CA1290089C - Branched polymer containing silyl groups, a process for the preparationthereof, coating agents based on the polymer, and the use thereof - Google Patents
Branched polymer containing silyl groups, a process for the preparationthereof, coating agents based on the polymer, and the use thereofInfo
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- CA1290089C CA1290089C CA000546383A CA546383A CA1290089C CA 1290089 C CA1290089 C CA 1290089C CA 000546383 A CA000546383 A CA 000546383A CA 546383 A CA546383 A CA 546383A CA 1290089 C CA1290089 C CA 1290089C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
Abstract of the disclosure A branched polymer containing silyl groups, a pro-cess for the preparation thereof, coating agents based on the polymer, and the use thereof.
The invention relates to polymers containing silyl groups, the silyl groups being introduced into the poly-mer through ethylenically unsaturated monomers of the gen-eral formula (a) where R1 = alkyl, aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable double bond, X = a hydrolyzable group, and n = 1, 2 or 3.
The polymers can be obtained by copolymerization of a) 0.1 to 40% by weight of the silane monomers (a), b) 5 to 30% by weight, preferably 8 to 25% by weight, of monomers containing at least 2 polymerizable, ethyl-enically unsaturated double bonds, and c) 30 to 90% by weight of ethylenically unsaturated mono-mers without groups containing active hydrogen.
The invention also relates to moisture-hardening coating agents based on the polymers containing silyl groups. The coating agents are suitable, in particular, for automobile repair paintwork.
The invention relates to polymers containing silyl groups, the silyl groups being introduced into the poly-mer through ethylenically unsaturated monomers of the gen-eral formula (a) where R1 = alkyl, aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable double bond, X = a hydrolyzable group, and n = 1, 2 or 3.
The polymers can be obtained by copolymerization of a) 0.1 to 40% by weight of the silane monomers (a), b) 5 to 30% by weight, preferably 8 to 25% by weight, of monomers containing at least 2 polymerizable, ethyl-enically unsaturated double bonds, and c) 30 to 90% by weight of ethylenically unsaturated mono-mers without groups containing active hydrogen.
The invention also relates to moisture-hardening coating agents based on the polymers containing silyl groups. The coating agents are suitable, in particular, for automobile repair paintwork.
Description
9~89 August Z7, 1986 BASF Lacke + Farben Aktiengesellschaft, Munster ~ranched polymer conta;ning silyl gro ps, a process for polymer, and the use thereof The invention relates to a polymer containing S silyl groups, the silyl groups being introduced into the polymer through ethylenically unsaturated monomers of the general formuLa Rl .
3-n 2 (a) R - Si - Xn uhere R1 = alkyl, aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable-double bond, X = a hydrolyzable group, and n = 1, 2 or 3.
EP-A-158,161 discloses branched acrylate copoly-mers containing hydruxyl groups which are obtained by copolymerization of acrylates or methacrylates containing hydroxyl groups, monomers containing at least 2 polymeri-zable, olefinically unsaturated double bonds and further Z0 ethylenically unsaturated ~onomers. The branched acrylate copolymers can be combined ~ith melamine-formaldehyde ~k resins or with polyisocyanates to form a coating agent which can be hardened at lo~ temperatures. The coating agents have sood properties with regard to resistance to petroleum and long-term subjection to water or water S vapor, these properties being attributable, in particular, to the branched structure of the acrylate copolymers.
EP-A-48,461 and EP-A-63,753 disclose vinyl resins which contain silyl groups to ~hich a hydrolyzable radical is linked. The polymers containing silyl groups san be obtained, inter alia, through free-radical polymerization of silyl monomers of the general formula R 3-n R2 _ Si Xn (a) where R1 = alkyl, aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable double bond, X = a hydrolyzable group, and n = 1, 2 or 3.
In addition, the polymers can be prepared by catalyt;c hydrosilylation at the double bonds of a poly-mer having olefinically unsaturated groups. Dissolved in an organic solvent, the resins described give one-com-ponent coating compositions which harden undPr the influ-ence of moisture, even at low temperatures, ~hen suitable hardening catalysts are used.
. . .
EP-A-53,817 discloses a metallic base coat ~hich contains polymers containing silyl groups, the silyl groups being bonded to hydrolyzable groups, an acrylate resin and/or a cellulose compound and/or a reactive sili-cone component.
US Patent Specification Nos. 4,499,150 and4,499,151 discLose base coat/clear coat systems in which either the base coat~ the clear coat or both the base and the clear coat contain polyaddition products with alkoxy-or acyloxysilane units. After brief drying, the basecoat can be overpainted with the clear coat. According to these two patent specifications, all conventional monomers containing at least one double bond can be used for the polyacrylate. In the description and in the ilLustrative embodiments, only monomers containing an ethylenically unsaturated doubLe bond are used for the preparation of the acrylate copolymers containing silyl groups.
EP-A-159,715 describes a siliçone polymer which is obtainabLe through polymerization of at least one ethylenically unsaturated monomer containing reactive, hydrolyzable silicone groups and a compound containing at least two ethylenically unsaturated groups, in the pre-sence of a free-rad;cal initiator or a polymerization regulator containing reactive silicone groups. The or-ganic polymer used is, for example, a polyalkylene oxide containing reactive si~icone groups. These reactive silicone groups are capable of undergoing condensation reactions in the presence of mo;sture and in the presence of suitable catalysts. The moisture-hardenable polymer described can be obtained, for example, by react;ng 100 parts of the unsaturated monomer, 10 to 1,000 parts of the silicone polymer, 0.5 to 50 parts of the monomers con-tain;ng at least two independent ethylenically unsaturated groups and 0.01 to 20 parts o~ the silicone regulator or the silicone initiator. If the proportion of polyfunc-tional monomer is too high, gelling occurs, and in addi-tion the tendency to~ards gelling is dependent of boththe reguLator and the initiator content.
Under the reaction conditions mentioned, a graft reaction of the ethylenically unsatura$ed monomers onto the silicone resin present cannot be excluded. EP-A-159,715 states that if the proportion of polyfunctional monomers is too high, gelling of the product can occur.
The compositions described lead to improved ten-sile strength of the hardened polymer. A disadvantage of the compositions described is that it is possible for a large number of undesired side reactions to occur. The publication mentioned does not indicate any relationship between the tendency towards gelling and the polymeriza-tion temperature.
EP-A-159,716 describes silicone resins which are prepared by polymerization of at least one unsaturated compound in the presence of an organic polymer containing reactive, hydrolyzable silicsne groups and containing ethylenically unsaturated groups and at least one component 8~3 from the group comprising silicone regulators or silicone initiators. The organic polymer is based, for example, on polyalkylene oxides. Together with ethylenically un-saturated monomers, compounds containing at least two ethylenically unsaturated double bonds can also be poly-merized, sil;cone-modified monomers also being used.
GelLing occurs if the proportion of ethylenically poly-unsaturated monomers is too high, the polymerization tem-perature not being critical for the tendency towards gelling, according to the description in EP-A-159,716.
EP-A-169,536 describes moisture-hardening systems based on a polymer containing a~t least one reactive sili-cone group per molecule and based on silanol compounds or compounds which can be hydrolyzed into silanols. During ~oisture hardening, the silicone groups of the polymer react with the silanol compound in a fashion such that some of the reactive silicone groups are no longer avail-able as crosslinking points, but serve only for chain pro-pagation. The composi~ions described harden under the influence of moisture into an elastomeric material having good tensile strength and good surface properties. The compositions are preferably used as sealant materials.
The polymer containing at least one reactive sili-cone group per molecule can be formed by addition polymer-ization, monomers containing reactive silicone groups alsobeing used. In this addition polymerization~ monomers containing at least two ethYlenically unsaturated double bonds can also be incorporated into the addition polymer.
In the illustrative embodiments, these are used in the addition polymerizat;on in a proportion of less than 4%
by weight, relative to the total weight of the monomers.
The improvement in eLasticity of the coatings obtained is S attributable, in particular, ~o the addition df the sil-anol component.
The object of the present invention was to pro-vide binders for moisture-hardening one-component coat-ing agents, where the latter should harden at low tem-perature and the resultant coatings, compared to kno~nmoisture-hardening silicone resins, should have improved properties regarding petroLeum-resistance and regarding resistance to long-term subjection to water or water vapor. It should be possible to for~ coating agents with-out problems and substantially avoiding side reactions.
The object of the invention is solved by a poly-mer, of the type ment;oned initially, which contains silyl groups, wherein the polymer can be obtained by co-polymerizat;on of a) 0.1 to 40~ by ~eight of the silane monomers (a), b) S to 30% by weight, preferably 8 to Z5% by weight, of monomers containing at least two polymerizable, e~hy-lenically unsatura~ed double bonds, and c) 30 to 90% by weight of ethylenically unsaturated mono-mers without groups containing an active hydrogen, where the sum of a), b) and c) is 1UOX by weight.
The silane monomers employed (component a) are ethylenically unsaturated monomers of the general formula R 3-n R - Si - Xn (component a) where R1 = alkylr aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = 3" organic radical having a polymer;zable double bond, X = a hydrolyzable group, and n = 1~ 2 or 3~
The hydrolyzable group X can b~, for example, a halogen radical, an alkoxy radical, an acyloxy radical, a mer-capto radical or an alkenyloxy radical~
Suitable examples of the silane monomers are given belo~:
f CHa~CHSilOcH~a~ CH,=CHSiCI2, I::H2=CHSllOCHJ;" CH2=t:HSiCI"
CH, CH,'ClHCOOlCH~,SilClCH,32, CH2=CHCOO~CH,I,Si~OcH,!,.
CH, CH,=CHCOO(CH,),StCI" CH2=CHCOOlCH2~$iCI~
C~i~
CH2=CjCH,)COOlCH,),SilOCH,~3, CH~=ClCll,)COOlCH2),5ilOCH,~3, ~Ha CH2=ClCH,)COOlCH,1,SlCI2, CH,=ClCH,~COOlCH2),5iCI,, CH2-CH_CH2_oc ~co(cH2)3sl(ocH3)2, 38~
CH2~cH-cH2-oc ~ C-O( ~ )3SI(OC~
O o CH
C~2-CH-CH2~B ~ co(CH2)3!1C12 -o o Il 11 CH2_CH--CH2--OC__;~ C(C~2)3S5C12 y-Methacryloxypropyltrimethoxysilane is particu- -larly preferabLy employed as component a).
Compounds nf the general formula R O O R
CH2 = C - C - Y - (CH2)n ~ Y - C - C = CH2 ~here R ~ H, CH3 or alkyl, Y = 0, NH or S, and n - 2 to 8, may advantageously be used as component b). Examples of sush compounds are hexanediol diacrylate, hexanediol di-methacrylate, glycol diacrylate, glycol dimethacrylate, butanedio~ diacrylate, butanediol dimethacrylate, tri-methylolpropane triacrylate and tr;methylolpropane tri-methacrylate. In addition, divinylbenzene is also suit-abLe as component b). Of course, cQmbinations of these polyunsaturated monomers can also be usedO
In addition, component b) can advantageously be ' 1~9~18~3 a polycarboxylic acid or unsaturated monocarbaxylic asid which ;s esterified with an unsaturated alcohoL containing a polymerizable double bond.
Furthermore, component b) used may advantageously S be a product of the reaction of a polyisocyanate and an unsaturated alcohol or an am;ne. An example of this which may be mentioned is the product of the reaction of one mole of hexamethylene diisocyanate and two moles of allyl alcohol or the product of the reaction of isophorone di-isocyanate and hydroxyethyl acrylate.
A further advantageous component b) is a di-ester of poLyethylene glycol and/or polypropylene glycol having an average molecular weight of less than 1,500, preferably less than 1,000, and acryLic acid and/or meth-acrylic acid.
In addition, products o-f the reaction of a car-boxyl;c acid containing a polymerizable, olefinically unsaturated double bond and glycidyl acrylate and/or gly-cidyl methacrylate, and products of the reaction of di-carboxylic acids ~ith glycidyl acrylate and/or glycidylmethacrylate are suitable as component b). However, such-ethylenically polyunsaturated monomers should only be empLoyed in small amounts according to the invention since they c~ntain hydroxyl groups, which can react with the silane monomers (a). This also applies to ethyleni-cally polyunsaturated monomers which are formed from di-epoxy compounds and ethylenically unsaturated monomers containing a primary or secondary amino group since these l~sooa~
products likewise contain hydroxyl groups.
The choice of ethylenically unsaturated neutral monomers (component c) is not particularly critical.
These may be selected from the group comprising styrene, vinyltoluene, alkyl esters of acryL;c acid and methacrylic acid, alkoxye~hyl acrylates and aryloxyethyl acryl3tes and the corresponding methacrylates, and esters of maleic and fumaric acid~ Examples of these are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyi acrylate, isoamyl acry-late, hexyl acrylate, 2-ethylhexyl acrylate, octyL acry-late, 3,5,5-trimethylhexyl acrylate, decyl acrylate, do-decy~ acrylate, hexadecyl acrylate, octadecyl acrylate, octadecenyl acrylate, pentyl methacrylate, isoamyl meth-acrylate, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate~
dacyl methacrylate, dodecyl methacryla~e, hexadecyl meth-acrylate, octadecyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, methyl methacrylate, ethyl ZO methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl meth-acrylate, acrylonitrile, methacrylonitrile9 vinyl ace-tate, vinyl chloride and phenoxyethyl acrylate. Other monomers may be employed so long as they do not lead to undesired properties of the copolymer.
In order to make possible more rapid water take-up during crosslinking under the influence of atmospheric moistura, it is particularly advantageous when, as an ~9~08g additional comonomer d) besides the ethylenically un-saturated monomers a), b) and c), up to 10% by weight, relative to the sum of a) to d), of an ethylenically un- -saturated carboxamide are used.
Suitable components d) are, for example, acryla-mide, methacrylamide, itaconamide, a-ethylacrylamide, crotonamide, fumaramide and maleimide.
If desired, up to 5% by weight of ethylenically unsaturated monomers containing a hydroxyl group, a car-boxyl group or an amino group can also be used (component e). Examples of ethylenically unsaturated monomers con-taining hydroxyl groups are hydroxyalkyl esters of acry-lic acid and/or methacrylic acid, for example hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acryLate, hydroxyamyl acrylate, hydroxyhexy~ acrylate, hydroxyoctyl acrylate and the corresponding methacrylates.
Component e) may also be a product of the reaction of one mole o~ hydroxyethyl acrylate and/or hydroxyethyl meth-acrylate and an average of 2 moles of E-caprolactone~
Z0 Component e) can also be a hydroxyl group-containing ester of acrylic acid or of msthacrylic acid which con-~ains a secondary hydroxyl group, such as, for example~
2-hydroxypropyl acrylate, Z-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates.
2S A suitable polymerizable monomer containing hydroxyl groups is also a product of the reaction of acrylic acid and~or methacrylic acid w;~h the glycidyl ester of a car-boxylic acid containing a tertiary a-carbon atom.
~l~9~389 E~ampLes of ethylenically unsaturated monomers containing a carboxyl group are methacrylic acid and acrylic acid.
A suitable ethylenically unsaturated monomer containing an amino group is N-tert~-butylaminoethyl acrylate.
The copolymerization reactions for the prepara-tion of the polymers according to the invention are carried out using at least 2% by weight, reLative to the total weight of the ethylenically unsaturated monomers, of a polymerization regulator without active OH or NH
groups, preferred regulators being mercaptosilanes. It is apparent that, in many cases, only certain regulators are suitable for certain combinations of the monomers a) to e) to be polymerized.
If, for example, diacrylates or dimethacrylates of the general formula R O O R
CH2 = C - C - Y - (CH2)n - Y - C - C -- CH2 ~here R = H, CH3 or alkyl, Y = O, NH or S, and n = 2 to 8, are polymerized as component b) in a proport;on of more than 10% by weight, relative to the total weight of all the monomers, the polymerization should be carried out using more than 5% by weight, relative to the total weight of the monomers, of mercaptoethyltriethoxysilane and/or mercaptopropylmethyldimethoxysilane, if appropriate to-gether with other mercapto compounds, in a temperature 1~9~189 range between 100C and 1209C.
If the abovementioned, ethylenically polyunsatura-ted acrylate or methacrylate compounds are copolymerized in a proportion of at least 15% by weight, relative to the weight of monomers, mainly acrylate monomers and/or metha-crylate monomers and/or maleates and/or fumarates should be used as monomers without groups containing act;ve hy-drogen (component c)~ The copolymerization should be car-ried out in the presence of more than 6% by weight, rela-tive to the weight of monomers, of a mercaptosilane, pre-ferably mercaptoethyltrietho~ysilane or mercaptopropyl-methyldimethoxysilane, if appropriate together with other mercapto compounds.
If more than 10% by weight of divinylaromatics, such as, for example, divinylbenzene, are copolymerized as component b) together with monomers a), c), if appro-priate d) and if appropriate e), more than 10% by weight, relative to the ~eight of monomers~ of mercaptoethyltri-etho~ysilane and/or mercaptopropylmethyldimethoxysilane 2~ should preferably be employed as regulators in order to prevent gelling of the copolymer.
The present invention 3lso relates to a process for the preparation of the abovementioned polymers con-taining silyl groups.
The present invention also relates to a process for the preparation of a polymer containing silyl groups, where the silyl groups are ;ntroduced 1nto the polymer through ethylenically unsaturated monomers of the general ~9~89 formula 1 3-n R - Si - Xn ( ) where R1 = alkyl, aryL, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable double bond, X = a hydroly~able group~ and n = 1, 2 or 3, wherein, for its preparation~
a) 001 to 40% by weight of the silane monomers (a), b~ S to 30~ by weight~ preferably 8 to 25% by weight, of monomers containing a$ least two polymerizable, ethyl-enically unsaturated double bonds, and c) 30 to 90% by ~eight of ethylenically unsaturated neu-tral monomers, where the sum of a), b) and c) is 100~ by weight~ are co-polymerized in an organic solvent using initiators and using at Least 2% by weight, relative to the total weight of the monomers, of polymerization regulators without OH
and NH groups at 80C to 130C, preferably at 90C to 120C.
Examples of suitable ethylenically unsaturated monomers a) to c), and monomers d) and e) which can addi-tionally be used if desired, are the abovementioned exam-ples of components a) to e) of the polymer described con-taining silyl groups.
A precrosslinked, but ungelled copolymer can be gLZ9~8~
obtained through suitable polymerization conditions.
Suitable initiators are preferably azo initiators, such as, for example, azobisisobutyronitrile. If a small amount of ethylenically polyunsaturated monomers (com-S ponent b)) is employed, pero~y esters can also be used asinitiators. An example of these which may be mentioned is tert.-butyl peroxy-2-ethylhexanoate. Of course, azo initiators containing reactive silicone groups can also be used~ These are e0ployed in an amount of 0~01 to 20 parts by weight per 100 parts by weight of the polymeri-zable monomers~
Examples of azo initiators containing reactive silicone groups which can be employed are given in EP-A-159,715 and EP-A-159,716.
The polymerization regulators used are preferably mercaptosilanes or mixtures of mercaptosilanes with other ~ercapto compounds. In this case, only those mercapto compounds which do not react with silyl groups, iOe. have no OH or NH groups, are suitable. Examples of suitable ~ercaptosilanes which can be employed as polymerization regulators are listed below:
12~0~89 (CH30) 2 (CH3 ) SiCH ~CH2CH2SH
(C~3CH20) 3SiCH2CH2SH
(~:EI33~) 3~ 3 ~3) 2slcE~2c~2c225ElJ
C~ ?3~82c~2ct~ S~, C~;33 o .. ~c~3c~20) 2SlC~2C~2~i2S~I' ~C~3ll0~ a ~6E~5~ slC8~1~SE~ (CE~30) 3s~ 2SEl~
Cl Ic831 2SlC:~23~, 6CE~30~ 3sl~cE~2Br~
c~3 ~C80) 3SlC~2C~2CE~28t~, c~3 ~(CE130i351CR2~R~cR25 )2 f~3 (~ ~3~) 2SlCR2C~2C~2S-1 2' ~ ) ~30?3Sl~-gl2' f~3 IH3 C1130) 2sio-Sl-c~2c~cH2 ~, . ___ CH3 CIH3 S (C1~30~ 2510- 1~C~2C~2C~2Sl ~ 3 2, ~g~
Examples of other mercapto compounds are n- and t-dodecyl mercaptan.
Reactivity differences occur in the mercapto-silanes. The particularly preferred polymerization regu-lator is mercaptoethyltriethoxysilane~
The polymerization regulators are advantageouslyemployed in an amount of at least 4~ by ~eight, relative to the total weight of the monomers.
The free-radical polymerization is carried out at temperatures of 80-130C, preferably 90-120C. The free-radical polymerization for the preparation of the polymer containing silyl groups is advantageously carried out in a fashion such that a solution of the polymer having a solids content of 40-65% by weight results.
Suitable solvents for the free-radical polymeri-zation are nonreactive solvents, such as, for example, esters, ethers, hydrocarbons, alcohols and ketones~
The present invention also relates to 00isture-hardenable coating agents which contain the silyl group-containing polymer described above, organic solvent, ifappropriate pigments, fillers and conventional auxiliar-ies and additives and also a crosslinking cataLyst~ The coating compositions have an adequately long potlife without additior/ of a crosslinking ca~alyst~ If suitable Z5 crosslinking catalysts are added, the coating compositions-rapidly harden with moisture at room temperature or slightly elevated temperature.
Suitable crosslinking catalysts are, for example, 1;~9~0~39 phosphoric acid, p-toluenesulfonic acid, dibutyltin di-laurate, d;octyltin dilaurate, amines, for example ali-phatic diamines, such as ethylenediamine and hexanedi-amine, aliphatic polyamines, such as diethylenetriamine, triethylenetetramine and t~traethylenepentamine, al;cyclic amines, such as piperidine and piperazine, aromatic amines, ethanolamine and triethylamine, furthermore alkali metal catalysts, such as, for exampLe, potassium hydroxide or sodiu~ hydroxide. In an advantageous fashion, 0.01 to 10 parts by ~eight of the catalyst are used per 100 parts by weight of the polymer.
Organotin compounds which can be employed as cross-linking catalysts and ~hich may be mentioned are further-more compounds containing tin/sulfur single or double bonds, such as, for example, ( n-C4Hg ) 2 Sn ( SCH2 COO ), ( n-C8H 1 7 ) 2 Sn ( SCH2CH2COO ), 8 17 ) 2 Sn( SCH2COO CH2 CH2 OCO CH S ) (n-C8H17)2 Sn(SCH2 COO CH2 CH2 CH2 CH2 OCO CH2S), ( n-C4Hg ) 2 Sn( SCH2 COO CgH17~ ) 2 ' 8H17)2 Sn(SCH2 COO C12H25-n)2~
4 9)2 Sn(SCH2 COO C8H17~iso)2 and (~ C8H17)2 Sn = S-.
Mixtures of the abovementioned tin/sulfur com-pounds with tin compounds, such as, for example, with d;-alkyltin dimaleates, are also suitable for the catalysis.
EP-A-48,461 and EPA-A-63,753 disclose further, like~ise suitable catalysts.
9~89 The invention aLso relates to processes for the preparation of the coating agents described above, wherein the silyl group-containing polymer, an organic solvent, if appropriate pigments~ fillers and additives are processed into a coating composition by mix;ng and, if appropriate, dispersing, and the composit;on is admixed with a cross-linking catalyst shortly before use.
Due to the low hardening temperatures, the coating agents described are suitable, in particular, for repair painting of automobile bodywork.
The coating agents according to the invention are likewise highly suitable as base coats containing pigments and/or metallic pigments or as top coats or as base and top coats of mult;layer paintwork, which can ~e applied, if desired~ by the two-coat ~et-on-wet procsss.
The coating agents described have improved pro-perties with regard to petroleum resistance and with regard to stability on long-term subjection to water or ~ater vapor, compared to known silicone-modified copoly-~ers~
The invention is described below in greater detail with reference to ilLustrative embodiments:
A) Preparation of the copolymers according to the invention Unless other~ise stated, all percentage data in the following examples relate to parts by weight. The solids contents were determined in a circulation oven after 2 hours at 100C. The viscosities were determined 12~0~9 at 23C on a cone-plate viscometer ~ICI viscometer).
The proportions of the individual monomers, amounts of solvent, amounts of initiator and regulator, the polymerization temperature and the binder data can be seen from Table I. The acrylates are prepared in standard apparatuses (Z-liter glass reactors) equipped with stirrers, reflux condensers and feed vessels. The solvent used was a 1:1 mixture of xylene and 1-methoxy-propyl-2-acetate. The solvent mixture was introduced into the flasks, and part was used for dissolving the ;nitiator. The initiators used were 2,Z'-azobis(iso-butyronitrile) = I1 and 2,2'-azobis(methylbutyronitrile) - IZ. The follo~ing polymerization regulators were em-ployed:
mercaptoethyltrisethoxysilane = R1, mercaptopropyltrimethoxysilane - R2 and mercaptopropylmethyldimethoxysilane = R3 The solvent mixture was heated to the polymeri zation temperature specified, and the temperature was maintained during the entire polymer;~ation time. The monomer mixture~ (including regulat-or) and initiator solutions specified were metered in sep~rately.
The addition times were 3 hours for the monomer mixture (including regulator) and 3.5 hours for the ini-tiator solution, and the initiator feed was started 10minutes after the monomer fee'd in Example S, otherw;se the two feeds were begun simultaneously; the 'feed took place uniformly over the specified time, and polymerization 1290(:389 was cont;nued at the polymerization temperature specified for a further 2 hours after the initiator feed was complete. The amounts of monomers, solvents etc. are specified in P = p~rts by weight.
Table I
Example No. 1 2 3 4 5 6 Initial amount o~ solvent 389.6P 360.8P 348.8P 348.8P 572.4 607.0P
y-Methacryloxy-propyltrimethoxy-silane 180.0P 180~0P 180.0P 180~0P 180.0P 96.0P
Hexanediol diacrylate 120.0P 120.0P 120.0P 120.0P 90.0P
Divinylbenzo~
(64X strength in ethylstyrene) ~ 84.0P
Methyl meth-acrylate 180.0P 180.0P 180.0P 60.0P 90.0P 180.0P
tert.-Putyl acrylate 120.0P 120.0P 120.0P 60.0P 60.0P
Styrene - - - 120.0P 120.0P
n-Butyl acrylate60.0P 60.0P 60.0P 60.0P 60.0P
2-EthylhexyL
acrylate - - - - - 120.0P
Cyclohexyl methacrylate - - - - 120.0P
Regulator 88.8R2 60~0R1 48.0R2 57.0RZ 54.0R2 90.0R1 Initiator 20.4 I1 20.4 I1 20.4 I1 20~4 If 20.4 I2 21.0 I2 Solvent for initiator 319.6P 319.6P 319.6P 319.6P 102.0P 104.0P
Polymerization temperature 110C 110C 110C 110C 110C 90C
Solids content48.5X gelled 49.6% gelled 48.5% 48.7X
V;sc. (dPa.s) 0.3 2.2 1.4 1.9 1~9~89 The acrylate resins from Examples 3 and 6 ~ere concentrated to a solids content of 64.4 (3) and 59.8~
(6) by removing solvent mixture by distillation, and were employed in this form in the paints.
The copolymers sf Examples 6, 8 and 10 ~ere analyzed by gel-permeation chromat3graphy. The following values were obtained:
Exam~lë Fn lMw 6 2 830 60 000 21,2 8 3 000 80 000 26,3 3 500 95 000 26,9 ~L2~
Example No. 7 8 9 10 11 Initial amount of solvent 637.0P6Z1.4P 556.6P 557.2P 519.3P
~-Methacryloxy-propyltrimethosy-silane 60.0P 60.0P 180.0P 180.0P 180.0P
Hexanediol diacrylate - - 120.0P 12~.0P 120.0P
D;vinylbenzene (64% strength in ethyLstyrene)120.ûP120.0P - - -Methyl meth-acrylate 180.0P180.0P 120~0P 120.0P 120.0P
tert.-Putyl acrylate - - 120.0P 10g.0P 84.0P
n-~utyl acrylate - - 60.0P 60.0P 60.0P
2-Ethylhexyl acrylate 120.0P120.0P
Cyclohexyl methacrylate120.0P120.0P
Acrylamide - - - 12.0P
Acrylic acid/
Card. adduct (48.8% strength Z5 in toluene)* - - - - 73.5P
Regulator 90.0R1 104.4R338.4Q338.4R3 38.4R3 Initiator 21.0 I2 Z1.0 I2 20.4 IZ 20.4 I2 20.4 I2 Solvent for initiator 104.0P 10~.0P 102.0P . 102.0P102.0P
30 Polymerization temperature 90C ~0C 110C 110C 110C
Solids content gelled 49% 49% 49O5X 50.1X
Visc. (dPa.sj 2.0 1~55 2.8 3.8 The acrylic acid/Cardura E 10 adduct was prepared as follo~s:
750 parts of Cardura E 10 (glycidyl ester of a branched ~ p ~
12'900B9 C-10 carboxylic ac;d) and 988 parts of toluene were heated to 100C together with 0.988 parts of hydroquinone, and 238 parts of acrylic acid were metered in within 30 min-utes. The mixture was kept at 100C, 1 part of a chromium S salt complex was added 2.5 hours after the acrylic acid additionr a further 0.1 parts of a chromium salt complex were added after a further 5 hours at 110C, and an acid number of 18.5 (mg of KOH~ was reached after a further 5 hours. The product had a solids content of 48.8%.
9~08~
~) Preparation of paints according to the invention Clear-coat composition1) Paint 1 Paint 2 Acrylate resin from Example 6 76 Acrylate resin fro~ Example 3 - 47 Acrylate resin from Example 1 - 27 Polysiloxane/polyether solution (0.006X strength) 4 4 Light-screen (HALS product)2) 1~2 1.2 UY absorber (oxalanilide)3) Butyl glycol acetate 2 Z
HutyL acetate 14.3 16.3 Dibutyltin dilaurate solution (10% strength in xylene) 1.5 1.5 100.0 100.0 Paint thinner4) 27 9 11 9 Spray viscosity tDIN 4 beaker) 18 s 18 s Processing solids content (1 h/130C) 36.5Z 40%
1) The positions are stirred successively with a dissol-ver.
B 2) Tinuvin~292, Ciba Geigy 3) Sanduvo ~VSU, Sandoz AG
3-n 2 (a) R - Si - Xn uhere R1 = alkyl, aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable-double bond, X = a hydrolyzable group, and n = 1, 2 or 3.
EP-A-158,161 discloses branched acrylate copoly-mers containing hydruxyl groups which are obtained by copolymerization of acrylates or methacrylates containing hydroxyl groups, monomers containing at least 2 polymeri-zable, olefinically unsaturated double bonds and further Z0 ethylenically unsaturated ~onomers. The branched acrylate copolymers can be combined ~ith melamine-formaldehyde ~k resins or with polyisocyanates to form a coating agent which can be hardened at lo~ temperatures. The coating agents have sood properties with regard to resistance to petroleum and long-term subjection to water or water S vapor, these properties being attributable, in particular, to the branched structure of the acrylate copolymers.
EP-A-48,461 and EP-A-63,753 disclose vinyl resins which contain silyl groups to ~hich a hydrolyzable radical is linked. The polymers containing silyl groups san be obtained, inter alia, through free-radical polymerization of silyl monomers of the general formula R 3-n R2 _ Si Xn (a) where R1 = alkyl, aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable double bond, X = a hydrolyzable group, and n = 1, 2 or 3.
In addition, the polymers can be prepared by catalyt;c hydrosilylation at the double bonds of a poly-mer having olefinically unsaturated groups. Dissolved in an organic solvent, the resins described give one-com-ponent coating compositions which harden undPr the influ-ence of moisture, even at low temperatures, ~hen suitable hardening catalysts are used.
. . .
EP-A-53,817 discloses a metallic base coat ~hich contains polymers containing silyl groups, the silyl groups being bonded to hydrolyzable groups, an acrylate resin and/or a cellulose compound and/or a reactive sili-cone component.
US Patent Specification Nos. 4,499,150 and4,499,151 discLose base coat/clear coat systems in which either the base coat~ the clear coat or both the base and the clear coat contain polyaddition products with alkoxy-or acyloxysilane units. After brief drying, the basecoat can be overpainted with the clear coat. According to these two patent specifications, all conventional monomers containing at least one double bond can be used for the polyacrylate. In the description and in the ilLustrative embodiments, only monomers containing an ethylenically unsaturated doubLe bond are used for the preparation of the acrylate copolymers containing silyl groups.
EP-A-159,715 describes a siliçone polymer which is obtainabLe through polymerization of at least one ethylenically unsaturated monomer containing reactive, hydrolyzable silicone groups and a compound containing at least two ethylenically unsaturated groups, in the pre-sence of a free-rad;cal initiator or a polymerization regulator containing reactive silicone groups. The or-ganic polymer used is, for example, a polyalkylene oxide containing reactive si~icone groups. These reactive silicone groups are capable of undergoing condensation reactions in the presence of mo;sture and in the presence of suitable catalysts. The moisture-hardenable polymer described can be obtained, for example, by react;ng 100 parts of the unsaturated monomer, 10 to 1,000 parts of the silicone polymer, 0.5 to 50 parts of the monomers con-tain;ng at least two independent ethylenically unsaturated groups and 0.01 to 20 parts o~ the silicone regulator or the silicone initiator. If the proportion of polyfunc-tional monomer is too high, gelling occurs, and in addi-tion the tendency to~ards gelling is dependent of boththe reguLator and the initiator content.
Under the reaction conditions mentioned, a graft reaction of the ethylenically unsatura$ed monomers onto the silicone resin present cannot be excluded. EP-A-159,715 states that if the proportion of polyfunctional monomers is too high, gelling of the product can occur.
The compositions described lead to improved ten-sile strength of the hardened polymer. A disadvantage of the compositions described is that it is possible for a large number of undesired side reactions to occur. The publication mentioned does not indicate any relationship between the tendency towards gelling and the polymeriza-tion temperature.
EP-A-159,716 describes silicone resins which are prepared by polymerization of at least one unsaturated compound in the presence of an organic polymer containing reactive, hydrolyzable silicsne groups and containing ethylenically unsaturated groups and at least one component 8~3 from the group comprising silicone regulators or silicone initiators. The organic polymer is based, for example, on polyalkylene oxides. Together with ethylenically un-saturated monomers, compounds containing at least two ethylenically unsaturated double bonds can also be poly-merized, sil;cone-modified monomers also being used.
GelLing occurs if the proportion of ethylenically poly-unsaturated monomers is too high, the polymerization tem-perature not being critical for the tendency towards gelling, according to the description in EP-A-159,716.
EP-A-169,536 describes moisture-hardening systems based on a polymer containing a~t least one reactive sili-cone group per molecule and based on silanol compounds or compounds which can be hydrolyzed into silanols. During ~oisture hardening, the silicone groups of the polymer react with the silanol compound in a fashion such that some of the reactive silicone groups are no longer avail-able as crosslinking points, but serve only for chain pro-pagation. The composi~ions described harden under the influence of moisture into an elastomeric material having good tensile strength and good surface properties. The compositions are preferably used as sealant materials.
The polymer containing at least one reactive sili-cone group per molecule can be formed by addition polymer-ization, monomers containing reactive silicone groups alsobeing used. In this addition polymerization~ monomers containing at least two ethYlenically unsaturated double bonds can also be incorporated into the addition polymer.
In the illustrative embodiments, these are used in the addition polymerizat;on in a proportion of less than 4%
by weight, relative to the total weight of the monomers.
The improvement in eLasticity of the coatings obtained is S attributable, in particular, ~o the addition df the sil-anol component.
The object of the present invention was to pro-vide binders for moisture-hardening one-component coat-ing agents, where the latter should harden at low tem-perature and the resultant coatings, compared to kno~nmoisture-hardening silicone resins, should have improved properties regarding petroLeum-resistance and regarding resistance to long-term subjection to water or water vapor. It should be possible to for~ coating agents with-out problems and substantially avoiding side reactions.
The object of the invention is solved by a poly-mer, of the type ment;oned initially, which contains silyl groups, wherein the polymer can be obtained by co-polymerizat;on of a) 0.1 to 40~ by ~eight of the silane monomers (a), b) S to 30% by weight, preferably 8 to Z5% by weight, of monomers containing at least two polymerizable, e~hy-lenically unsatura~ed double bonds, and c) 30 to 90% by weight of ethylenically unsaturated mono-mers without groups containing an active hydrogen, where the sum of a), b) and c) is 1UOX by weight.
The silane monomers employed (component a) are ethylenically unsaturated monomers of the general formula R 3-n R - Si - Xn (component a) where R1 = alkylr aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = 3" organic radical having a polymer;zable double bond, X = a hydrolyzable group, and n = 1~ 2 or 3~
The hydrolyzable group X can b~, for example, a halogen radical, an alkoxy radical, an acyloxy radical, a mer-capto radical or an alkenyloxy radical~
Suitable examples of the silane monomers are given belo~:
f CHa~CHSilOcH~a~ CH,=CHSiCI2, I::H2=CHSllOCHJ;" CH2=t:HSiCI"
CH, CH,'ClHCOOlCH~,SilClCH,32, CH2=CHCOO~CH,I,Si~OcH,!,.
CH, CH,=CHCOO(CH,),StCI" CH2=CHCOOlCH2~$iCI~
C~i~
CH2=CjCH,)COOlCH,),SilOCH,~3, CH~=ClCll,)COOlCH2),5ilOCH,~3, ~Ha CH2=ClCH,)COOlCH,1,SlCI2, CH,=ClCH,~COOlCH2),5iCI,, CH2-CH_CH2_oc ~co(cH2)3sl(ocH3)2, 38~
CH2~cH-cH2-oc ~ C-O( ~ )3SI(OC~
O o CH
C~2-CH-CH2~B ~ co(CH2)3!1C12 -o o Il 11 CH2_CH--CH2--OC__;~ C(C~2)3S5C12 y-Methacryloxypropyltrimethoxysilane is particu- -larly preferabLy employed as component a).
Compounds nf the general formula R O O R
CH2 = C - C - Y - (CH2)n ~ Y - C - C = CH2 ~here R ~ H, CH3 or alkyl, Y = 0, NH or S, and n - 2 to 8, may advantageously be used as component b). Examples of sush compounds are hexanediol diacrylate, hexanediol di-methacrylate, glycol diacrylate, glycol dimethacrylate, butanedio~ diacrylate, butanediol dimethacrylate, tri-methylolpropane triacrylate and tr;methylolpropane tri-methacrylate. In addition, divinylbenzene is also suit-abLe as component b). Of course, cQmbinations of these polyunsaturated monomers can also be usedO
In addition, component b) can advantageously be ' 1~9~18~3 a polycarboxylic acid or unsaturated monocarbaxylic asid which ;s esterified with an unsaturated alcohoL containing a polymerizable double bond.
Furthermore, component b) used may advantageously S be a product of the reaction of a polyisocyanate and an unsaturated alcohol or an am;ne. An example of this which may be mentioned is the product of the reaction of one mole of hexamethylene diisocyanate and two moles of allyl alcohol or the product of the reaction of isophorone di-isocyanate and hydroxyethyl acrylate.
A further advantageous component b) is a di-ester of poLyethylene glycol and/or polypropylene glycol having an average molecular weight of less than 1,500, preferably less than 1,000, and acryLic acid and/or meth-acrylic acid.
In addition, products o-f the reaction of a car-boxyl;c acid containing a polymerizable, olefinically unsaturated double bond and glycidyl acrylate and/or gly-cidyl methacrylate, and products of the reaction of di-carboxylic acids ~ith glycidyl acrylate and/or glycidylmethacrylate are suitable as component b). However, such-ethylenically polyunsaturated monomers should only be empLoyed in small amounts according to the invention since they c~ntain hydroxyl groups, which can react with the silane monomers (a). This also applies to ethyleni-cally polyunsaturated monomers which are formed from di-epoxy compounds and ethylenically unsaturated monomers containing a primary or secondary amino group since these l~sooa~
products likewise contain hydroxyl groups.
The choice of ethylenically unsaturated neutral monomers (component c) is not particularly critical.
These may be selected from the group comprising styrene, vinyltoluene, alkyl esters of acryL;c acid and methacrylic acid, alkoxye~hyl acrylates and aryloxyethyl acryl3tes and the corresponding methacrylates, and esters of maleic and fumaric acid~ Examples of these are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyi acrylate, isoamyl acry-late, hexyl acrylate, 2-ethylhexyl acrylate, octyL acry-late, 3,5,5-trimethylhexyl acrylate, decyl acrylate, do-decy~ acrylate, hexadecyl acrylate, octadecyl acrylate, octadecenyl acrylate, pentyl methacrylate, isoamyl meth-acrylate, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate~
dacyl methacrylate, dodecyl methacryla~e, hexadecyl meth-acrylate, octadecyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, methyl methacrylate, ethyl ZO methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl meth-acrylate, acrylonitrile, methacrylonitrile9 vinyl ace-tate, vinyl chloride and phenoxyethyl acrylate. Other monomers may be employed so long as they do not lead to undesired properties of the copolymer.
In order to make possible more rapid water take-up during crosslinking under the influence of atmospheric moistura, it is particularly advantageous when, as an ~9~08g additional comonomer d) besides the ethylenically un-saturated monomers a), b) and c), up to 10% by weight, relative to the sum of a) to d), of an ethylenically un- -saturated carboxamide are used.
Suitable components d) are, for example, acryla-mide, methacrylamide, itaconamide, a-ethylacrylamide, crotonamide, fumaramide and maleimide.
If desired, up to 5% by weight of ethylenically unsaturated monomers containing a hydroxyl group, a car-boxyl group or an amino group can also be used (component e). Examples of ethylenically unsaturated monomers con-taining hydroxyl groups are hydroxyalkyl esters of acry-lic acid and/or methacrylic acid, for example hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acryLate, hydroxyamyl acrylate, hydroxyhexy~ acrylate, hydroxyoctyl acrylate and the corresponding methacrylates.
Component e) may also be a product of the reaction of one mole o~ hydroxyethyl acrylate and/or hydroxyethyl meth-acrylate and an average of 2 moles of E-caprolactone~
Z0 Component e) can also be a hydroxyl group-containing ester of acrylic acid or of msthacrylic acid which con-~ains a secondary hydroxyl group, such as, for example~
2-hydroxypropyl acrylate, Z-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates.
2S A suitable polymerizable monomer containing hydroxyl groups is also a product of the reaction of acrylic acid and~or methacrylic acid w;~h the glycidyl ester of a car-boxylic acid containing a tertiary a-carbon atom.
~l~9~389 E~ampLes of ethylenically unsaturated monomers containing a carboxyl group are methacrylic acid and acrylic acid.
A suitable ethylenically unsaturated monomer containing an amino group is N-tert~-butylaminoethyl acrylate.
The copolymerization reactions for the prepara-tion of the polymers according to the invention are carried out using at least 2% by weight, reLative to the total weight of the ethylenically unsaturated monomers, of a polymerization regulator without active OH or NH
groups, preferred regulators being mercaptosilanes. It is apparent that, in many cases, only certain regulators are suitable for certain combinations of the monomers a) to e) to be polymerized.
If, for example, diacrylates or dimethacrylates of the general formula R O O R
CH2 = C - C - Y - (CH2)n - Y - C - C -- CH2 ~here R = H, CH3 or alkyl, Y = O, NH or S, and n = 2 to 8, are polymerized as component b) in a proport;on of more than 10% by weight, relative to the total weight of all the monomers, the polymerization should be carried out using more than 5% by weight, relative to the total weight of the monomers, of mercaptoethyltriethoxysilane and/or mercaptopropylmethyldimethoxysilane, if appropriate to-gether with other mercapto compounds, in a temperature 1~9~189 range between 100C and 1209C.
If the abovementioned, ethylenically polyunsatura-ted acrylate or methacrylate compounds are copolymerized in a proportion of at least 15% by weight, relative to the weight of monomers, mainly acrylate monomers and/or metha-crylate monomers and/or maleates and/or fumarates should be used as monomers without groups containing act;ve hy-drogen (component c)~ The copolymerization should be car-ried out in the presence of more than 6% by weight, rela-tive to the weight of monomers, of a mercaptosilane, pre-ferably mercaptoethyltrietho~ysilane or mercaptopropyl-methyldimethoxysilane, if appropriate together with other mercapto compounds.
If more than 10% by weight of divinylaromatics, such as, for example, divinylbenzene, are copolymerized as component b) together with monomers a), c), if appro-priate d) and if appropriate e), more than 10% by weight, relative to the ~eight of monomers~ of mercaptoethyltri-etho~ysilane and/or mercaptopropylmethyldimethoxysilane 2~ should preferably be employed as regulators in order to prevent gelling of the copolymer.
The present invention 3lso relates to a process for the preparation of the abovementioned polymers con-taining silyl groups.
The present invention also relates to a process for the preparation of a polymer containing silyl groups, where the silyl groups are ;ntroduced 1nto the polymer through ethylenically unsaturated monomers of the general ~9~89 formula 1 3-n R - Si - Xn ( ) where R1 = alkyl, aryL, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable double bond, X = a hydroly~able group~ and n = 1, 2 or 3, wherein, for its preparation~
a) 001 to 40% by weight of the silane monomers (a), b~ S to 30~ by weight~ preferably 8 to 25% by weight, of monomers containing a$ least two polymerizable, ethyl-enically unsaturated double bonds, and c) 30 to 90% by ~eight of ethylenically unsaturated neu-tral monomers, where the sum of a), b) and c) is 100~ by weight~ are co-polymerized in an organic solvent using initiators and using at Least 2% by weight, relative to the total weight of the monomers, of polymerization regulators without OH
and NH groups at 80C to 130C, preferably at 90C to 120C.
Examples of suitable ethylenically unsaturated monomers a) to c), and monomers d) and e) which can addi-tionally be used if desired, are the abovementioned exam-ples of components a) to e) of the polymer described con-taining silyl groups.
A precrosslinked, but ungelled copolymer can be gLZ9~8~
obtained through suitable polymerization conditions.
Suitable initiators are preferably azo initiators, such as, for example, azobisisobutyronitrile. If a small amount of ethylenically polyunsaturated monomers (com-S ponent b)) is employed, pero~y esters can also be used asinitiators. An example of these which may be mentioned is tert.-butyl peroxy-2-ethylhexanoate. Of course, azo initiators containing reactive silicone groups can also be used~ These are e0ployed in an amount of 0~01 to 20 parts by weight per 100 parts by weight of the polymeri-zable monomers~
Examples of azo initiators containing reactive silicone groups which can be employed are given in EP-A-159,715 and EP-A-159,716.
The polymerization regulators used are preferably mercaptosilanes or mixtures of mercaptosilanes with other ~ercapto compounds. In this case, only those mercapto compounds which do not react with silyl groups, iOe. have no OH or NH groups, are suitable. Examples of suitable ~ercaptosilanes which can be employed as polymerization regulators are listed below:
12~0~89 (CH30) 2 (CH3 ) SiCH ~CH2CH2SH
(C~3CH20) 3SiCH2CH2SH
(~:EI33~) 3~ 3 ~3) 2slcE~2c~2c225ElJ
C~ ?3~82c~2ct~ S~, C~;33 o .. ~c~3c~20) 2SlC~2C~2~i2S~I' ~C~3ll0~ a ~6E~5~ slC8~1~SE~ (CE~30) 3s~ 2SEl~
Cl Ic831 2SlC:~23~, 6CE~30~ 3sl~cE~2Br~
c~3 ~C80) 3SlC~2C~2CE~28t~, c~3 ~(CE130i351CR2~R~cR25 )2 f~3 (~ ~3~) 2SlCR2C~2C~2S-1 2' ~ ) ~30?3Sl~-gl2' f~3 IH3 C1130) 2sio-Sl-c~2c~cH2 ~, . ___ CH3 CIH3 S (C1~30~ 2510- 1~C~2C~2C~2Sl ~ 3 2, ~g~
Examples of other mercapto compounds are n- and t-dodecyl mercaptan.
Reactivity differences occur in the mercapto-silanes. The particularly preferred polymerization regu-lator is mercaptoethyltriethoxysilane~
The polymerization regulators are advantageouslyemployed in an amount of at least 4~ by ~eight, relative to the total weight of the monomers.
The free-radical polymerization is carried out at temperatures of 80-130C, preferably 90-120C. The free-radical polymerization for the preparation of the polymer containing silyl groups is advantageously carried out in a fashion such that a solution of the polymer having a solids content of 40-65% by weight results.
Suitable solvents for the free-radical polymeri-zation are nonreactive solvents, such as, for example, esters, ethers, hydrocarbons, alcohols and ketones~
The present invention also relates to 00isture-hardenable coating agents which contain the silyl group-containing polymer described above, organic solvent, ifappropriate pigments, fillers and conventional auxiliar-ies and additives and also a crosslinking cataLyst~ The coating compositions have an adequately long potlife without additior/ of a crosslinking ca~alyst~ If suitable Z5 crosslinking catalysts are added, the coating compositions-rapidly harden with moisture at room temperature or slightly elevated temperature.
Suitable crosslinking catalysts are, for example, 1;~9~0~39 phosphoric acid, p-toluenesulfonic acid, dibutyltin di-laurate, d;octyltin dilaurate, amines, for example ali-phatic diamines, such as ethylenediamine and hexanedi-amine, aliphatic polyamines, such as diethylenetriamine, triethylenetetramine and t~traethylenepentamine, al;cyclic amines, such as piperidine and piperazine, aromatic amines, ethanolamine and triethylamine, furthermore alkali metal catalysts, such as, for exampLe, potassium hydroxide or sodiu~ hydroxide. In an advantageous fashion, 0.01 to 10 parts by ~eight of the catalyst are used per 100 parts by weight of the polymer.
Organotin compounds which can be employed as cross-linking catalysts and ~hich may be mentioned are further-more compounds containing tin/sulfur single or double bonds, such as, for example, ( n-C4Hg ) 2 Sn ( SCH2 COO ), ( n-C8H 1 7 ) 2 Sn ( SCH2CH2COO ), 8 17 ) 2 Sn( SCH2COO CH2 CH2 OCO CH S ) (n-C8H17)2 Sn(SCH2 COO CH2 CH2 CH2 CH2 OCO CH2S), ( n-C4Hg ) 2 Sn( SCH2 COO CgH17~ ) 2 ' 8H17)2 Sn(SCH2 COO C12H25-n)2~
4 9)2 Sn(SCH2 COO C8H17~iso)2 and (~ C8H17)2 Sn = S-.
Mixtures of the abovementioned tin/sulfur com-pounds with tin compounds, such as, for example, with d;-alkyltin dimaleates, are also suitable for the catalysis.
EP-A-48,461 and EPA-A-63,753 disclose further, like~ise suitable catalysts.
9~89 The invention aLso relates to processes for the preparation of the coating agents described above, wherein the silyl group-containing polymer, an organic solvent, if appropriate pigments~ fillers and additives are processed into a coating composition by mix;ng and, if appropriate, dispersing, and the composit;on is admixed with a cross-linking catalyst shortly before use.
Due to the low hardening temperatures, the coating agents described are suitable, in particular, for repair painting of automobile bodywork.
The coating agents according to the invention are likewise highly suitable as base coats containing pigments and/or metallic pigments or as top coats or as base and top coats of mult;layer paintwork, which can ~e applied, if desired~ by the two-coat ~et-on-wet procsss.
The coating agents described have improved pro-perties with regard to petroleum resistance and with regard to stability on long-term subjection to water or ~ater vapor, compared to known silicone-modified copoly-~ers~
The invention is described below in greater detail with reference to ilLustrative embodiments:
A) Preparation of the copolymers according to the invention Unless other~ise stated, all percentage data in the following examples relate to parts by weight. The solids contents were determined in a circulation oven after 2 hours at 100C. The viscosities were determined 12~0~9 at 23C on a cone-plate viscometer ~ICI viscometer).
The proportions of the individual monomers, amounts of solvent, amounts of initiator and regulator, the polymerization temperature and the binder data can be seen from Table I. The acrylates are prepared in standard apparatuses (Z-liter glass reactors) equipped with stirrers, reflux condensers and feed vessels. The solvent used was a 1:1 mixture of xylene and 1-methoxy-propyl-2-acetate. The solvent mixture was introduced into the flasks, and part was used for dissolving the ;nitiator. The initiators used were 2,Z'-azobis(iso-butyronitrile) = I1 and 2,2'-azobis(methylbutyronitrile) - IZ. The follo~ing polymerization regulators were em-ployed:
mercaptoethyltrisethoxysilane = R1, mercaptopropyltrimethoxysilane - R2 and mercaptopropylmethyldimethoxysilane = R3 The solvent mixture was heated to the polymeri zation temperature specified, and the temperature was maintained during the entire polymer;~ation time. The monomer mixture~ (including regulat-or) and initiator solutions specified were metered in sep~rately.
The addition times were 3 hours for the monomer mixture (including regulator) and 3.5 hours for the ini-tiator solution, and the initiator feed was started 10minutes after the monomer fee'd in Example S, otherw;se the two feeds were begun simultaneously; the 'feed took place uniformly over the specified time, and polymerization 1290(:389 was cont;nued at the polymerization temperature specified for a further 2 hours after the initiator feed was complete. The amounts of monomers, solvents etc. are specified in P = p~rts by weight.
Table I
Example No. 1 2 3 4 5 6 Initial amount o~ solvent 389.6P 360.8P 348.8P 348.8P 572.4 607.0P
y-Methacryloxy-propyltrimethoxy-silane 180.0P 180~0P 180.0P 180~0P 180.0P 96.0P
Hexanediol diacrylate 120.0P 120.0P 120.0P 120.0P 90.0P
Divinylbenzo~
(64X strength in ethylstyrene) ~ 84.0P
Methyl meth-acrylate 180.0P 180.0P 180.0P 60.0P 90.0P 180.0P
tert.-Putyl acrylate 120.0P 120.0P 120.0P 60.0P 60.0P
Styrene - - - 120.0P 120.0P
n-Butyl acrylate60.0P 60.0P 60.0P 60.0P 60.0P
2-EthylhexyL
acrylate - - - - - 120.0P
Cyclohexyl methacrylate - - - - 120.0P
Regulator 88.8R2 60~0R1 48.0R2 57.0RZ 54.0R2 90.0R1 Initiator 20.4 I1 20.4 I1 20.4 I1 20~4 If 20.4 I2 21.0 I2 Solvent for initiator 319.6P 319.6P 319.6P 319.6P 102.0P 104.0P
Polymerization temperature 110C 110C 110C 110C 110C 90C
Solids content48.5X gelled 49.6% gelled 48.5% 48.7X
V;sc. (dPa.s) 0.3 2.2 1.4 1.9 1~9~89 The acrylate resins from Examples 3 and 6 ~ere concentrated to a solids content of 64.4 (3) and 59.8~
(6) by removing solvent mixture by distillation, and were employed in this form in the paints.
The copolymers sf Examples 6, 8 and 10 ~ere analyzed by gel-permeation chromat3graphy. The following values were obtained:
Exam~lë Fn lMw 6 2 830 60 000 21,2 8 3 000 80 000 26,3 3 500 95 000 26,9 ~L2~
Example No. 7 8 9 10 11 Initial amount of solvent 637.0P6Z1.4P 556.6P 557.2P 519.3P
~-Methacryloxy-propyltrimethosy-silane 60.0P 60.0P 180.0P 180.0P 180.0P
Hexanediol diacrylate - - 120.0P 12~.0P 120.0P
D;vinylbenzene (64% strength in ethyLstyrene)120.ûP120.0P - - -Methyl meth-acrylate 180.0P180.0P 120~0P 120.0P 120.0P
tert.-Putyl acrylate - - 120.0P 10g.0P 84.0P
n-~utyl acrylate - - 60.0P 60.0P 60.0P
2-Ethylhexyl acrylate 120.0P120.0P
Cyclohexyl methacrylate120.0P120.0P
Acrylamide - - - 12.0P
Acrylic acid/
Card. adduct (48.8% strength Z5 in toluene)* - - - - 73.5P
Regulator 90.0R1 104.4R338.4Q338.4R3 38.4R3 Initiator 21.0 I2 Z1.0 I2 20.4 IZ 20.4 I2 20.4 I2 Solvent for initiator 104.0P 10~.0P 102.0P . 102.0P102.0P
30 Polymerization temperature 90C ~0C 110C 110C 110C
Solids content gelled 49% 49% 49O5X 50.1X
Visc. (dPa.sj 2.0 1~55 2.8 3.8 The acrylic acid/Cardura E 10 adduct was prepared as follo~s:
750 parts of Cardura E 10 (glycidyl ester of a branched ~ p ~
12'900B9 C-10 carboxylic ac;d) and 988 parts of toluene were heated to 100C together with 0.988 parts of hydroquinone, and 238 parts of acrylic acid were metered in within 30 min-utes. The mixture was kept at 100C, 1 part of a chromium S salt complex was added 2.5 hours after the acrylic acid additionr a further 0.1 parts of a chromium salt complex were added after a further 5 hours at 110C, and an acid number of 18.5 (mg of KOH~ was reached after a further 5 hours. The product had a solids content of 48.8%.
9~08~
~) Preparation of paints according to the invention Clear-coat composition1) Paint 1 Paint 2 Acrylate resin from Example 6 76 Acrylate resin fro~ Example 3 - 47 Acrylate resin from Example 1 - 27 Polysiloxane/polyether solution (0.006X strength) 4 4 Light-screen (HALS product)2) 1~2 1.2 UY absorber (oxalanilide)3) Butyl glycol acetate 2 Z
HutyL acetate 14.3 16.3 Dibutyltin dilaurate solution (10% strength in xylene) 1.5 1.5 100.0 100.0 Paint thinner4) 27 9 11 9 Spray viscosity tDIN 4 beaker) 18 s 18 s Processing solids content (1 h/130C) 36.5Z 40%
1) The positions are stirred successively with a dissol-ver.
B 2) Tinuvin~292, Ciba Geigy 3) Sanduvo ~VSU, Sandoz AG
4) Xylene/butyl acetate~methoxypropyl acetate 1/1/1 D~
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Claims (41)
1. A polymer containing silyl groups, the silyl groups having been introduced into the polymer by means of an ethyleni-cally unsaturated monomer of the general formula (a) where R1 = alkyl, aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an organic radical having a polymerizable double bond, X = a hydrolyzable group, and n = 1, 2 or 3, wherein the polymer can be obtained by copolymerization of a) 0.1 to 40% by weight of the silane monomer (a), b) 5 to 30% by weight of a monomer containing at least 2 polymerizable, ethylenically unsaturated double bonds, and c) 30 to 90% by weight of an ethylenically unsaturated monomer without groups containing active hydrogen, where the sum of a), b) and c) is 100% by weight.
2. A polymer as claimed in claim 1 wherein component c) is present in an amount of 8 to 25% by weight.
3. A polymer as claimed in claim 1, wherein component a) is .gamma.-methacryloxypropyltrimethoxysilane.
4. A polymer as claimed in claim 1, wherein component b) corresponds to the general formula CH2 = where R = H, CH3 or alkyl, Y - 0, NH or S, and n = 2 to 8.
5. A polymer as claimed in claim 1, 2 or 3, wherein compon-ent b) is a polycarboxylic acid or unsaturated monocarboxylic acid which is esterified with an unsaturated alcohol containing a polymerizable double bond.
6. A polymer as claimed in claim 1, 2 or 3, wherein compon-ent b) is a product of the reaction of a polyisocyanate and an unsaturated alcohol or an unsaturated amine.
7. A polymer as claimed in claim 1, 2 or 3, wherein compon-ent b) is a diester of polyethylene glycol and/or polypropylene glycol having an average molecular weight of less than 1,500, and acrylic acid and/or methacrylic acid.
8. A polymer as claimed in claim 1, a or 3 wherein component b) is a diester of polyethylene glycol and/or polypropy-lene glycol having an average molecular weight of less than 1,000, and acrylic acid and/or methacrylic acid.
9. A polymer as claimed in claim 1, 2 or 3, wherein, in addition to the ethylenically unsaturated monomers a), b) and c), up to 10% by weight of an ethylenically unsaturated carboxamide d) is used, where the sum of a), b), c) and d) is 100% by weight.
10. A polymer as claimed in claim 1, 2 or 3, wherein, in addition to the ethylenically unsaturated monomers a), b), c) and up to 10% by weight of an ethylenically unsaturated carboxamide d), up to 5% by weight of e) ethylenically unsaturated monomers having a hydroxyl, carboxyl or amino group are used, where the sum of a), b), c), if present d) and e) is 100% by weight.
11. A polymer as claimed in claim 4, wherein there are used more than 10% by weight of the monomers b), up to 10% by weight of an ethylenically unsaturated carboxamide d) and up to 5% by weight of ethylenically unsaturated monomers having a hydroxyl, carboxyl or amino group e) are also copolymerized, where the sum of a), b), c), if present d) and if present e) is 100% by weight, and the copolymerization is carried out using more than 5% by weight, re-lative to the total weight of the monomers, of mercaptoethyltri-ethoxysilane or mercaptopropylmethyldimethoxysilane.
12. A polymer as claimed in claim 4, wherein the ethyleni-cally unsaturated monomers of component b) are employed in a proportion of at least 15% by weight, component c) is mainly acrylate monomers and/or methacrylate monomers and/or maleates and/or fumarates, where the sum of all ethylenically unsaturated monomers is 100% by weight, and the copolymerization is carried out using more than 6% by weight, relative to the weight of monomers, of a mercaptosilane.
13. A polymer as claimed in claim 4, wherein the ethyleni-cally unsaturated monomers of component b) are employed in a pro-portion of at least 15% by weight, component c) is mainly acrylate monomers and/or methacrylate monomers and/or maleates and/or fumarates, where the sum of all ethylenically unsaturated monomers is 100% by weight, and the copolymerization is carried out using more than 6% by weight, relative to the weight of monomers, of mercaptoethyltriethoxysilane or mercaptopropylmethyl-dimethoxy-silane.
14. A polymer as claimed in claim 1, wherein component b) is more than 10% by weight of divinylaromatics and the polymeriza-tion is carried out using more than 10% by weight, relative to the weight of monomers, of mercaptoethyltriethoxysilane or mercapto-propylmethyldimethoxysilane.
15. A process for the preparation of a polymer containing silyl groups, the silyl groups being introduced into the polymer by means of ethylenically unsaturated monomers of the general formula (a) where R1 = alkyl, aryl, acyl or aralkyl having 1 to 10 carbon atoms, R2 = an-organic radical having a polymerizable double bond, X = a hydrolyzable group, and n = 1, 2 or 3, wherein, for its preparation, a) 0.1 to 40% by weight of the silane monomers (a), b) 5 to 30% by weight of a monomer containing at least 2 polymerizable, ethylenically unsaturated double bonds, and c) 30 to 90% by weight of an ethylenically unsaturated monomer without groups containing active hydrogen, where the sum of a), b) and c) is 100% by weight, are copolymerized in an organic solvent using an initiator and using at least 2% by weight, relative to the total weight of the monomers, of a polymerization regulator without OH and NH groups at 80°C to 130°C.
16. A process as claimed in claim 15, wherein component a) is .gamma.-methacryloxypropyltrimethoxysilane.
17. A process as claimed in claim 15, wherein component b) corresponds to the general formula CH2 = where R = H, CH3 or alkyl, Y = 0, NH or S, and n = 2 to 8.
18. A process as claimed in claim 15, 16 or 17, wherein component b) is apolycarboxylic acid or unsaturated monocarboxylic acid which is esterified with an unsaturated alcohol containing a polymerizable double bond.
19. A process as claimed in claim 15, 16 or 17, wherein component b) is a product of the reaction of a polyisocyanate and an unsaturated alcohol or an unsaturated amine.
20. A process as claimed in claim 15, 16 or 17, wherein component b) is a diester of polyethylene glycol and/or polypropy-lene glycol having an average molecular weight of less than 1,500 and acrylic acid and/or methacrylic acid.
21. A process as claimed in claim 15, 16 or 17, wherein component b) is a diester of polyethylene glycol and/or polypropy-lene glycol having an average molecular weight of less than 1,000, and acrylic acid and/or methacrylic acid.
22. A process as claimed in claim 15, 16 or 17, wherein, in addition to the ethylenically unsaturated monomers a), b) and c), up to 10% by weight of an ethylenically unsaturated carboxamide d) is used, where the sum of a), b?, c) and d) is 100% by weight.
23. A process as claimed in claim 15, 16 or 17, wherein, in addition to the ethylenically unsaturated monomers a), b), c) and up to 10% by weight of an ethylenically unsaturated carboxamide d), up to 5% by weight of e) ethylenically unsaturated monomers having a hydroxyl, carboxyl or amino group are used, where the sum of a), b), c), if present d) and e) is 100% by weight.
24. A process as claimed in claim 17, wherein there are used more than 10% by weight of the monomers b), up to 10% by weight of an ethylenically unsaturated carboxamide d) and up to 5% by weight of ethylenically unsaturated monomers having a hydroxyl, carboxyl or amino group e) are also copolymerized, where the sum of a), b), c), if present d) and if present e) is 100% by weight, and the copolymerization is carried out using more than 5% by weight, re-lative to the total weight of the monomers, of mercaptoethyltri-ethoxysilane or mercaptopropylmethyldimethoxysilane.
25. A process as claimed in claim 17, wherein there are used more than 10% by weight of the monomers b), up to 10% by weight of an ethylenically unsaturated carboxamide d) and up to 5% by weight of ethylenically unsaturated monomers having a hydroxyl, carboxyl or amino group e) are also copolymerized, where the sum of a), b), c), if present d) and if present e) is 100% by weight, and the copolymerization is carried out using more than 5% by weight, relative to the total weight of the monomers, of mercaptoethyltri-ethoxysilane or mercaptopropylmethyldimethoxysilane, together with one or more other mercapto compounds at a temperature between 100°
and 120°C.
and 120°C.
26. A process as claimed in claim 17, wherein the ethyleni-cally unsaturated monomers of component b) are employed in a pro-portion of at least 15% by weight, component c) is mainly acrylate monomers and/or methacrylate monomers and/or maleates and/or fumarates, where the sum of all ethylenically unsaturated monomers is 100% by weight, and the copolymerization is carried out using more than 6% by weight, relative to the weight of monomers of mercaptosilane.
27. A process as claimed in claim 17, wherein the ethyleni-cally unsaturated monomers of component b) are employed in a pro-portion of at least 15% by weight, component c) is mainly acrylate monomers and/or methacrylate monomers and/or maleates and/or fumarates, where the sum of all ethylenically unsaturated monomers is 100% by weight, and the copolymerization is carried out using more than 6% by weight, relative to the weight of monomers, of mercaptoethyltriethoxysilane or mercaptopropylmethyl-dimethoxysilane.
28. A process as claimed in claim 17, wherein the ethyleni-cally unsaturated monomers of component b) are employed in a pro-portion of at least 15% by weight, component c) is mainly acrylate monomers and/or methacrylate monomers and/or maleates and/or fumarates, where the sum of all ethylenically unsaturated monomers is 100% by weight, and the copolymerization is carried out using more than 6% by weight, relative to the weight of monomers, of a mercaptosilane, together with one or more other mercapto compounds.
29. A process as claimed in claim 15, wherein component b) is more than 10% by weight of divinylaromatics and the polymeriza-tion is carried out using more than 10% by weight, relative to the weight of monomers, of mercaptoethyltriethoxysilane or mercapto-propylmethyldimethoxysilane.
30. A process as claimed in claim 15, 16 or 17, wherein the initiator is an azo compound or a peroxy ester.
31. A process as claimed in claim 15, 16 or 17, wherein the polymerization regulator is a mercaptosilane.
32. A process as claimed in claim 15, 16 or 17, wherein the polymerization regulator is a mercaptosilane together with other mercapto compounds.
33. A process as claimed in claim 15, 16 or 17, wherein the polymerization regulator is mercaptoethyltriethoxysilane.
34. A process as claimed in claim 15, 16 or 17, wherein at least 4% by weight, relative to the total weight of the monomers, of a polymerization regulator are used.
35. A process as claimed in claim 15, 16 or 17, wherein the free-radical polymerization for the preparation of the polymer containing silyl groups is carried out in a fashion such that a solution of the polymer having a solids content of 40-65% by weight results.
36. A coating agent which can be hardened through moisture and which contains a silyl group-containing polymer as claimed in claim 1, an organic solvent, and also a crosslinking catalyst.
37. A coating agent as claimed in claim 36 which also con-tains a pigment, a filler and auxiliaries and additives.
38. A process for the preparation of a coating agent which contains the polymer prepared by the processes as claimed in claim 15, wherein the silyl group-containing polymer and an organic solvent are processed into a coating composition by mixing and, if appropriate, dispersing, and the composition is admixed with a crosslinking catalyst shortly before use.
39. A process as claimed in claim 38 wherein a pigment, a filler and auxiliaries and additives are admixed as components of the coating agent.
40. A process for repairing automobile repair paintwork which includes the step of applying a coating agent as claimed in claim 36 to the automobile.
41. A process as claimed in claim 40 wherein the coating agent as claimed in claim 36 is used as a base coat containing metal pigments and/or pigments and/or a top coat of multilayer paintwork.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3630793.9 | 1986-09-10 | ||
| DE19863630793 DE3630793A1 (en) | 1986-09-10 | 1986-09-10 | BRANCHED POLYMERISATE CONTAINING SILYL GROUPS, METHOD FOR THE PRODUCTION THEREOF, COATING AGENTS BASED ON THE POLYMERISATE AND THE USE THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1290089C true CA1290089C (en) | 1991-10-01 |
Family
ID=6309291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000546383A Expired - Lifetime CA1290089C (en) | 1986-09-10 | 1987-09-09 | Branched polymer containing silyl groups, a process for the preparationthereof, coating agents based on the polymer, and the use thereof |
Country Status (11)
| Country | Link |
|---|---|
| EP (2) | EP0263306A1 (en) |
| JP (1) | JPH0649843B2 (en) |
| KR (1) | KR950003048B1 (en) |
| AU (1) | AU607712B2 (en) |
| BR (1) | BR8707852A (en) |
| CA (1) | CA1290089C (en) |
| DE (2) | DE3630793A1 (en) |
| DK (1) | DK248288D0 (en) |
| ES (1) | ES2019971B3 (en) |
| WO (1) | WO1988002010A1 (en) |
| ZA (1) | ZA876577B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3803450A1 (en) * | 1988-02-05 | 1989-08-17 | Hoechst Ag | EMISSIONS OF DISPERSION PAINT, PAINT PAINT, AND PLASTIC DISPERSION SPOUSE, AND METHOD OF MANUFACTURING THEM |
| US5204404A (en) * | 1989-03-21 | 1993-04-20 | E. I. Du Pont De Nemours And Company | Waterbased acrylic silane and polyurethane containing coating composition |
| EP0601219B1 (en) * | 1990-08-16 | 1997-09-10 | E.I. Du Pont De Nemours And Company | Waterbased acrylic silane and polyurethane containing coating composition |
| DE3942803A1 (en) * | 1989-12-23 | 1991-06-27 | Basf Lacke & Farben | METHOD FOR PRODUCING A MULTILAYER, PROTECTIVE AND / OR DECORATIVE COATING |
| DE4016999A1 (en) * | 1990-05-26 | 1991-11-28 | Basf Lacke & Farben | METHOD FOR PRODUCING A HARDENABLE COMPOSITION, THE HARDENABLE COMPOSITION PRODUCED BY THIS METHOD AND THEIR USE |
| JP3094044B2 (en) * | 1991-11-15 | 2000-10-03 | 鐘淵化学工業株式会社 | Curable composition |
| DE4329088A1 (en) * | 1993-08-30 | 1995-03-02 | Huels Chemische Werke Ag | Aqueous, silanol group-modified dispersions |
| DE4430729C2 (en) | 1994-08-30 | 2002-05-23 | Degussa | Acryloxypropylalkoxysilanes, process for their preparation and their use |
| ES2226345T3 (en) | 1998-03-12 | 2005-03-16 | Lucite International Uk Limited | POLYMER COMPOSITION. |
| WO2001089720A1 (en) * | 2000-11-02 | 2001-11-29 | Corus Staal Bv | Solution polymerized vinyl resin for primer applications |
| DE102007023282A1 (en) * | 2007-05-18 | 2008-11-20 | Bayer Materialscience Ag | Silane coatings of aminosilanes and epoxy-functional polyacrylates |
| WO2009007276A1 (en) * | 2007-07-06 | 2009-01-15 | Jotun A/S | Branched polymer and antifouling coating composition comprising the polymer |
| CN102369226B (en) * | 2009-02-04 | 2013-12-25 | 道康宁公司 | Method of forming non-random copolymer |
| DE102009016195A1 (en) | 2009-04-03 | 2010-10-07 | Basf Coatings Ag | Moisture-curing coating compositions based on aprotic solvents containing binders with alkoxysilane groups and their use |
| US9683125B2 (en) | 2013-01-03 | 2017-06-20 | Basf Coatings Gmbh | One-component, curable coating compositions, processes for making and using them, and coatings and articles prepared with them |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5114934A (en) * | 1974-07-30 | 1976-02-05 | Saiden Kagaku Kk | EKIJOSETSU CHAKURYOKUKYOKAHIFUKU SOSEIBUTSU |
| US4152508A (en) * | 1978-02-15 | 1979-05-01 | Polymer Technology Corporation | Silicone-containing hard contact lens material |
| US4216303A (en) * | 1979-01-26 | 1980-08-05 | George F. Tsuetaki | Oxygen-permeable contact lens compositions, methods and articles of manufacture |
| JPS5792004A (en) * | 1980-11-29 | 1982-06-08 | Dainippon Printing Co Ltd | Electron radiation curing composition |
| GB2089826B (en) * | 1980-12-18 | 1985-01-03 | Gen Electric | Abrasion resistant ultraviolet light curable hard coating compositions |
| CA1186436A (en) * | 1981-09-30 | 1985-04-30 | Michael J. Michno, Jr. | Curable molding compositions containing a poly(acrylate) |
| JPS5919918A (en) * | 1982-07-27 | 1984-02-01 | Hoya Corp | Oxygen permeable hard contact lens |
| JPS6157612A (en) * | 1984-08-23 | 1986-03-24 | Nippon Contact Lens:Kk | Contact lens material |
| DE3587828T2 (en) * | 1984-07-26 | 1994-09-29 | Kanegafuchi Chemical Ind | Crosslinkable polymer composition. |
| JPS6160771A (en) * | 1984-08-31 | 1986-03-28 | Kanegafuchi Chem Ind Co Ltd | Pressure-sensitive adhesive composition |
| JPS61141761A (en) * | 1984-12-12 | 1986-06-28 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
-
1986
- 1986-09-10 DE DE19863630793 patent/DE3630793A1/en not_active Withdrawn
-
1987
- 1987-09-03 ZA ZA876577A patent/ZA876577B/en unknown
- 1987-09-04 DE DE8787905748T patent/DE3766708D1/en not_active Expired - Lifetime
- 1987-09-04 KR KR1019880700516A patent/KR950003048B1/en not_active IP Right Cessation
- 1987-09-04 ES ES87905748T patent/ES2019971B3/en not_active Expired - Lifetime
- 1987-09-04 EP EP87112924A patent/EP0263306A1/en active Pending
- 1987-09-04 JP JP62505352A patent/JPH0649843B2/en not_active Expired - Lifetime
- 1987-09-04 WO PCT/EP1987/000499 patent/WO1988002010A1/en active IP Right Grant
- 1987-09-04 BR BR8707852A patent/BR8707852A/en not_active IP Right Cessation
- 1987-09-04 AU AU78777/87A patent/AU607712B2/en not_active Ceased
- 1987-09-04 EP EP87905748A patent/EP0324747B1/en not_active Expired - Lifetime
- 1987-09-09 CA CA000546383A patent/CA1290089C/en not_active Expired - Lifetime
-
1988
- 1988-05-06 DK DK248288A patent/DK248288D0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| ES2019971B3 (en) | 1991-07-16 |
| KR950003048B1 (en) | 1995-03-30 |
| AU607712B2 (en) | 1991-03-14 |
| DK248288A (en) | 1988-05-06 |
| ZA876577B (en) | 1988-03-07 |
| JPH0649843B2 (en) | 1994-06-29 |
| KR880701747A (en) | 1988-11-04 |
| DE3766708D1 (en) | 1991-01-24 |
| DE3630793A1 (en) | 1988-03-24 |
| BR8707852A (en) | 1989-10-03 |
| DK248288D0 (en) | 1988-05-06 |
| JPH01502342A (en) | 1989-08-17 |
| EP0263306A1 (en) | 1988-04-13 |
| AU7877787A (en) | 1988-04-07 |
| EP0324747A1 (en) | 1989-07-26 |
| EP0324747B1 (en) | 1990-12-12 |
| WO1988002010A1 (en) | 1988-03-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |