Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C265/00—Derivatives of isocyanic acid
  • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
• • 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • 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
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
  • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• • 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

Definitions

• the invention relates to diisocyanates having radiation-curable groups and radiation-crosslinkable organopolysiloxane-polyurea block copolymers obtainable therefrom and to their use.
• Organopolysiloxane-polyurea block copolymers are known and can be prepared from aminoalkyl-terminated siloxanes and diisocyanates.
• such polymers may be thermoplastic elastomers, i. above the softening point they are plastic, while underneath they have elastic properties. With this they can e.g. be used as a hot melt adhesive.
• the disadvantage of this is that by increasing the temperature beyond the softening point, the bond is reversible again.
• moldings or bonds made from such polymers are subject to a cold flow, because even under the softening point, hydrogen bonds can constantly loosen and re-bond, so that deformations and therefore failure of the desired function are possible.
• the field of application is limited to applications in which no elevated temperatures and / or forces act on the thermoplastic elastomer.
• thermoplastic elastomers are crosslinked during production by using, for example, trifunctional building blocks, the processing properties (eg melt viscosity) are adversely affected. Networking after application is therefore more useful.
• Reaction products of polyisocyanates, for example isocyanurate triisocyantes, with hydroxyl-containing acrylates are known (JP 2004137439 A2, JP 2004143303 A2), and only the isocyanate-free urethane acrylates (EP 430209 A2) are prepared and used.
• Light-curable elastomers are known and described, for example, in DE 42 11 391 A1. Photo-curable liquid silicone compositions are described, for example, in DE 697 17 935 T2 and US Pat. No. 5,635,544. Photosensitive thermoplastic compositions are described in DE 689 06 723 T2.
• the invention relates to copolymers of the general formula
• (B) may be the same or different and is a unit of the formula
• (C) may be the same or different and is a unit of the 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 700 carbon atoms, in which non-adjacent methylene units are represented by -O-, -COO groups -, -OCO- or -Oc00- may be substituted, or 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 which non-adjacent methylene units by groups -0 - may be replaced, or the radical - (CH 2 ) 3 -NH- SiR 2 - (CH 2 ) 3 -NH-
• Z may be the same or different and a (r + 2) -valent, optionally substituted hydrocarbon radical with 1 to 60 carbon atoms, which may be interrupted by heteroatoms, means
• Q denotes a divalent optionally substituted hydrocarbon radical having 1 to 30 carbon atoms which may be interrupted by heteroatoms,
• R 6 denotes a hydrogen atom or a monovalent hydrocarbon radical optionally substituted by fluorine or chlorine having 1 to 20 carbon atoms,
• R 7 may be identical or different and is hydrogen atom or a monovalent, optionally fluorine- or chlorine-substituted hydrocarbon radical having 1 to 20 carbon atoms, r may be identical or different and 0 or an integer of at least 1, D may be the same or different and represents hydrogen atom 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 may be identical or different and is a monovalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20 carbon atoms
• R 5 may be identical or different and a monovalent, optionally substituted by fluorine, chlorine or oxygen, optionally interrupted by oxygen
• C C-unsaturated hydrocarbon radical having 2 to 20 carbon atoms
• q is 0, 1 or 2
• G may be identical or different and is a divalent, optionally substituted hydrocarbon radical having 1 to 60 carbon atoms, which may be interrupted by heteroatoms means
• R '' is hydrogen or a radical -CO-NH-Z (L) r -NCO, preferably hydrogen atom
• R 'in the case of R'' is hydrogen, a radical HND-Y-Si (OR 1 ) 0R 2 O- ( O -SiR 2 ) n O-Si (OR 1 ) O R 2 - O -Y-ND-, HNR 4 -G-NR 4 - or HE-XE, preferably
• o can be the same or different and 0, 1 or 2, preferably 0, a is an integer of at least 1, b is 0 or an integer of at least 1 is c 0 or an integer is at least 1, with the proviso that in the molecule at least one residue L is present as well as 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.
• (2 + r) -valent radicals Z are alkylene radicals, such as the methylene, ethylene, n-propylene, iso-propylene, n-butylene, isobutylene, tert-butylene, n- Pentylene, iso-pentylene, neo-pentylene, tert-pentylene, hexylene, such as the n-hexylene, heptylene, such as the n-heptylene, octylene, such as the n-0ctylenrest and iso-octylene, such as 2,2,4-trimethylpentylene radical, nonylene radicals, such as the n-nonyl radical, decyl radicals, such as the n-decylene radical, dodecylene radicals, such as the n-diene radical decylene radical; Alkenylene radicals, such as the vinylene and allylene
• Radical Z is preferably alkylene groups having 1 to 24 carbon atoms and trihydric trialkylene isocyanurate radicals, particularly preferably hexylene, 4,4'-methylene-biscyclohexylene, 3-methylene-3,5,5-trimethylcyclohexylene radical and the trivalent trishexylisocyanurate radical.
• bivalent radicals Q are the bivalent groups given for Z.
• radicals Q are preferably unsubstituted or substituted alkylene radicals having from 1 to 30 carbon atoms, which may be interrupted by heteroatoms, or arylene radicals having from 6 to 22 carbon atoms. It is particularly preferred in the case of radical Q, it is alkylene groups having 1 to 12 carbon atoms, in particular alkylene groups having 1 or 4 carbon atoms.
• Examples of the bivalent radicals G are the bivalent examples listed for Z.
• Radical G is preferably alkylene radicals having 1 to ⁇ carbon atoms, arylene radicals such as the o-, m- or p-phenylene radical and aralkylene radicals such as the phenethylene radical, with the radical -CH 2 CH 2 - being particularly preferred.
• Z ⁇ are all bivalent 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.
• radical Y is alkylene groups having 1 to 6 carbon atoms, in particular alkylene groups having 1 or 3 carbon atoms.
• radical X examples are the butylene radical, ethylene radical, hexy- lenrest and radicals of the formulas - (CH 2 ) 3- (O-CH (CH 3 ) -CH 2 ) 2-300 0 -O- (CH 2 ) 3-, -CH (CH 3) -CH 2 - (O-CH (CH 3) -CH 2) 2-3000 "," (CH2) 3- (0-CH 2 -CH 2) 2- 300-0- ( CH 2 ) 3- and -CH 2 -CH 2 - (OCH 2 -CH 2 ) 2-300- •
• radicals X are preferably polyether radicals, particularly preferably polypropylene glycol radicals, in particular those having 2 to 600 carbon atoms.
• 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 radical hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical,
• Nonyl radicals 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 ⁇ - and the ß-phenylethyl radical.
• 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.
• radical R 5 examples are vinyl, allyl, 1,3-butadienyl, cyclohexenyl, 4-styryl, acryloxymethyl, acryloyloxypropyl, methacryloxymethyl and methacryloxypropyl radical, where vinyl and allyl radical are preferred and vinyl radical is particularly preferred are .
• radical R 1 examples are the examples given for radical R and alkoxyalkyl radicals.
• Radical R 1 is 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 having 1 to 12 carbon atoms, in particular to 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 , - (CH 2 CH (CH 3 ) CH 2 ) Si (OCH 3 ) 3 , - (CH 2 CH (CH 3 ) CH 2 ) Si (OCH 2 CH 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 ,
• radical R 6 examples are the radicals specified for R and hydrogen atom. Radical R 6 is preferably hydrogen atom and methyl radical.
• radical R 7 are the radicals specified for R and hydrogen atom.
• R 7 is hydrogen.
• 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 0 or an integer from 1 to 1000, particularly preferably 0 or an integer from 5 to 1000, in particular 0.
• 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.
• r has the meaning of an integer from 1 to 100, particularly preferably from 1 to 10, 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, and HO- (CH 2 CH (CH 3 ) O) 50 -.
• radicals R ' in the case where R "is -CO-NH-Z (L) r -NCO, are radicals which result from the unreacted end groups from the educts used, such as OCN- (CH 2 ) 6-NH-CO-HN- (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 1 O -CH 2 -C 6 H IO -NH-CO-HN-CH 2 -CH 2 -N- (CH 2 ) 3 Si (OCH 3 ) 3
• radicals R " are hydrogen atom, -CO-NH- (CH 2 ) 6 -NCO, -CO-NH-C 6 Hio-CH 2 -C 6 Hio-NCO and -CO-NH-C 6 H 3 ( CH 3 ) -NCO.
• n is an integer from 10 to 4000, especially be ⁇ vorzugt of 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. If the proportion of component (C) is too high, segregation phenomena occur between the organic and polysiloxane components, so that the transparency of the copolymers according to the invention is reduced and the copolymers become cloudy. Preference is given to polymers of the formula (II) where c is zero, 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 (II) according to the invention have a content of units A of the formula (III) of preferably greater than 70 wt .-%, more preferably greater than 80 wt .-%, each based on the total weight of the copolymer.
• copolymers of the formula (II) according to the invention are preferably rubber-elastic solids at room temperature with tensile strengths preferably between about 0.5 and 20 MPa and ultimate elongation preferably between about 50 to 1000%. They soften at temperatures preferably between 60 and 200 0 C and thereby lose their rubber-elastic properties.
• hydrolysable radicals OR 1 are present, they react by the action of moisture to form OH groups, which in turn can condense with further OR 1 or OH groups to form siloxane bonds.
• These additionally crosslinked polymers of the formula (II) according to the invention preferably have a softening point which has shifted significantly to higher temperatures than the starting polymer before crosslinking. This opens up the possibility of producing polymers that can be processed at relatively low temperatures but then exposed to higher temperatures during use.
• 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 outstanding physical properties, as are known from polyorganosiloxanes, such as, for example, low glass transition temperatures, transparency, low surface energies, low hydrophobicity, good dielectric properties and high permeability to gases.
• copolymers according to the invention are the high thermal and oxidative stability, good resistance to swelling and decomposition by above all polar organic solvents.
• the properties such as, for example, peel and peel strength, printability, tensile and tear-through properties speed or water vapor permeability, can be adjusted specifically.
• copolymers according to the invention can be prepared analogously to any processes which are already known to the person skilled in the art and are used, for example, for the synthesis of (prep) polymers for polyurethanes.
• Another object of the present invention is a process for the preparation of the copolymers of the formula (II) according to the invention by reacting
• r x is a number of at least 1 and / or their reaction products with phenols, ketoximes, malonic esters or nitrogen-containing heterocycles,
• diisocyanates such as the thermally unstable reaction products of isocyanates with, for example, phenols, ketoximes, malonic esters or nitrogen-containing heterocycles, d) optionally a compound of the formula
• X, Y, Z, L, D, E, G, R, R 1 , R 4 , R 5 , o and q have the abovementioned meaning.
• Formula (VI) are ⁇ , ⁇ -aminopropyldimethylsilyl-terminated polydimethylsiloxanes, ⁇ , ⁇ -aminopropyldimethoxysilyl-terminated polydimethylsiloxanes, ⁇ , ⁇ -aminomethyldimethylsilyl-terminated polydimethylsiloxanes and ⁇ , ⁇ -aminomethyldimethoxysilyl-terminated polydimethylsiloxanes.
• Preferred compounds of the formula (IX) which are used in the process according to the invention are 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) 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-trime
• isocyanates of the formula (VIII) used in accordance with the invention are hexylene diisocyanate, 4,4'-methylenedicyclohexyl-1-diisocyanate, 4,4'-methylenediphenylene diisocyanate, 1,3-diazetidine-2,4-dione bis (4,4 '- methylenedicyclohexyl) diisocyanate, 1,3-diazetidine-2,4-dione-bis (4,4'-methylene diphenyl) diisocyanate and isophorone diisocyanate, with hexylene diisocyanate, 4,4'-methylenedicyclohexylene diisocyanate, 4,4'-
• Methylene diphenylene diisocyanate and isophorone diisocyanate are preferred and hexylene diisocyanate, 4,4'-methylene-dicyclohexylene diisocyanate and isophorone diisocyanate are particularly preferred.
• Another object of the invention are diisocyanates of the general formula
• Z has one of the meanings given above and r "is equal to a number of at least 1.
• Examples of the compound 2 used according to the invention are 4-hydroxy-n-butyl acrylate, 4-hydroxy-n-butyl methacrylate, 3-hydroxy-n-butyl acrylate, 3-hydroxy-n-butyl methacrylate, 3-hydroxy-n-propyl acrylate, 3-hydroxy-n-propyl methacrylate, 2-hydroxy-n-propyl acrylate, 2-hydroxy-n-propyl methacrylate, hydroxypentyl acrylate and methacrylate, hydroxyhexyl acrylate and methacrylate, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, glycerine dimethacrylate, methacrylic acid 2- (tert-butylamino) ethyl ester, hydroxyoctyl acrylate and methacrylate, the reaction product of 1 mol of hydroxyethyl acrylate and / or hydroxyethyl methacrylate with an average of 2 mol ⁇ -caprolactone and
• Examples of the optionally used catalysts are all previously known catalysts which promote the addition of the isocyanate groups of the compounds 1 to the active groups of the compound 2, such as diorganotin compounds and bismuth compounds.
• the compound 1 and compound 2 used in the process according to the invention are commercially available products or can be prepared by processes known in the chemical art.
• Formula (X) are compounds known from polyurethane chemistry, such as diols, e.g. Ethylene glycol, polyethylene glycols, polypropylene glycols, polyester polyols, diamines such as e.g. Ethylenediamine, 5-amino-3- (aminomethyl) -1,3,3-trimethylcyclohexane), bis (4-amino-3-methylphenyl) methane, isomeric mixture of diaminodiethylmethylbenzene, bis (4-amino-3-chlorophenyl ) methane, 2-methylpropyl-4-chloro-3, 5-diaminobenzoate and amino-terminated polyethers (ATPE).
• diols e.g. Ethylene glycol, polyethylene glycols, polypropylene glycols, polyester polyols
• diamines such as e.g. Ethylenediamine, 5-amino-3- (amino
• the stoichiometry of the reactants for the preparation of the copolymers according to the invention is preferably chosen such that the molar ratio of the isocyanate groups from the compounds of the formula (VII) and (VIII) to the sum of the isocyanate-reactive EH and NH groups from the compounds of the formulas (VI), (IX) and (X) is in the range of preferably 0.7 to 1.3, particularly preferably 0.95 to 1.05, in particular 1.
• R 'radicals as defined above at the other end of the polymer chains.
• catalysts examples include all previously known catalysts which the addition the isocyanate groups of the compounds of the general formulas (VII) and (VIII) to promote the active groups of the polymers according to the formulas (VI), (IX) and (X), such as diorganotin compounds and bismuth compounds.
• catalysts are used in the process according to the invention, these are amounts of preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.1 part by weight, in each case based on 100 parts by weight of the total mixture.
• solvents optionally used in the process according to the invention are tetrahydrofuran, dimethylformamide, isopropanol and methyl ethyl ketone.
• 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 educts used in the process according to the invention for the preparation of copolymers of the formula (II) are commercial products or can be prepared by processes customary in the chemical industry.
• the reaction according to the invention can be carried out in solution or in substance, a reaction in substance being preferred. 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.
• temperatures above the softening point of the copolymer produced of the formula (II) are preferred.
• the process according to the invention is preferably carried out at a pressure of the surrounding atmosphere, ie between 900 and 1100 hPa.
• a pressure of the surrounding atmosphere ie between 900 and 1100 hPa.
• the mixture is operated at a pressure of preferably up to 15 MPa in some sections of the extruder and for degassing at pressures of preferably 0.1 to 1100 hPa.
• the inventive method is preferably carried out in the absence of moisture ⁇ and actinic radiation, it is also possible to work in the presence of water.
• the preparation of the copolymers according to the invention of the general formula (II) 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 preparation of the copolymers according to the invention can be carried out continuously or batchwise. Preferably, the preparation is carried out continuously.
• siloxane copolymers prepared according to the invention can now be prepared by any desired known methods of reactants which may still be present or solvents which may be used. be freed agents or catalysts, such as by distillation or extraction.
• 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 can be prepared with great variability.
• the process according to the invention has the advantage that copolymers can be prepared in a well-defined manner.
• copolymers of the formula (II) according to the invention can be prepared and processed by the customary processing methods for radiation-crosslinkable and optionally moisture-crosslinkable 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 (II) according to the invention or prepared according to the invention are uses as a constituent in adhesives and sealants, as a base material for thermoplastic elastomers such as cable sheathings, hoses, seals, keyboard mats, for membranes, such as selectively gas-permeable membranes Additives in polymer blends, or for coating applications, for example, in non-stick coatings, tissue-compatible coatings, flame-retardant coatings, and as biocompatible materials.
• sealants and adhesives for example hot melt adhesives, adhesives to be applied as a solution, Primers for improving the adhesion of sealants and adhesives on various substrates, additives for polymer processing, anti-fouling coatings, cosmetics, personal care products, paint additives, detergent additives and textile processing, for modifying resins or for bitumen modification.
• copolymers according to the invention or copolymers according to the invention is conceivable in many applications, for example in sealants, adhesives, as a material for the modification of fibers, as a plastic additive, for example as an impact modifier or flame retardant, as a material for antifoam formulations, as a high-performance polymer (thermoplastic, thermoplastic elastomer , Elastomer), as packaging material for electronic components, in insulation or shielding materials, in cable sheathing, in antifouling materials, as an additive for cleaning, cleaning or care agents, as an additive for personal care products, as a coating material for wood, paper and cardboard , as a mold release agent, as a biocompatible material in medical applications such as contact lenses, as a coating material for textile fibers or textile fabrics, as a coating material for natural products such as Leather and furs, as material for membranes and as material for photoactive systems, for example for lithographic processes, flexographic printing plates, optical data backup or optical data transmission.
• a plastic additive for example as an
• copolymers according to the invention are further given to using the copolymers according to the invention as a release coating for adhesive tapes and labels, fiber coating for textiles, extrusion aids for thermoplastic processing, medical articles, such as catheters, infusion bags or hoses, hot melt adhesives, PSA coatings, paintable overcoats and the like.
• recoatable components for the automotive industry additive for the polymer modification, such as plasticizers or impact modifiers, laminated safety glass or joint sealant for the construction industry.
• copolymers according to the invention can be used wherever previously also organopolysiloxane-polyurea copolymers were used.
• copolymers of formula (II) according to the invention are suitable for use in crosslinkable compositions, such as light-crosslinkable compositions.
• a further subject of the present invention are crosslinkable compositions comprising copolymers of the formula (II) according to the invention or prepared according to the invention.
• crosslinkable compositions of the invention are preferably compositions which can be crosslinked by actinic radiation.
• crosslinkable compositions comprising (i) copolymer of the formula (II), if appropriate (ii) crosslinker, if appropriate
• a photopolymerization initiator optionally (iv) filler, optionally (v) coupling agent, optionally (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).
• crosslinkable compositions according to the invention are preferably one-component compositions.
• the constituents used in each case can be mixed together in any desired and previously known manner. This mixing is preferably carried out at room temperature or at a temperature which occurs when the components are combined 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 lower pressures to avoid gas inclusions.
• compositions according to the invention and their storage are preferably carried out under substantially radiation-free, optionally anhydrous conditions in order to avoid premature reaction of the masses.
• Crosslinker (ii) is preferably acrylates.
• crosslinkers (ii) which may be used are monofunctional oligo (ethers) and monomeric acrylates and methacrylates.
• acrylates such as 2- (2-ethoxyethoxy) ethyl acrylate, 2-phenoxyethyl acrylate, caprolactone acrylate, cyclic trimethylolpropaneformacrylate, ethoxylated nonylphenolacrylate, isobornylacrylate, isodecylacrylate, laurylacrylate, octyldecylacrylate, stearylacrylate, tetrahydrofurfurylacrylate, tridecylacrylate, 2-phenoxyethylmethacrylate, ethoxylated hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, methoxypolyethylene glycol (350) monomethacrylate, methoxypolyethylene glycol (550) monomethacrylate, polypropylene
• Difunctional oligo (ethers) and monomeric acrylates and methacrylates such as 1,6-hexanediol diacrylate, alkoxylated diacrylates, alkoxylated hexanediol diacrylates, diethylene glycol diacrylate, dipropylene glycol diacrylate, ester diol diacrylate, ethoxylated bisphenol A diacrylates, polyethylene glycol (200) diacrylate , Polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tricyclodecanedimethanol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, ⁇ -hexanediol dimethacrylate, diethylene glycol dimethacrylate,
• Tri- and higher functional oligo (ethers) and monomeric acrylates and methacrylates such as dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate, ethoxylated trimethylolpropane tri-acrylates, pentaerythritol tetraacrylate, pentaerythritol triacrytate, propoxylated glycerol triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate Trimethylolpropane trimethacrylate;
• Epoxy acrylates such as bisphenol A epoxy acrylate, epoxidized soybean oil acrylate, epoxy novolac acrylate oligomer, fatty acid modified bisphenol A epoxy acrylate;
• crosslinkable compositions according to the invention contain crosslinkers (ii), these are amounts of preferably 0.05 to 70 parts by weight, more preferably 0.2 to 30 parts by weight, based in each case on 100 parts by weight of crosslinkable composition.
• photopolymerization initiators (iii) used it is possible to use all initiators or mixtures thereof known to the person skilled in the art.
• initiators (iii) are benzil dimethyl ketal, 2-hydroxy-2-methylphenyl-propan-1-one, 1-hydroxycyclohexylphenyl ketone, isopropylthioxanthone, bisacylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methylpropan-1-one, benzoin n-butyl ether, polymeric hydroxyketones, such as oligo (2-hydroxy-2-methyl-1, 4- (1-methylvinyl) phenylpropanone), acenaphthylquinone, ⁇ - Aminoacetophenone, benzanthraquinone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, benzil dimethylacetal, benzil 1-methyl-1-ethylacetal, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy
• a photopolymerization initiator may also be used in combination with coinitiators, e.g. Ethylanthraquinone with 4,4'-bis (dimethylamino) benzophenone, benzoin methyl ether with triphenylphosphine, benzil dimethyl ketal with benzophenones, diacylphosphine oxides with tertiary amines or acyldiarylphosphinoxides with benzil dimethyl acetal.
• coinitiators e.g. Ethylanthraquinone with 4,4'-bis (dimethylamino) benzophenone, benzoin methyl ether with triphenylphosphine, benzil dimethyl ketal with benzophenones, diacylphosphine oxides with tertiary amines or acyldiarylphosphinoxides with benzil dimethyl acetal.
• crosslinkable compositions according to the invention comprise photopolymerization initiator (iii), these are amounts of preferably 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
• 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 and non-reinforcing fillers, ie fillers having a BET surface area of less than 30 m 2 / g, such as, for example, powders of quartz, cristobalite, diatomaceous earth, calcium silicate, zirconium silicate, montmorillonites, such as benzonites, 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,
• Filler (iv) is preferably pyrogenic kiesiklaren, wherein a BET surface area of at least 30 m 2 / g is particularly preferred.
• compositions according to the invention contain 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) As adhesion promoter (s) optionally used, it is possible to use all adhesion promoters which hitherto have been used in compositions which can be crosslinked by radiation.
• adhesion promoters (v) are silanes with SiC-bonded vinyl, acryloyloxy, methacryloxy groups and their partial and mixed hydrolysates, acrylates such as 2- (2-ethoxyethoxy) ethyl acrylate, 2-phenoxyethyl acrylate, cyclic trimethylolpropane formalacylate, 1, ⁇ -hexanediol diacrylate, pentaerythritol tetraacrylate, tetrahydrofurfuryl methacrylate, methoxy-polyethylene glycol (550) -monomethacrylate, stearyl methacrylate.
• 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.
• plasticizers such as trimethylsilyl-terminated polydimethylsiloxanes and hydrocarbons having from about 16 to 30 carbon atoms
• stabilizers such as 2-ethylhexyl phosphate, octylphosphonic acid, polyethers, anti- oxidants, flame retardants, such as phosphoric acid esters, light stabilizers and pigments, such as titanium dioxide, iron oxides.
• the optionally used further substances (vi) are preferably plasticizers, such as trimethylsilyl-terminated polydimethylsiloxanes and hydrocarbons having about 16 to 30 carbon atoms, stabilizers, such as 2-ethylhexyl phosphate, octylphosphonic acid, polyethers, flame retardants, such as phosphoric acid esters and pigments, such as titanium dioxide, iron oxides, with stabilizers and pigments being particularly preferred.
• plasticizers such as trimethylsilyl-terminated polydimethylsiloxanes and hydrocarbons having about 16 to 30 carbon atoms
• stabilizers such as 2-ethylhexyl phosphate, octylphosphonic acid, polyethers
• flame retardants such as phosphoric acid esters and pigments, such as titanium dioxide, iron oxides, with stabilizers and pigments being particularly preferred.
• 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.
• the crosslinkable compositions of the invention may contain crosslinkable polymers (vii) such as organopolysiloxanes having reactive groups and aliphatic and aromatic urethane acrylates and polyester acrylates.
• crosslinkable polymers (vii) such as organopolysiloxanes having reactive groups and aliphatic and aromatic urethane acrylates and polyester acrylates.
• crosslinkable siloxanes are ⁇ , ⁇ -diacryloxymethylpolydimethylsiloxanes, ⁇ , ⁇ -divinylpolydimethylsiloxanes, poly (dimethyl-co-methylvinyl) siloxanes and ⁇ , ⁇ -methacryloypropyl-terminated polydimethylsiloxanes.
• the component (vii) optionally used in the crosslinkable compositions of the invention are preferably polydiorganosiloxanes having at least one radiation-crosslinkable group, particularly preferably polydimethylsiloxanes having at least one acrylic group at the chain ends and poly (dimethyl-co-methylvinyl ) siloxanes, in particular ⁇ , ⁇ -diacryloxy-methylpolydimethylsiloxanes, ⁇ , ⁇ -methacryloypropyl-terminated polyisocyanates, dimethylsiloxanes and poly (dimethyl-co-methylvinyl) siloxanes having a viscosity of 100 to 500,000 mPas.
• crosslinkable compositions according to the invention preferably contain component (vii). This ingredient is preferably used to adjust processing properties such as viscosity.
• component (vii) 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 a 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).
• crosslinkable compositions according to the invention are prepared by methods known to the person skilled in the art, for example by means of extruders, kneaders, roll mills, dynamic or static mixers.
• the preparation of the compositions according to the invention can be carried out continuously or batchwise. Preferably, the preparation is carried out continuously.
• Vulcanizates of the compositions according to the invention are obtainable by irradiation.
• Radiation sources such as UV lamps, lasers, sunlight are known in the art.
• the irradiation wavelengths and durations are based on the photopolymerization matched initiators and the compounds to be polymerized.
• the crosslinking of the compositions of the invention is preferably carried out at room temperature. It can, if desired, also at higher or lower temperatures than Griffintempera- structure, such as for example at -50 to 15 ° C or at 30 was carried out to 150 0 C.
• 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.
• Another object of the present invention are moldings prepared by crosslinking of the compositions of the invention.
• the vulcanizates of the copolymers according to the invention have a lower dependence of the mechanical properties on the temperature after radiation 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.
• the vulcanizates according to the invention thus have better mechanical properties over a wider temperature range, so that they can be used in more diverse fields of application.
• crosslinkable compositions according to the invention are preferably used as hotmelt adhesive, adhesive, PSA (Pressure Sensitive Adhesive), sealant, coating for example paper, textile, fibers or silicate surfaces, impregnating agent, paint, component in composites, additive for polymers, molding and component for medical purposes and used for automotive or laminated glass.
• PSA Pressure Sensitive Adhesive
• sealant coating for example paper, textile, fibers or silicate surfaces
• impregnating agent paint, component in composites, additive for polymers, molding and component for medical purposes and used for automotive or laminated glass.
• the compositions of the invention have the advantage that they have all of the abovementioned advantages of the copolymers of 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 polar, organic solvents.
• compositions according to the invention have the advantage that 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.
• 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.
• the Shore A hardness is determined according to DIN (German Industrial Standard) 53505 (March 2000 edition).
• trimer of hexamethylene diisocyanate commercially available under the trademark Desmodur® N3600 from Bayer AG,
• Example 3 18.3 g of trimer of hexamethylene diisocyanate (commercially available under the trademark Desmodur N3600 of Bayer AG, Germany) are mixed with 6.4 g of methacrylic acid-2- (tert-butylaminoethyl no) ethyl ester at 40 0 C in the dark 4 Hours stirred. For stabilization 1000 ppm of 2, 6-di-tert-butyl-4-methylphenol are added. The identity of the product as monoacrylate and diisocyanate is confirmed by 13 C NMR spectroscopy.
• EXAMPLE 4 22.2 g of the product from Example 1 are dissolved in 50 ml of tetrahydrofuran (THF) and added to 90 g of a double-sidedly 3-aminopropyl-terminated polydimethylsiloxane having a viscosity of 50 mPas and dissolved in 200 ml of THF. The solution is poured into a ca. 2 mm deep PTFE mold and the solvent evaporated under exclusion of light. This is repeated until 2 mm thick films are obtained, from which test specimens are punched. Mechanical characteristics for S2 rods are given in Table 1.
• Example 4 66 g of the product prepared in Example 4 are dissolved in 400 g of tetrahydrofuran (THF). 14 g of a double-sided trimethylsilyl-terminated polydimethylsiloxane having a viscosity of 10 mPas, 9.3 g of tetrahydrofurfuryl acrylate, 1.12 g of ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone (benzil dimethyl ketal) are mixed. The solution is poured into a ca. 2 mm deep PTFE mold and the solvent evaporated under exclusion of light. This is repeated until a 2 mm thick film is obtained, from which test specimens are punched. Mechanical characteristics for S2 rods are given in Table 1.
• Example 6 8.37 g of the product from Example 2 and 1.37 g of isophorone diisocyanate are dissolved in 30 ml of tetrahydrofuran (THF) and added to 40 g of a polydimethylsiloxane having a viscosity of 2: 3-aminopropyl-terminated polydimethylsiloxane dissolved in 200 ml of THF Given 50 mPas.
• THF tetrahydrofuran
• One of the films produced is irradiated for 1 minute with a second film for 5 minutes with the UV lamp.
• Mechanical characteristics for S2 rods are given in Table 2.

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