copolymere (I) genannten Appa- raturen erfolgen, die dem Fachmann bekannt sind.The preparation of the crosslinkable compositions according to the invention can be carried out with the apparatuses mentioned for the preparation of copolymers (I) which are known to the person skilled in the art.
Vulkanisate der erfindungsgemäßen Massen sind durch gegebenenfalls nötige Hydrolyse hydrolysierbarer Reste und anschließender Kondensation der entstandenen Silanolgruppen erhältlich. Die Hydrolyse kann durch Luftfeuchtigkeit oder durch Wasserdampf, Wasserbäder oder wasserhaltige Lösungen erfolgen im Kontakt mit dem erfindungsgemäßen Copolymer gemäß der allgemeinen Formel (I) .Vulcanizates of the compositions according to the invention can be obtained by optionally necessary hydrolysis of hydrolyzable radicals and subsequent condensation of the resulting silanol groups. The hydrolysis can be carried out by atmospheric moisture or by steam, water baths or aqueous solutions in contact with the copolymer of the invention according to the general formula (I).
Für die Vernetzung der erfindungsgemäßen Massen reicht vorzugsweise der übliche Wassergehalt der Luft aus. Die Vernetzung der erfindungsgemäßen Massen erfolgt vorzugsweise bei Raumtemperatur. Sie kann, falls erwünscht, auch bei höheren oder niedrige- ren Temperaturen als Raumtemperatur, wie beispielsweise bei -5 bis 15°C oder bei 30 bis 500C beispielsweise auch mittels den normalen Wassergehalt der Luft übersteigenden Konzentrationen von Wasser durchgeführt werden. Vorzugsweise wird die Vernet- zung bei einem Druck von 100 bis 1100 hPa, insbesondere beim Druck der umgebenden Atmosphäre, also etwa 900 bis 1100 hPa, durchgeführt .For the crosslinking of the compositions according to the invention, the usual water content of the air is preferably sufficient. The crosslinking of the compositions of the invention is preferably carried out at room temperature. If desired, it can also be used at higher or lower Ren temperatures as room temperature, such as at -5 to 15 ° C or at 30 to 50 0 C, for example, by means of the normal water content of the air excess concentrations of water are performed. Preferably, the crosslinking is carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Form- körper, hergestellt durch Vernetzung der erfindungsgemäßen Massen .Another object of the present invention are molded body, prepared by crosslinking of the compositions of the invention.
Im Vergleich zu nicht vernetzten thermoplastischen Siloxan- Harnstoff-Copolymeren gemäß Stand der Technik weisen die Vulka- nisate der erfindungsgemäßen Copolymere nach Feuchtigkeitsvernetzung eine geringere Abhängigkeit der mechanischen Eigenschaften von der Temperatur auf. Durch die Vernetzung werden die Vulkanisate der erfindungsgemäßen Copolymere bei Temperaturerhöhung nicht mehr plastisch, können also nicht mehr flie- ßen und sind somit formbeständiger. Insgesamt weisen die erfindungsgemäßen Vulkanisate also im Allgemeinen bessere mechanische Eigenschaften über einen weiteren Temperaturbereich auf, so dass sie in vielfältigeren Einsatzgebieten verwendet werden können .In comparison with non-crosslinked thermoplastic siloxane-urea copolymers according to the prior art, the vulcanizates of the copolymers according to the invention have, after moisture crosslinking, a lower dependence of the mechanical properties on the temperature. As a result of the crosslinking, the vulcanizates of the copolymers according to the invention no longer become plastic when the temperature increases, so they can no longer flow and are thus more dimensionally stable. Overall, therefore, the vulcanizates according to the invention generally have better mechanical properties over a wider temperature range, so that they can be used in more diverse fields of application.
Die erfindungsgemäßen vernetzbaren Massen können für alle Zwecke, für die auch bisher durch Kondensationsreaktion vernetzbare Massen eingesetzt worden, verwendet werden.The crosslinkable compositions according to the invention can be used for all purposes for which compositions crosslinkable by condensation reactions have also been used.
Die erfindungsgemäßen vernetzbaren Massen werden vorzugsweise als Schmelzkleber, Klebstoff, PSA (Pressure Sensitve Adhesive) , Dichtstoff, Beschichtung für beispielsweise Papier, Textil, Fasern oder silikatische Oberflächen, Imprägniermittel, Anstrich, Bestandteil in Verbundwerkstoffen, Additiv für Polymere, Formteil und Komponente für medizinische Zwecke sowie für den Einsatz im Automobilbau oder Laminatglas verwendet.The crosslinkable compositions of the invention are preferably used as hot melt adhesive, adhesive, PSA (Pressure Sensitive Adhesive), sealant, coating for example paper, textile, fibers or silicate surfaces, impregnating agent, paint, Component used in composites, additive for polymers, molding and component for medical purposes as well as for use in automotive or laminated glass.
Die erfindungsgemäßen Massen haben den Vorteil, dass sie alle der oben genannten Vorteile der eingesetzten erfindungsgemäßen Copolymere besitzen.The compositions of the invention have the advantage that they possess all of the abovementioned advantages of the copolymers according to the invention used.
Die erfindungsgemäßen Massen haben den Vorteil, dass sie sehr gute mechanische Eigenschaften aufweisen.The compositions of the invention have the advantage that they have very good mechanical properties.
Weitere Vorteile der erfindungsgemäßen Massen sind die hohe thermische und oxidative Beständigkeit, gute Beständigkeiten gegenüber Quellung und Zersetzung durch Kohlenwasserstoffe ent- haltende Lösemitteln.Further advantages of the compositions according to the invention are the high thermal and oxidative stability, good resistance to swelling and decomposition by solvents containing hydrocarbons.
Die erfindungsgemäßen Massen haben den Vorteil, dass die Eigenschaften, wie beispielsweise Schäl- und Ablösefestigkeit, Be- druckbarkeit, Zug- und Durchreißfestigkeit oder Wasserdampf- durchlässigkeit, gezielt eingestellt werden können.The compositions of the invention have the advantage that the properties, such as peel and peel strength, printability, tensile and tear propagation resistance or water vapor permeability, can be adjusted in a targeted manner.
Die erfindungsgemäßen Formkörper haben den Vorteil, dass sie eine geringere Abhängigkeit der mechanischen Eigenschaften von der Temperatur, insbesondere bei höheren Temperaturen, besit- zen.The shaped bodies according to the invention have the advantage that they have a lower dependence of the mechanical properties on the temperature, in particular at higher temperatures.
Die erfindungsgemäßen Formkörper haben des Weiteren den Vorteil, dass sie eine sehr gute Haftung auf Substraten besitzen.The shaped bodies according to the invention furthermore have the advantage that they have a very good adhesion to substrates.
In den nachstehend beschriebenen Beispielen beziehen sich alle Viskositätsangaben auf eine Temperatur von 25°C. Sofern nicht anders angegeben, werden die nachstehenden Beispiele bei einem Druck der umgebenden Atmosphäre, also etwa bei 1000 hPa, und bei Raumtemperatur, also bei etwa 23°C, bzw. bei einer Temperatur, die sich beim Zusammengeben der Reaktanden bei Raumtemperatur ohne zusätzliche Heizung oder Kühlung einstellt, sowie bei einer relativen Luftfeuchtigkeit von etwa 50 % durchge- führt. Des Weiteren beziehen sich alle Angaben von Teilen und Prozentsätzen, soweit nichts anderes angegeben ist, auf das Gewicht .In the examples described below, all viscosity data refer to a temperature of 25 ° C. Unless indicated otherwise, the following examples are at a pressure of the surrounding atmosphere, that is about 1000 hPa, and at room temperature, ie at about 23 ° C, or at a temperature that occurs when combining the reactants at room temperature without additional heating or cooling, and carried out at a relative humidity of about 50%. Furthermore, all parts and percentages are by weight unless otherwise specified.
Die Shore-A-Härte wird nach DIN (Deutsche Industrie Norm) 53505 (Ausgabe August 2000) bestimmt.The Shore A hardness is determined according to DIN (German Industrial Standard) 53505 (August 2000 edition).
Zugfestigkeit, Reißdehnung und Modul (Spannung bei 100 % De- hung) wurden nach DIN 53504 (Ausgabe Mai 1994) an Probekörpern der Form S2 bestimmt.Tensile strength, elongation at break and modulus (stress at 100% depression) were determined according to DIN 53504 (May 1994 edition) on test specimens of the form S2.
Der Druckverformungsrest (DVR) wurde nach ISO 815 bei 700C bestimmt .The compression set (DVR) was determined according to ISO 815 at 70 0 C.
Beispiel 1 17,1 g Isophorondiisocyanat werden mit 0,7 g Wasser und 10 mg Dibutylzinndilaurat in 100 ml Tetrahydrofuran 2 Stunden auf 70 °C erwärmt. Dazu werden 99,3 g eines CC,CO-aminopropylterminier- ten Polydimethylsiloxans mit einem Molgewicht Mw von 2890 g/mol und einer Viskosität von 50 mPas gegeben. Die viskose Lösung wurde in PTFE-Formen gegossen und das Lösungsmittel durch Abdampfen entfernt.Example 1 17.1 g of isophorone diisocyanate are heated to 70 ° C. for 2 hours with 0.7 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran. For this purpose, 99.3 g of a CC, CO-aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are added. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
Es wurde ein farbloses thermoplastisches Material erhalten. Aus diesem Material wurden Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 82 Shore A, Zugfestigkeit 7,8 MPa, Reißdehnung 461 %, Spannung bei 100 % Dehnung 4,07 MPa. Der DVR beträgt 88 %. Vergleichsbeispiel 1A colorless thermoplastic material was obtained. For this material, test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 82 Shore A, tensile strength 7.8 MPa, elongation at break 461%, stress at 100% elongation 4.07 MPa. The DVR is 88%. Comparative Example 1
7,7 g Isophorondiisocyanat werden in 100 ml Tetrahydrofuran gelöst. Dazu werden 99,3 g eines CCCO-aminopropylterminierten PoIy- dimethylsiloxans mit einem Molgewicht Mw von 2890 g/mol und ei- ner Viskosität von 50 mPas gegeben. Die viskose Lösung wurde in PTFE-Formen gegossen und das Lösungsmittel durch Abdampfen entfernt .7.7 g of isophorone diisocyanate are dissolved in 100 ml of tetrahydrofuran. For this purpose, 99.3 g of a CCCO-aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are added. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
Es wurde ein farbloses thermoplastisches Material erhalten. Aus diesem Material wurden Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 50 Shore A, Zugfestigkeit 5 MPa, Reißdehnung 450 %, Spannung bei 100 % Dehnung 1,2 MPa. Der DVR beträgt 102 %.A colorless thermoplastic material was obtained. For this material, test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 50 Shore A, tensile strength 5 MPa, elongation at break 450%, stress at 100% elongation 1.2 MPa. The DVR is 102%.
Beispiel 2Example 2
20,0 g 4 , 4 ' -Methylendicyclohexylendiisocyanat werden mit 0,7 g Wasser und 10 mg Dibutylzinndilaurat in 100 mlL Tetrahydrofuran 2 Stunden auf 700C erwärmt. Dazu werden 99,3 g eines CC,C0-amino- propylterminierten Polydimethylsiloxans mit einem Molgewicht Mw von 2890 g/mol und einer Viskosität von 50 mPas gegeben. Die viskose Lösung wurde in PTFE-Formen gegossen und das Lösungsmittel durch Abdampfen entfernt.20.0 g of 4, 4 '-Methylendicyclohexylendiisocyanat be with 0.7 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran for 2 hours at 70 0 C heated. For this purpose, 99.3 g of a CC, C0-amino-propyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are added. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
Es wurde ein farbloses thermoplastisches Material erhalten. Aus diesem Material wurden Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 81 Shore A, Zugfestigkeit 8,4 MPa, Reißdehnung 301 %, Spannung bei 100 % Dehnung 5,49 MPa. Der DVR beträgt 90 %.A colorless thermoplastic material was obtained. For this material, test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 81 Shore A, tensile strength 8.4 MPa, elongation at break 301%, stress at 100% elongation 5.49 MPa. The DVR is 90%.
Vergleichsbeispiel 2Comparative Example 2
9, 1 g 4, 4' -Methylendicyclohexylendiisocyanat werden in 100 ml Tetrahydrofuran gelöst. Dazu werden 99,3 g eines CC,CO-aminopro- pylterminierten Polydimethylsiloxans mit einem Molgewicht Mw von 2890 g/mol und einer Viskosität von 50 mPas gegeben. Die viskose Lösung wurde in PTFE-Formen gegossen und das Lösungsmittel durch Abdampfen entfernt.9.1 g of 4,4'-methylenedicyclohexylenediisocyanate are dissolved in 100 ml of tetrahydrofuran. For this purpose, 99.3 g of a CC, CO-aminopro pylterminierten polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
Es wurde ein farbloses thermoplastisches Material erhalten. Aus diesem Material wurden Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 55 Shore A, Zugfestigkeit 5,3 MPa, Reißdehnung 450 %, Spannung bei 100 % Dehnung 1,6 MPa. Der DVR beträgt 98 %.A colorless thermoplastic material was obtained. For this material, test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 55 Shore A, tensile strength 5.3 MPa, elongation at break 450%, stress at 100% elongation 1.6 MPa. The DVR is 98%.
Beispiel 3Example 3
1700,0 g eines α,ω-aminopropylterminierten Polydimethylsiloxans mit einem Molgewicht Mw von 2890 g/mol und einer Viskosität von 50 mPas werden mit 300 g Wasser kräftig verrührt und dann 14 Tage stehen gelassen und vom Wasser abgetrennt. Das Polydime- thylsiloxan enthält danach 3032 ppm Wasser. 100 g des wasserhaltigen Polydimethylsiloxans wurden in 340 ml Tetrahydrofuran (THF) gelöst und mit 11,5 g Isophorondiisocyanat und 10 mg Di- butylzinndilaurat versetzt. Anschließend wurde das Gemisch für 1 Stunde auf 700C erwärmt. Die viskose Lösung wurde in PTFE- Formen gegossen und das Lösungsmittel durch Abdampfen entfernt.1700.0 g of an α, ω-aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are vigorously stirred with 300 g of water and then allowed to stand for 14 days and separated from the water. The polydimethylsiloxane then contains 3032 ppm of water. 100 g of the hydrous polydimethylsiloxane were dissolved in 340 ml of tetrahydrofuran (THF) and admixed with 11.5 g of isophorone diisocyanate and 10 mg of di-butyltin dilaurate. Subsequently, the mixture was heated to 70 0 C for 1 hour. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
Es wurde ein farbloses thermoplastisches Material erhalten. Aus diesem Material wurden Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 61 Shore A, Zugfestigkeit 6,1 MPa, Reißdehnung 557 %, Spannung bei 100 % Dehnung 2,25 MPa.A colorless thermoplastic material was obtained. For this material, test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 61 Shore A, tensile strength 6.1 MPa, elongation at break 557%, stress at 100% elongation 2.25 MPa.
Beispiel 4 4,4 g Isophorondiisocyanat werden mit 0,18 g Wasser und 10 mg Dibutylzinndilaurat in 100 ml Tetrahydrofuran 2 Stunden auf 700C erwärmt. Dazu werden 99,3 g eines CCCO-aminopropylterminierten Polydimethylsiloxans mit einem Molgewicht Mw von 10100 g/mol und einer Viskosität von 600 mPas gegeben. Die viskose Lösung wurde in PTFE-Formen gegossen und das Lösungsmittel durch Abdampfen entfernt.Example 4 4.4 g of isophorone diisocyanate are heated to 70 ° C. with 0.18 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran for 2 hours. For this purpose, 99.3 g of a CCCO aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 10100 g / mol and a viscosity of 600 mPas given. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
Es wurde ein farbloses thermoplastisches Material erhalten. Aus diesem Material wurden Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 31 Shore A, Zugfestigkeit 3,4 MPa, Reißdehnung 601 %, Spannung bei 100 % Dehnung 0,81 MPa. Der DVR beträgt 51 %.A colorless thermoplastic material was obtained. For this material, test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 31 Shore A, tensile strength 3.4 MPa, elongation at break 601%, stress at 100% elongation 0.81 MPa. The DVR is 51%.
Vergleichsbeispiel 4Comparative Example 4
2,18 g Isophorondiisocyanat werden in 100 ml Tetrahydrofuran gelöst. Dazu werden 100 g eines CC,CO-aminopropylterminierten Po- lydimethylsiloxans mit einem Molgewicht Mw von 2890 g/mol und einer Viskosität von 50 mPas gegeben. Die viskose Lösung wurde in PTFE-Formen gegossen und das Lösungsmittel durch Abdampfen entfernt .2.18 g of isophorone diisocyanate are dissolved in 100 ml of tetrahydrofuran. For this purpose, 100 g of a CC, CO-aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas be given. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
Es wurde ein farbloses thermoplastisches Material erhalten. Aus diesem Material wurden Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 15 Shore A, Zugfestigkeit 1,2 MPa, Reißdehnung 650 %, Spannung bei 100 % Dehnung 0,45 MPa. Der DVR beträgt 97 %.A colorless thermoplastic material was obtained. For this material, test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 15 Shore A, tensile strength 1.2 MPa, elongation at break 650%, stress at 100% elongation 0.45 MPa. The DVR is 97%.
Beispiel 5Example 5
60,9 g Isophorondiisocyanat werden mit 2,46 g Wasser und 10 mg Dibutylzinndilaurat bei 25°C gerührt. Die Mischung erwärmt sich auf ca. 800C und es entsteht ein farbloser Feststoff. Das Produkt schmilzt zwischen 90 und 1000C und weist bei 135°C eine Viskosität von 851 Pas auf.60.9 g of isophorone diisocyanate are stirred with 2.46 g of water and 10 mg of dibutyltin dilaurate at 25 ° C. The mixture warms to about 80 0 C and it produces a colorless solid. The product melts between 90 and 100 0 C and has a viscosity of 851 Pas at 135 ° C.
In einem beheizten IKA-Laborkneter werden 115 g eines OC,ω- aminopropylterminierten Polydimethylsiloxans mit einem Molge- wicht Mw von 2890 g/mol und einer Viskosität von 50 mPas bei 1600C vorgelegt und 21,1 g des im ersten Schritt hergestellten Reaktionsgemisches portionsweise zugegeben. Es wird eine farblose, thermoplastische Masse erhalten. Diese wird in einer Presse bei 1700C zu einer 2 mm dicken Platte gepresst. Aus diesem Material wurden Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 80 Shore A, Zugfestigkeit 4,2 MPa, Reißdehnung 440 %, Spannung bei 100 % Dehnung 1,2 MPa.In a heated IKA laboratory kneader, 115 g of an OC, ω-aminopropyl-terminated polydimethylsiloxane with a molecular weight M w weight of 2890 g / mol and a viscosity of 50 mPas initially charged at 160 0 C and added 21.1 g of the reaction mixture prepared in the first step in portions. This gives a colorless, thermoplastic mass. This is pressed in a press at 170 0 C to a 2 mm thick plate. For this material, test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 80 Shore A, tensile strength 4.2 MPa, elongation at break 440%, stress at 100% elongation 1.2 MPa.
Beispiel 6Example 6
In den ersten Sektor eines gleichläufigen Leistritz-Doppelschneckenextruders (18 mm Schneckendurchmesser, L/D = 45) wurden 1000 g/h eines CC,CO-aminopropylterminierten Polydimethylsilo- xans mit einem Molgewicht Mw von 2890 g/mol, einer Viskosität von 50 mPas und einem Wassergehalt von 3032 ppm dosiert. Die Temperatur betrug an dieser Stelle des Extruders 1500C. Im zweiten Sektor des Extruders wurde ein Gemisch von 115 g Iso- phorondiisocyanat und 10 mg Dibutylzinndilaurat pro Stunde da- zudosiert. Die Temperatur des Extruders betrug an dieser Stelle 170°C. Die restlichen Sektoren wurden auf 180°C gehalten. Am Ende des Extruders trat ein glasklarer farbloser thermoplastischer Extrudatstrang aus, der in einem sich anschließenden Granulator zerkleinert wurde. Das so erhaltene Granulat wurde in einer Presse bei 1800C zu einer 2 mm dicken Platte gepresst und daraus Prüfkörper der Form S2 gemäß DIN 53504 gestanzt. Es wurden folgende mechanischen Kennwerte ermittelt: Härte 66 Shore A, Zugfestigkeit 6,8 MPa, Reißdehnung 543 %, Spannung bei 100 % Dehnung 2,3 MPa. In the first sector of a co-rotating Leistritz twin-screw extruder (18 mm screw diameter, L / D = 45) were 1000 g / h of a CC, CO-aminopropyl-terminated polydimethylsiloxane with a molecular weight M w of 2890 g / mol, a viscosity of 50 mPas and a water content of 3032 ppm. The temperature of the extruder at this point was 150 0 C. In the second sector of the extruder a mixture of 115 g iso- was phorondiisocyanat and 10 mg of dibutyl tin dilaurate per hour DA added. The temperature of the extruder was 170 ° C at this point. The remaining sectors were kept at 180 ° C. At the end of the extruder emerged a crystal clear colorless thermoplastic extrudate strand which was comminuted in a subsequent granulator. The granules thus obtained were pressed in a press at 180 0 C to a 2 mm thick plate and punched therefrom mold S2 according to DIN 53504. The following mechanical properties were determined: hardness 66 Shore A, tensile strength 6.8 MPa, elongation at break 543%, stress at 100% elongation 2.3 MPa.

Claims

Patentansprüche claims
1. Copolymere der allgemeinen Formel1. Copolymers of the general formula
R'- [(A)a(B)b(C)c] -R" (I),R'- [(A) a (B) b (C) c ] -R "(I),
worinwherein
(A) gleich oder verschieden sein kann und eine Einheit der For- mel (II)(A) may be the same or different and a unit of the formula (II)
- [CO-NH- { Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR1JoRa-O- (0-SiR2) n-O- Si(OR1J0R2-O-Y-ND]-,- [CO-NH- {Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1 J o Ra- O - ( O -SiR 2 ) nO-Si (OR 1 J 0 R 2 - O -Y-ND] -,
(B) gleich oder verschieden sein kann und eine Einheit der Formel (III)(B) may be the same or different and a unit of the formula (III)
- [CO-NH- {Z-NH-CO-NH}h-Z-NH-CO-NR4-G-NR4] -- [CO-NH- {Z-NH-CO-NH} h -Z-NH-CO-NR 4 -G-NR 4 ] -
undand
(C) gleich oder verschieden sein kann und eine Einheit der Formel (IV)(C) may be the same or different and a unit of the formula (IV)
- [CO-NH- { Z-NH-CO-NHJh-Z-NH-CO-E-X-E] -- [CO-NH- {Z-NH-CO-NHJ h -Z-NH-CO-EXE] -
darstellen, wobeirepresent, wherein
X gleich oder verschieden sein kann und einen gegebenenfalls durch Fluor, Chlor, d-C6-Alkyl- oder Ci-C6-Alkylester sub- stituierten Alkylenrest mit 1 bis 10000 Kohlenstoffatomen bedeutet, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -0-, -COO-, -OCO- oder -OCOO- ersetzt sein können, oder einen gegebenenfalls substituierten Ary- lenrest mit 6 bis 22 Kohlenstoffatomen bedeutet, Y gleich oder verschieden sein kann und einen zweiwertigen Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durchX may be identical or different and is an alkylene radical optionally substituted by fluorine, chlorine, C 1 -C 6 -alkyl or C 1 -C 6 -alkyl ester having 1 to 10 000 carbon atoms, in which non-adjacent methylene units are represented by groups -O-, - COO, -OCO or -OCOO- replaced or Y is an optionally substituted arylene radical having 6 to 22 carbon atoms, Y may be the same or different and a divalent hydrocarbon radical having 1 to 30 carbon atoms, in the non-adjacent methylene units
Gruppen -O- ersetzt sein können, oder den Rest - (CH2) 3-NH- SiR2-(CH2)3-NH- darstellt,Groups -O- may be replaced, or the radical is - (CH 2 ) 3 -NH- SiR 2 - (CH 2 ) 3 -NH-,
Z gleich oder verschieden sein kann und einen zweiwertigen, gegebenenfalls durch Fluor oder Chlor substituierten Koh- lenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen bedeutet,Z may be identical or different and is a bivalent hydrocarbon radical optionally substituted by fluorine or chlorine and having from 1 to 30 carbon atoms,
D gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest darstellt, E gleich oder verschieden sein kann und ein Sauerstoffatom oder eine Aminogruppe -ND- darstellt,D may be the same or different and represents hydrogen or a monovalent, optionally substituted hydrocarbon radical, E may be the same or different and represents an oxygen atom or an amino group -ND-,
R gleich oder verschieden sein kann und einen einwertigen, gegebenenfalls durch Fluor oder Chlor substituierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen bedeu- tet,R can be identical or different and denotes a monovalent hydrocarbon radical with 1 to 20 carbon atoms which is optionally substituted by fluorine or chlorine,
R1 gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls durch Fluor, Chlor oder Organyloxygruppen substituierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, -(C=O)-R oder -N=CR2 darstellt, R4 gleich oder verschieden sein kann und einen Rest der Formel -Z λ-SiRp (OR1) 3-p mit Zλ gleich einer für Z oben angegebenen Bedeutung und p gleich 0, 1 oder 2, Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest bedeutet, G gleich oder verschieden sein kann und eine für Z angegebene Bedeutung hat,R 1 may be identical or different and is hydrogen or a monovalent, optionally substituted by fluorine, chlorine or organyloxy groups hydrocarbon radical having 1 to 20 carbon atoms, - (C = O) -R or -N = CR 2 , R 4 be the same or different can and a radical of the formula -Z λ -SiR p (OR 1 ) 3-p with Z λ is equal to a meaning given above for Z and p is 0, 1 or 2, hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, G is the same or may be different and has a meaning given for Z,
R" Wasserstoffatom oder eine Einheit -CO-NH- { Z-NH-CO-NH}h-Z- NCO bedeutet, R' im Fall von R' ' gleich Wasserstoffatom einen Rest HND-Y-Si (OR1) 0R2-0- (0-SiR2) n-O-Si (OR1) 0R2_0-Y-ND-, HNR4-G-NR4- oder HE-X-E- bedeutet und im Fall von R'' gleich -CO-NH-(Z-NH-CO-NHJh-Z-NCO die Be- deutung vonR "represents hydrogen or a unit -CO-NH- {Z-NH-CO-NH} h -Z-NCO, R 'in the case of R''is a hydrogen atom is a radical HND-Y-Si (OR 1) 0 R2 0 - (0-SiR 2) n O-Si (OR 1) R 2 0 _ 0 -Y-ND-, HNR 4 -G-NR 4 - or HE-XE- and in the case of R '' equal to -CO-NH- (Z-NH-CO-NHJh-Z-NCO the meaning of
OCN- { Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR1) 0R2-0- (0-SiR2) n"0- Si (OR1J0R2-O-Y-ND-, OCN-iZ-NH-CO-NHJh-Z-NH-CO-NR^G-NR4- oder OCN- { Z-NH-CO-NH}h-Z-NH-CO-E-X-E- hat, n gleich oder verschieden sein kann und eine ganze Zahl von 1 bis 4000 ist, o gleich oder verschieden sein kann und 0, 1 oder 2 ist, a eine ganze Zahl von mindestens 1 ist, b 0 oder eine ganze Zahl von mindestens 1 ist, c 0 oder eine ganze Zahl von mindestens 1 ist, h 0 oder eine ganze Zahl von mindestens 1 ist,OCN- {Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1) 0 R2 0 - (0-SiR 2) n "0- Si (OR 1 J 0 R 2 - O- Y-ND, OCN-iZ-NH-CO-NHJ h -Z-NH-CO-NR ^ G-NR 4 - or OCN- {Z-NH-CO-NH} h -Z-NH-CO -EXE-, n may be the same or different and is an integer from 1 to 4000, o may be the same or different and is 0, 1 or 2, a is an integer of at least 1, b is 0 or an integer is at least 1, c is 0 or an integer of at least 1, h is 0 or an integer of at least 1,
mit der Maßgabe, dass das Copolymer der Formel (I) mindestens eine Einheit mit h verschieden 0 aufweist und die einzelnen Blöcke (A) , (B) und (C) im Polymer statistisch verteilt sein können.with the proviso that the copolymer of formula (I) has at least one unit with h different 0 and the individual blocks (A), (B) and (C) may be randomly distributed in the polymer.
2. Copolymere gemäß Anspruch 1, dadurch gekennzeichnet, dass c gleich 0 ist.2. Copolymers according to claim 1, characterized in that c is 0.
3. Verfahren zur Herstellung der Copolymere gemäß Anspruch 1 oder 2 durch Umsetzung von3. A process for the preparation of the copolymers according to claim 1 or 2 by reacting
(a) mindestens einem Polymer der Formel(a) at least one polymer of the formula
H-ND-Y-Si (OR1) 0R2-0- (0-SiR2) n-O-Si (OR1) OR2-O-Y-ND-H (V) ,H-ND-Y-Si (OR 1) 0R2-0- (0-SiR 2) n -O-Si (OR 1) 2 O R - O -Y-ND-H (V)
(b) mindestens einem Diisocyanat der Formel(B) at least one diisocyanate of the formula
OCN- { Z-NH-CO-NH}h. Z-NCO (VII) , (c) gegebenenfalls einer Verbindung der FormelOCN- {Z-NH-CO-NH} h . Z-NCO (VII), (c) optionally a compound of the formula
H-NR4-G-NR4-H (VI) ,H-NR 4 -G-NR 4 -H (VI),
(d) gegebenenfalls Verbindungen der Formel(d) optionally compounds of the formula
H-E-X-E-H (VIII)H-E-X-E-H (VIII)
undand
(e) gegebenenfalls Diisocyanaten der Formel OCN-Z-NCO (IX) ,(e) optionally diisocyanates of the formula OCN-Z-NCO (IX),
wobei X, Y, Z, D, E, G, R, R1, R4, und o eine der oben genannten Bedeutungen aufweisen und h' eine ganze Zahl von mindestens 1 ist.wherein X, Y, Z, D, E, G, R, R 1 , R 4 , and o have one of the meanings mentioned above and h 'is an integer of at least 1.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass es kontinuierlich erfolgt.4. The method according to claim 3, characterized in that it takes place continuously.
5. Vernetzbare Massen enthaltend Copolymere gemäß Anspruch 1 oder 2 oder hergestellt nach Anspruch 3 oder 4.5. Crosslinkable compositions comprising copolymers according to claim 1 or 2 or produced according to claim 3 or 4.
6. Vernetzbare Massen gemäß Anspruch 5, dadurch gekennzeichnet, dass es sich um durch Kondensationsreaktion vernetzbare Massen handelt .6. Crosslinkable compositions according to claim 5, characterized in that it is crosslinkable by condensation reaction masses.
7. Vernetzbare Massen gemäß Anspruch 6, dadurch gekennzeichnet, dass es sich um solche handelt enthaltend7. Crosslinkable compositions according to claim 6, characterized in that they are those containing
(i) Copolymer der Formel (I), welche kondensationsfähige Reste aufweisen, gegebenenfalls (ii) Vernetzer, gegebenenfalls (iii) Katalysator, gegebenenfalls (iv) Füllstoff, gegebenenfalls (v) Haftvermittler, gegebenenfalls(I) copolymer of formula (I) which have condensable groups, optionally (ii) crosslinker, optionally (iii) catalyst, optionally (iv) filler, optionally (v) coupling agent, optionally
(vi) weitere Stoffe ausgewählt aus der Gruppe enthaltend Weichmacher, Stabilisatoren, Antioxidantien, Flammschutzmittel, Lichtschutzmittel und Pigmente, und gegebenenfalls (vii) vernetzbare Polymere, die unterschiedlich sind zu (i) .(vi) other substances selected from the group consisting of plasticizers, stabilizers, antioxidants, flame retardants, light stabilizers and pigments, and optionally (vii) crosslinkable polymers other than (i).
8. Vernetzbare Massen gemäß Anspruch 7, dadurch gekennzeichnet, dass sie außer der Komponente (i) , gegebenenfalls (ii) , (iii) , (iv), (v) , (vi) und (vii) keine weiteren Bestandteile enthalten „8. Crosslinkable compositions according to Claim 7, characterized in that they contain no further constituents apart from component (i), optionally (ii), (iii), (iv), (v), (vi) and (vii) "
9. Formkörper, hergestellt durch Vernetzung der Massen gemäß einem oder mehreren der Ansprüche 5 bis 8. 9. Shaped body produced by crosslinking of the compositions according to one or more of claims 5 to 8.
PCT/EP2007/062695 2006-11-29 2007-11-22 Siloxane-urea copolymers WO2008065039A1 (en)

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CN108610466A (en) * 2018-05-17 2018-10-02 山东大学 A kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes

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DE102010036107A1 (en) * 2010-09-01 2012-03-01 Scheu-Dental Gmbh Thermoforming film or plate useful for producing an orthodontic splint or a mouth guard splint and dental thermoforming technique, comprises silicone blocks and organic blocks of a polymer material, preferably elastomeric silicone copolymer
DK2778267T3 (en) * 2013-03-11 2019-12-02 Parabeam Bv Upholstery material for an elastic, insulating or waterproof covering of objects or components
KR102193820B1 (en) * 2016-09-19 2020-12-24 다우 실리콘즈 코포레이션 Copolymer composition for coating and adhesive applications

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1496079A1 (en) * 2003-07-10 2005-01-12 Wacker-Chemie GmbH Crosslinkable polysiloxan-urea copolymers.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1496079A1 (en) * 2003-07-10 2005-01-12 Wacker-Chemie GmbH Crosslinkable polysiloxan-urea copolymers.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108610466A (en) * 2018-05-17 2018-10-02 山东大学 A kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes
CN108610466B (en) * 2018-05-17 2021-04-06 山东大学 Polyurea elastomer with polysiloxane completely replacing polyether and preparation method thereof

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