CA1244183A - Curable copolymers, a process for their preparation and their use - Google Patents
Curable copolymers, a process for their preparation and their useInfo
- Publication number
- CA1244183A CA1244183A CA000501325A CA501325A CA1244183A CA 1244183 A CA1244183 A CA 1244183A CA 000501325 A CA000501325 A CA 000501325A CA 501325 A CA501325 A CA 501325A CA 1244183 A CA1244183 A CA 1244183A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- alkyl
- weight
- hydroxyalkyl
- alkyl radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/22—Esters containing nitrogen
-
- 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
- C09D135/00—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 at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Fertilizers (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
Copolymers based on A) 5-95% by weight of at least one polymerizable carbamoyloxyalkyldicarboxylic acid ester, carrying hydroxyl groups, of the general formula I
in which R1 represents hydrogen or alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, R2 represents alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, or the radical subject to the pro-viso that R1 is hydrogen and x is an integer from 2 to 10, R3 represents linear or branched alkylene having 2 to 5 carbon atoms, R4 represents hydrogen or methyl and R5 represents hydroxyalkyl or hydroxyaminoalkyl having in each case 2 to 20 carbon atoms in the alkyl radical, or an alkyl radical of this type which also contains ester groups and/or ether groups, and 8) 5-95% by weight of at least one copolymerizable monomer belonging to the group comprising a) .alpha.,.beta.-olefinically unsaturated monocarboxylic acid and alkyl and hydroxyalkyl esters thereof having in each case 1 to 18 carbon atoms in the alkyl radical, and amides and nitriles thereof, and also monoalkyl and dial-kyl esters of .alpha.,.beta.-olefinically unsaturated dicarboxylic acids having 1 to 18 carbon atoms in the alkyl radical, b) vinyl-aromatic monomers, c) vinyl esters of organic mono-carboxylic acids having 1 to 18 carbon atoms in the car-boxylic acid radical, and d) glycidyl esters of unsatura-ted monocarboxylic and/or dicarboxylic acids, the sum of the components A) and B) being in all cases 100% by weight, and a process for their preparation.
The copolymers are used for the preparation of shaped articles and/or coatings which have excellent properties.
Copolymers based on A) 5-95% by weight of at least one polymerizable carbamoyloxyalkyldicarboxylic acid ester, carrying hydroxyl groups, of the general formula I
in which R1 represents hydrogen or alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, R2 represents alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, or the radical subject to the pro-viso that R1 is hydrogen and x is an integer from 2 to 10, R3 represents linear or branched alkylene having 2 to 5 carbon atoms, R4 represents hydrogen or methyl and R5 represents hydroxyalkyl or hydroxyaminoalkyl having in each case 2 to 20 carbon atoms in the alkyl radical, or an alkyl radical of this type which also contains ester groups and/or ether groups, and 8) 5-95% by weight of at least one copolymerizable monomer belonging to the group comprising a) .alpha.,.beta.-olefinically unsaturated monocarboxylic acid and alkyl and hydroxyalkyl esters thereof having in each case 1 to 18 carbon atoms in the alkyl radical, and amides and nitriles thereof, and also monoalkyl and dial-kyl esters of .alpha.,.beta.-olefinically unsaturated dicarboxylic acids having 1 to 18 carbon atoms in the alkyl radical, b) vinyl-aromatic monomers, c) vinyl esters of organic mono-carboxylic acids having 1 to 18 carbon atoms in the car-boxylic acid radical, and d) glycidyl esters of unsatura-ted monocarboxylic and/or dicarboxylic acids, the sum of the components A) and B) being in all cases 100% by weight, and a process for their preparation.
The copolymers are used for the preparation of shaped articles and/or coatings which have excellent properties.
Description
HOECHST AKTIENGcSELLSCHAFT HOE 85/F OZ~ Dr. K/gt Curable co olymers a proce their use It is kno~n to cure poLyacryl;c comoounds contain;ng hydroxyl groups by means of polyisocyanates or masked polyisocyanates.
Copolymers of carbamoyloxycarboxylates carrying no hy~
droxyl groups are also known (US Patent 3,479,3Z8)~ -~"
order to cure copolymers of th;s type, the latter are mo-dified with aldehydes o give compounds earrying alkyl~l groups. These alkylol groups can additionally also be etherified. The aldehyde-modified polymer5 are more reactive, but less stable than the etherif;ed polymer~
Polymers modified ;n this manner can be crosslinked b~
using crosslinking agents which are su;table ~or poly_ mers containin~ alkylol groups. These agents include, for example, methylolphenol-formaldehYde and melam;ne~
formaldehyde resins, and also ac;ds, such as P-toluen~
sulfonic acid.
It ;s also known ~German Patent 2,422,170) to prepare ZO copolymers from carbamoyloxyalkylcarboxylic acid este~S
and copolymerizable monomers. The curing of these co~
polymers by using polyisocyanates and/or amine resins cannot, however, be inferred from the state of the ar~.
The invention was therefore based on the object of pr~-paring co~olymers which, by virtue of the simultaneou~
presence of hydroxyl and urethane groups, exhib;t a h~gh functionality and hence a high reactivity and which are therefore distinguished by particularly advantageou~ Dro-perties.
The ;nvention relates to curable copolymers based on A) 5-95X by weight of at least one polymerizable carbamo~l-oxyalkyldicarboxylic acid ester, carrying hydroxyl groups, of the general formula (I) ~2~ L$~
~ 2 -R~ O R4 O
N-c-o-R3-o-c-c-cH-c-oR5 (I) R~
in wh;ch R1 represents hydrogen or alkyl or hydroxyalkyl hav;ng in each case 1 to 30 carbon atoms ;n the alkyl rad;-Scal, R2 represents alkyl or hydroxyalkyl having in each case1 to 30 carbon atoms in the alkyl radical, or the ra-dical R1O subject to the prov;so -(CH2)x-N-C-O-R -OH
that R1 is hydrogen and x is an ;nteger from Z to 10, R3 represents linear or branched alkylene having 2 to 5 carbon atoms, R4 represents hydrogen or methyl and R5 represents hydroxyalkyl or hydroxyaminoalkyl having in each case 2 to 20 carbon atoms in the alkyl radi-cal, or an alkyl radical of this type which also con-ta;ns ester and/or ether groups, and B) 5-95% by we;ght of at least one copolymer;zable mono mer belong;ng to the group compr;sing 2n a) an ~ olef;n;cally unsaturated monocarboxyl;c ac;d and alkyl and hydroxyalkyl esters thereof having ;n each case 1 to 18, preferably 1 to 8, carbon atoms ;n the alkyl radical, and amides and nitriles thereof, and also monoalkyl and dialkyl esters of ~ olefin;-cally unsaturated d;carboxylic acids having 1 to 18 carbon atoms ;n the alkyl rad;cal, b) v;nyl-aromat;c monomers, c) v;nyl esters of organic monocarboxylic ac;ds hav;ng 1 to 18 carbon atoms ;n the carboxyl;c ac;d rad;cal, and d) glycidyl esters of unsaturated monocarboxylic and/or dicarboxylic acids, the sum of the components ~ and B) be;ng in all cases 100%
by weight.
_ 3 The component B) contains at least one monomer, the rat;os being, in general, O - 95% by weight of the monomers a), 5 - 100X by weight of the monomers b), û - 95X by we;ght of the monomers c) and O - 50% by we;ght of the monomers S dl and the sum of all the monomers being in all cases 100Y. by weight.
The invention also relates to a process for the prepara-tion of the copolymers and to their use.
In the general formula (~), R1 preferably denotes hydrogen or alkyl or hydroxyalkyl having in each case Z to 2û carbon atoms 1n the alkyl radical, R2 preferably denotes alkyl or hydroxyalkyl having in each case 2 to 20 carbon atoms ;n the alkyl radical,
Copolymers of carbamoyloxycarboxylates carrying no hy~
droxyl groups are also known (US Patent 3,479,3Z8)~ -~"
order to cure copolymers of th;s type, the latter are mo-dified with aldehydes o give compounds earrying alkyl~l groups. These alkylol groups can additionally also be etherified. The aldehyde-modified polymer5 are more reactive, but less stable than the etherif;ed polymer~
Polymers modified ;n this manner can be crosslinked b~
using crosslinking agents which are su;table ~or poly_ mers containin~ alkylol groups. These agents include, for example, methylolphenol-formaldehYde and melam;ne~
formaldehyde resins, and also ac;ds, such as P-toluen~
sulfonic acid.
It ;s also known ~German Patent 2,422,170) to prepare ZO copolymers from carbamoyloxyalkylcarboxylic acid este~S
and copolymerizable monomers. The curing of these co~
polymers by using polyisocyanates and/or amine resins cannot, however, be inferred from the state of the ar~.
The invention was therefore based on the object of pr~-paring co~olymers which, by virtue of the simultaneou~
presence of hydroxyl and urethane groups, exhib;t a h~gh functionality and hence a high reactivity and which are therefore distinguished by particularly advantageou~ Dro-perties.
The ;nvention relates to curable copolymers based on A) 5-95X by weight of at least one polymerizable carbamo~l-oxyalkyldicarboxylic acid ester, carrying hydroxyl groups, of the general formula (I) ~2~ L$~
~ 2 -R~ O R4 O
N-c-o-R3-o-c-c-cH-c-oR5 (I) R~
in wh;ch R1 represents hydrogen or alkyl or hydroxyalkyl hav;ng in each case 1 to 30 carbon atoms ;n the alkyl rad;-Scal, R2 represents alkyl or hydroxyalkyl having in each case1 to 30 carbon atoms in the alkyl radical, or the ra-dical R1O subject to the prov;so -(CH2)x-N-C-O-R -OH
that R1 is hydrogen and x is an ;nteger from Z to 10, R3 represents linear or branched alkylene having 2 to 5 carbon atoms, R4 represents hydrogen or methyl and R5 represents hydroxyalkyl or hydroxyaminoalkyl having in each case 2 to 20 carbon atoms in the alkyl radi-cal, or an alkyl radical of this type which also con-ta;ns ester and/or ether groups, and B) 5-95% by we;ght of at least one copolymer;zable mono mer belong;ng to the group compr;sing 2n a) an ~ olef;n;cally unsaturated monocarboxyl;c ac;d and alkyl and hydroxyalkyl esters thereof having ;n each case 1 to 18, preferably 1 to 8, carbon atoms ;n the alkyl radical, and amides and nitriles thereof, and also monoalkyl and dialkyl esters of ~ olefin;-cally unsaturated d;carboxylic acids having 1 to 18 carbon atoms ;n the alkyl rad;cal, b) v;nyl-aromat;c monomers, c) v;nyl esters of organic monocarboxylic ac;ds hav;ng 1 to 18 carbon atoms ;n the carboxyl;c ac;d rad;cal, and d) glycidyl esters of unsaturated monocarboxylic and/or dicarboxylic acids, the sum of the components ~ and B) be;ng in all cases 100%
by weight.
_ 3 The component B) contains at least one monomer, the rat;os being, in general, O - 95% by weight of the monomers a), 5 - 100X by weight of the monomers b), û - 95X by we;ght of the monomers c) and O - 50% by we;ght of the monomers S dl and the sum of all the monomers being in all cases 100Y. by weight.
The invention also relates to a process for the prepara-tion of the copolymers and to their use.
In the general formula (~), R1 preferably denotes hydrogen or alkyl or hydroxyalkyl having in each case Z to 2û carbon atoms 1n the alkyl radical, R2 preferably denotes alkyl or hydroxyalkyl having in each case 2 to 20 carbon atoms ;n the alkyl radical,
2 x l1~l H
R O
proviso that R1 is hydrogen and x is an integer from 2 to 6, R3 preferably denotes alkylene having 2 to 3 carbon atoms, R4 preferably denotes hydrogen or methyl and R5 preferably denotes a hydroxyalkyl ester radical of a branched, saturated fatty acid having 9 to 11 carbon atoms in the acid radical, or hydroxyalkyl, each hav-ing 2 to 14 carbon atoms in the alkyl groupO
The compounds used as the starting material, carbamoyl-oxyalkyldicarboxylic acid esters of the general formula (I) are described in Canadian Patent Application Serial No. 501,331 filed on the same day, "Polymerizable, carbamoyloxyalkyl-dicarboxyl;c acid esters carrying hydroxyl groups, a pro-cess for their preparation and their use". The startingmaterials are prepared by the processes mentioned in the parallel application, to which reference is hereby made, including the preferred embodiments. One or more monomers from the following groups can be employed for the copoly-h 35 merization of the compound of the formula (I):
.,sj ~
~ 4 --a) ~ olefinically unsaturated monocarboxyl;c acids, alkyl and hyclroxyalkyl esters thereof having in each case 1 to 1~, preferably 1 to 8 carbon atoms in the alkyl radical, and amides and nitriles thereof, and S monoalkyl and dialkyl esters of ~,~-olefinically un-saturated dicarboxylic acids having 1 to 18, prefer-ably 1 to 8 carbon atoms in the alkyl radical, such as acrylic acid and ~ethacrylic acid, methyl and ethyl esters thereof, the various isopropyl esters, the va-rious butyl esters, 2-ethylhexyl ester or stearyl ester, preferably acrylic acid, acrylonitrile~ acryl-amide, methyl acrylate, butyl acrylate, Z-ethylhexyl acrylate and methyl methacrylate, and also Z-hydroxy (neth)acrylate, 2-hydroxypropyl (meth)acrylate~ 4-hydroxybutyl (meth)acrylate and also reaction pro-ducts of (meth)acrylic acid with a glycidyl ester of ~-alkylalkanemonocarboxylic acicls of the empirical formula C12-14H22-263, individually or as a mixture.
The glycidyl radical in the glycidyl ester of the ~-alkylalkanemonocarboxylic acids and/or ~,~-dialkyl-alkanemonocarboxylic acids has the empirical formula C3HsO. The mixtures of ~-alkylalkanoic acids and mixtures of ~,~-dialkylalkanoic acids are monocar-boxylic acids containing a C9, C10 and C11 chain (de-scribed as glycidyl esters in the following text), b) vinyl-aromatic monomers~ such as styrene, o-methyl-styrene, p-methylstyrene, ~-methylstyrene and styrene derivatives alkylated in the nucleus, such as ~-methyl-p-isopropylstyrene and ~-methyl-m-isopropylstyrene, but preferably styrene, c~ vinyl esters of organic monocarboxylic acids having 1 to 18, preferably 2 to 11, carbon atoms in the acid component, such as vinyl acetate and vinyl propionate, preferably vinyl acetate, and the vinyl ester of Versatic acid and d3 glycidyl esters of ~ olefinically unsaturated monocarboxylic and/or dicarboxylic acids, such as gly-cidyl ~meth)acrylate.
The proportion of rompounds of the formula (I) ;n the co-polymer (component A) is 5 to 95, preferably 10 to 7D, %
by ~eight, whereas the proport;on of copolymerizable mo-nomers B3amounts to 5 to 95, preferably 30 to 90, Z by ~eight. The sum of the components A)and ~);s in all cases 1 dox u At least one of the monomers a~ to d) can be used as component B). How-ever, preferred amounts are 0 to 95% by weight of the monomers a), 5 to 100% by weight of the monomers b), 0 to 95X by weight of the mono-mers c) and 0 to 50% by weight of the monomers d), the sum of the monomers being in all cases 100% by weight.
The process for the preparation of the copolymers is, ;n general, well known. The polymerization is preferably effected by the radical chain mechanism in the presence of substances uhich provide free radicals. Substances suitable for this are inorganic per-compounds, such as potassium persulfate or ammonium persulfate, alkali metal percarbonates, organic peroxide compounds, such as acyl peroxides, for example benzoyl peroxide, dibenzoyL perox-ide, di-tert.-butyl peroxide, d;lauryl peroxide, dicumyl peroxide and tert~-butyl perbenzoate, alkyl hydroperox-idesO such as tert.-butyl hydroperoxide, cumene hydro-peroxide, tert.-butyl hydroperoxide and tert.-butyl per-octoate, or azo compounds, such as ~ azobisisobutyro-nitr;le, and also peroxodicarbonates, such as dicyrlo-hexyl and dicetyl peroxodicarbonate. The amount of cata-Lyst is within the limits usually suitable, ie;, for in-stance, between 0.01 and 5, preferably 0.01 and 2, % by weight, calculated on the total amount of monomers. In many cases it can also be desirable to add to the mixture of polymers molecular weight regulators, such as chain transfer agents or cha;n stoppers. Mercaptans, such as dc,decyL mercaptan are normally used for this purpose, but it is also possible to add other agents which modify the chain length, such as cyclopentadiene, allyl carba-mate, dimerized ~-methylstyrene and similar agents which ~ ~44~33 result in the formation of polymers of Low molecular weight. In gene-ral, 0.01 to 2, preferably 0.01 to 1, % by weight of these compounds, relative to the total amount of monomers, ;s added.
The poLymerization can be carried out in one stage or in several stages at temperatures from 20 to Z70C, prefer-ably 60 to 180C~ if necessary under pressure, and in accordance with the customary methods of mass Polymer;~a tion, solution po(ymerization, precipitation polymeriza-tion, dispersion polymer;zation, emulsion polymeri~ation or bead polymerization. Mass, solution and emulsion poly-merization, especiaLly solution po;ymerization, are pre-ferred. ~T polymerization is carried out in soLution, the customarily used solvents, such as halogenated hydro-carbons, for example methylene chloride, trichloroethy-lene or tetrachloroethane, ketones, such as acetone or methylethyL ketone, esters, such as butyL acetate, ethyl-glycoL acetate or methyLglycol acetate, ethylene gLycol bismethyl ether, diethylene glycol bismethyl ether, or aromatic hydrocarbons, such as toluene and xylene, are employed, in each case individually or as a mixture. A
preferred solvent is xylenep preferably mixed with an aro-matic sûlvent having a boiling range from 154 to 178C
(Solvesso 100, ShelL AG) and butyl acetate.
The copolymers formed generally have OH numbers of 30 to 200, preferabLy 45 ts 180 and particularly 50 to 140. The acid numbers of the copoLymers are, ;n general, <15, pre-ferabLy <9. The viscos;ty of the copolymers at 20C is generalLy 200 to 3,000, preferabLy 400 to 2,500, mPa.s.
The vaLues were determined from the resuLting solutions of the copolymers, after dilution with xylene to a solids content of 50X by weight (described in the following text as "20C, 50% strength in xylene").
The copolymers according to the invention can be cured by means of the customary compounds which can be used for Polymers containing OH groups. Compounds containing ter-minaL isocyanate groups are particularly su;tab~e~ Ex-amples of compounds of this type are polyisocyanates, ~2~
such as the aliphatic trimethylene, tetranethylene, pen-tamethylene, hexamethylene, 1,2-propylene, 1,2-butylene, 2,3-butylene, 1,3-butylene, ethylidene and butylidene diisocyanate, dicycloalkylené d;;socyanates, such as 1,3-cyclopentane, 1,~-cyclopentane and 1,2-cyclohexane d;;so-cyanates~ and also ;sophorone and hexamethylene d;;socya-nate, the aromat;c d;;socyanates, such as m-phenylene, p-phenylene, 4,4'-biphenyl, 1,5-naphthalene and 194-naph-thalene d;;socyanates, the al;phat;c-aromatic diisocyan-tes~ such as 4,4'-d;phenylenemethane, 2,4-toluylene or 2,6-toluylene ~or mixtures thereof), ~ toluidine and 1,4~xylylene diisocyanates, the nuclear-substituted aro-matic compounds, such as d;anisid;ne diisocyanate, 4,4'-diphenyl-ether di;socyanate and chlorod;phenylene di;so-cyanate, the triisccyanates, such as triphenylmethane4,4'-triisocyanate or 4"-triisocyanate, 1,3,5~benzene tr;;socyanate and 2,4,6-toluene tr;isocyanate, and~the tetraisocyanates, such as 4,4'-d;phenyld;methyld;methane 2,2'-5,5'-tetra;socyanate.
Instead of the poly;socyanates, ;t ;s also possible to use compounds wh;ch split off polyisocyanates, and also reaction products, conta;n;ng isocyanate groups, of poly-hydr;c alcohols w;th polyisocyanates, for example the reaction product of 1 mol of trimethylolpropane w;th 3 mol of toluylene diisocyanate, and also the polymer;zed poly;socyanates, such as the d;mer of tolylene di;socya nate and the like, or tr;meriied or polymer;zed ;socya-nates such as are descr;bed, for ;nstance~ ;n German Patent 951,168. Addit;onally, a react;on product formed from 1 mol of ~ater and 3 mol of hexamethylene d;;socya-nate hav;ng an NC0 content of 16-17% by weight is also suitable. The last-mentioned react;on product formed from water and hexamethylene diisocyanate is part;cularly preferred. The NC0 content of the react;on product app-l;es to a 75% strength by we;ght solut;on in xylene/ethyleneglycol acetate.
Amine resins are also suitable for curing the polymers according to the invention. Amine-aldehyde resins, i.e~ aldehyde condensation products of melamine, urea, aceto-guanamine or similar compounds may be mentioned as an example. Preferred aldehyde condensation products of melam;ne ;nclude hexamethoxy~ethylmelam;ne, hexakis-(methoxymethyl)melamine, ethoxymethoxy~ethylmelamine, hexamethylated methylolmelamine and the like and aLso benzyl urea and benzoguanamine.
The amount of crossl;nking agent employed depends on the OH number of the copolymers according to the invention.
In general, equimolar amounts are employed.
Curing is generally carr;ed out at a tempera~ure between O and 260C, preferably 20 to 150C. The temperature is dependent on the curing time. However, it is preferable to carry out the reaction at lou temperatures.
~y virtue of their va,ious functional groups, the copoly-mers prepared in accordance ~ith the invention have excel-lent properties. They exhibit, surprisingly, a very good resistance to chemicals at a relatively low hydroxyl num-ber~ for example resistance against gasoline, whereas theknown polyacryl;c resins in general only reach an adequate resistance to chemicals at OH numbers of at least 1ZO.
Furthermore, the copolymers according to the invention possess a high flexibility, toughness and elasticity anrJ
a good adhesion, so that they can, if desired, also be employed in mixtures of adhesives.
The copolymers according to the invention can be used in industry in a versatile manner, for example for the pre-paration of shaped articles and/or coatings. As a resultof the presence of urethane groups, they produce a very good adhesion on substrates. For this reason they are suitable, for example, for linings and coatings, for ex-ample for vessels used in the chemical industry and for articles exposed to weathering. They are employed as paints and coatings above all for vehicle components, par-ticularly for motor vehicles, industrial paints, house-hold equipment, furniture and in the building industry or the like. It is also possible to add pigments and other _ 9 _ customary additives to the coat;ng mater;als. Thus they are used, for example, as b;nders for p;gmented and clear prim;ng pa;nts andtor f;n;shing paints; they can also be employed in ;ntegrated plast;cs/metal coatings.
In the examples ~hich follow, p denotes parts by ~eight and X denotes percent by ~e;~ht.
Examples Starting materials The preparation of the carbamoyloxyalkyld;carboxylic 1~ ac;d esters~ carry;ng hydroxyl groupsr ~hich are used as the start;ng material and which are shown in Ta~le 1 can be carried out in accsrdance with d;rections such as are described in Canadian Patent Application Serial No. 501,331 already mentioned~
Table 1 Compound ~o_ ~ -CH2~ e A /~_~O_C~2_ ~ -OLC-~CH-C-0-GE
~0. ~ _ ~
~ ~ e IOH
B ~ ( ~ )3-C~ H-G~ ~ - ~ -O-C-~ ~ C-O~ ~ -CH-C~3-C~2 0 C C~( ~ )3-~-C~-N~ ~ ~ = ~ 0-GE
8~
Table 1 (contd~
- trtmpound O O
O O O' O
E ~ CH2~ 6 ~2 2 O O O 0 0~1 ~~ ~ - ~ -0-C-~H~ 6~ ~ c-c-cH=
GE = glycidyl ester The compounds Listed in Table 1 ~ere polymeri~ed, under nitrogen and ~;th st;rr;ng, ~ith the monomers l;sted ;n Table 2 in a solvent mixture co~posed of xylene, an aro-matic mixture of hydrocarbons having a boiling po;nt of 154 to 178C and butyl acetate t2~ Th;s ~as effected~ on the one hand, by initially taking the compounds of Table 1 together uith the solvent mixture and heating to 14~C, after ~hich the added monomer mixture 1 ~as metered in in the course of three hours at a rate determined by the exo-thermic reaction. The first stage of the copolymeriza-tion can also be carried out by initially taking part of ehe soLvent mixture, and the monomer mixture 1 is composed of the rest of the solvent, monomers and compounds of TabLe 1 and further additives (Example 3). In this case too, the monomer mixture 1 ;s added dropwise to the soL-vent mixture which has been heated to 140C.
After the total amount of the monomer mixture 1 had been ~dded, the monomer m;xture 2 was added in the course of four hours ~t 140C and~ ~hen the addition ~as co~plete, the ~ixture ~as allowed to stand at 140C for one hour.
Details of the resulting copolymers in respect of OH num-5 ber, acid number, solids con~ent and viscosity at 20C
t50X strength solution in xylene) are given ;n Table 2.
- 8 and 9 _.
The procedure of Ex~mples 1 to 7 was carried out using eompounds E and F from Table 1, ~i~h the difference that the copolymerization temperature was 150C and the sol-vent employed ~as ethylglycol acetate. Details relating to the monomers used, the proportions of ingred;ents and the physicaL data of the resulting copolymers are given in Tahle 2.
Table Z
Solvent P 1200 . 200 . ~3~ ~200 Compound from Tab. 1 A B C C
amount P 644 217 305 644 Monomer mixture 2n Solvent P - 100 167 Styr~ne P 57.2 22,2 27 57.2 DTDBP p 9~2 2.25 3.75 9.2 DDM P 6.0 1.35 2.25 6.0 ZS Monomer mixture Styrene 696 200 269 696 MMA P 272 28.4 116 272 HEMA P 80 34.5 34 8.0 30 DTD0P P g.2 2.253.75 g.2 DDM ~ 6.~ l ~52.25 ~.Q
'~
. - 12 -Table 2 (contd.) OH number 123100 60 60 Ac;d number 5-32.0 5,0 9 Sol;ds content (1hr/125C)60 60 59.6 59.3 5 Viscosity (20, 4902300 454 1053 5QX solution in xylene, mPa.s) DTD8P = di-tertO-d;butyl peroxide DDM - dodecyl mercaptan MMA = methyL methacrylate HEMA = hydroxyethyl methacrylate EGA = ethylglycol acetate Table 2 (contd.) Solvent P 500 500 lOOO 233 113 Co~pound from Tab. 1 B B C ~ ~
amount P 197 281 473 185 49 Monomer mixture Solvent P - - 200 lOO 66 Styrene P 31,6 151 7617.5 5 10 DTDBP P 3,75 3,75 9 2.5 1.5 DDM P 2.25 2.25 5.4 I.5 0.9 .
Monomer m;xture Styrene P 348 46 835 65 138 DTD8P P 3 75 3 75 9 2.5 1.5 DDM P 2.25 2.25 ~,4 1.5 0.4 OH number 60 lOO 51 140 71 2Q Acid number 4.8 4.6 3.1 8,1 3.C
Solids content (1hr/125C) 59.8 58.2 59.9 53 60 Viscosity (20, 842 1310 575 - 965 50% solution in (in ~A) xy(ene, mPa.s) 21 DTDBP = di-tert.-dibutyl peroxide DDM = dodecyl mercaptan MMA = methyl methacrylate HEMA = hydroxyethyL methacrylate EGA = ethylglycol acetate
R O
proviso that R1 is hydrogen and x is an integer from 2 to 6, R3 preferably denotes alkylene having 2 to 3 carbon atoms, R4 preferably denotes hydrogen or methyl and R5 preferably denotes a hydroxyalkyl ester radical of a branched, saturated fatty acid having 9 to 11 carbon atoms in the acid radical, or hydroxyalkyl, each hav-ing 2 to 14 carbon atoms in the alkyl groupO
The compounds used as the starting material, carbamoyl-oxyalkyldicarboxylic acid esters of the general formula (I) are described in Canadian Patent Application Serial No. 501,331 filed on the same day, "Polymerizable, carbamoyloxyalkyl-dicarboxyl;c acid esters carrying hydroxyl groups, a pro-cess for their preparation and their use". The startingmaterials are prepared by the processes mentioned in the parallel application, to which reference is hereby made, including the preferred embodiments. One or more monomers from the following groups can be employed for the copoly-h 35 merization of the compound of the formula (I):
.,sj ~
~ 4 --a) ~ olefinically unsaturated monocarboxyl;c acids, alkyl and hyclroxyalkyl esters thereof having in each case 1 to 1~, preferably 1 to 8 carbon atoms in the alkyl radical, and amides and nitriles thereof, and S monoalkyl and dialkyl esters of ~,~-olefinically un-saturated dicarboxylic acids having 1 to 18, prefer-ably 1 to 8 carbon atoms in the alkyl radical, such as acrylic acid and ~ethacrylic acid, methyl and ethyl esters thereof, the various isopropyl esters, the va-rious butyl esters, 2-ethylhexyl ester or stearyl ester, preferably acrylic acid, acrylonitrile~ acryl-amide, methyl acrylate, butyl acrylate, Z-ethylhexyl acrylate and methyl methacrylate, and also Z-hydroxy (neth)acrylate, 2-hydroxypropyl (meth)acrylate~ 4-hydroxybutyl (meth)acrylate and also reaction pro-ducts of (meth)acrylic acid with a glycidyl ester of ~-alkylalkanemonocarboxylic acicls of the empirical formula C12-14H22-263, individually or as a mixture.
The glycidyl radical in the glycidyl ester of the ~-alkylalkanemonocarboxylic acids and/or ~,~-dialkyl-alkanemonocarboxylic acids has the empirical formula C3HsO. The mixtures of ~-alkylalkanoic acids and mixtures of ~,~-dialkylalkanoic acids are monocar-boxylic acids containing a C9, C10 and C11 chain (de-scribed as glycidyl esters in the following text), b) vinyl-aromatic monomers~ such as styrene, o-methyl-styrene, p-methylstyrene, ~-methylstyrene and styrene derivatives alkylated in the nucleus, such as ~-methyl-p-isopropylstyrene and ~-methyl-m-isopropylstyrene, but preferably styrene, c~ vinyl esters of organic monocarboxylic acids having 1 to 18, preferably 2 to 11, carbon atoms in the acid component, such as vinyl acetate and vinyl propionate, preferably vinyl acetate, and the vinyl ester of Versatic acid and d3 glycidyl esters of ~ olefinically unsaturated monocarboxylic and/or dicarboxylic acids, such as gly-cidyl ~meth)acrylate.
The proportion of rompounds of the formula (I) ;n the co-polymer (component A) is 5 to 95, preferably 10 to 7D, %
by ~eight, whereas the proport;on of copolymerizable mo-nomers B3amounts to 5 to 95, preferably 30 to 90, Z by ~eight. The sum of the components A)and ~);s in all cases 1 dox u At least one of the monomers a~ to d) can be used as component B). How-ever, preferred amounts are 0 to 95% by weight of the monomers a), 5 to 100% by weight of the monomers b), 0 to 95X by weight of the mono-mers c) and 0 to 50% by weight of the monomers d), the sum of the monomers being in all cases 100% by weight.
The process for the preparation of the copolymers is, ;n general, well known. The polymerization is preferably effected by the radical chain mechanism in the presence of substances uhich provide free radicals. Substances suitable for this are inorganic per-compounds, such as potassium persulfate or ammonium persulfate, alkali metal percarbonates, organic peroxide compounds, such as acyl peroxides, for example benzoyl peroxide, dibenzoyL perox-ide, di-tert.-butyl peroxide, d;lauryl peroxide, dicumyl peroxide and tert~-butyl perbenzoate, alkyl hydroperox-idesO such as tert.-butyl hydroperoxide, cumene hydro-peroxide, tert.-butyl hydroperoxide and tert.-butyl per-octoate, or azo compounds, such as ~ azobisisobutyro-nitr;le, and also peroxodicarbonates, such as dicyrlo-hexyl and dicetyl peroxodicarbonate. The amount of cata-Lyst is within the limits usually suitable, ie;, for in-stance, between 0.01 and 5, preferably 0.01 and 2, % by weight, calculated on the total amount of monomers. In many cases it can also be desirable to add to the mixture of polymers molecular weight regulators, such as chain transfer agents or cha;n stoppers. Mercaptans, such as dc,decyL mercaptan are normally used for this purpose, but it is also possible to add other agents which modify the chain length, such as cyclopentadiene, allyl carba-mate, dimerized ~-methylstyrene and similar agents which ~ ~44~33 result in the formation of polymers of Low molecular weight. In gene-ral, 0.01 to 2, preferably 0.01 to 1, % by weight of these compounds, relative to the total amount of monomers, ;s added.
The poLymerization can be carried out in one stage or in several stages at temperatures from 20 to Z70C, prefer-ably 60 to 180C~ if necessary under pressure, and in accordance with the customary methods of mass Polymer;~a tion, solution po(ymerization, precipitation polymeriza-tion, dispersion polymer;zation, emulsion polymeri~ation or bead polymerization. Mass, solution and emulsion poly-merization, especiaLly solution po;ymerization, are pre-ferred. ~T polymerization is carried out in soLution, the customarily used solvents, such as halogenated hydro-carbons, for example methylene chloride, trichloroethy-lene or tetrachloroethane, ketones, such as acetone or methylethyL ketone, esters, such as butyL acetate, ethyl-glycoL acetate or methyLglycol acetate, ethylene gLycol bismethyl ether, diethylene glycol bismethyl ether, or aromatic hydrocarbons, such as toluene and xylene, are employed, in each case individually or as a mixture. A
preferred solvent is xylenep preferably mixed with an aro-matic sûlvent having a boiling range from 154 to 178C
(Solvesso 100, ShelL AG) and butyl acetate.
The copolymers formed generally have OH numbers of 30 to 200, preferabLy 45 ts 180 and particularly 50 to 140. The acid numbers of the copoLymers are, ;n general, <15, pre-ferabLy <9. The viscos;ty of the copolymers at 20C is generalLy 200 to 3,000, preferabLy 400 to 2,500, mPa.s.
The vaLues were determined from the resuLting solutions of the copolymers, after dilution with xylene to a solids content of 50X by weight (described in the following text as "20C, 50% strength in xylene").
The copolymers according to the invention can be cured by means of the customary compounds which can be used for Polymers containing OH groups. Compounds containing ter-minaL isocyanate groups are particularly su;tab~e~ Ex-amples of compounds of this type are polyisocyanates, ~2~
such as the aliphatic trimethylene, tetranethylene, pen-tamethylene, hexamethylene, 1,2-propylene, 1,2-butylene, 2,3-butylene, 1,3-butylene, ethylidene and butylidene diisocyanate, dicycloalkylené d;;socyanates, such as 1,3-cyclopentane, 1,~-cyclopentane and 1,2-cyclohexane d;;so-cyanates~ and also ;sophorone and hexamethylene d;;socya-nate, the aromat;c d;;socyanates, such as m-phenylene, p-phenylene, 4,4'-biphenyl, 1,5-naphthalene and 194-naph-thalene d;;socyanates, the al;phat;c-aromatic diisocyan-tes~ such as 4,4'-d;phenylenemethane, 2,4-toluylene or 2,6-toluylene ~or mixtures thereof), ~ toluidine and 1,4~xylylene diisocyanates, the nuclear-substituted aro-matic compounds, such as d;anisid;ne diisocyanate, 4,4'-diphenyl-ether di;socyanate and chlorod;phenylene di;so-cyanate, the triisccyanates, such as triphenylmethane4,4'-triisocyanate or 4"-triisocyanate, 1,3,5~benzene tr;;socyanate and 2,4,6-toluene tr;isocyanate, and~the tetraisocyanates, such as 4,4'-d;phenyld;methyld;methane 2,2'-5,5'-tetra;socyanate.
Instead of the poly;socyanates, ;t ;s also possible to use compounds wh;ch split off polyisocyanates, and also reaction products, conta;n;ng isocyanate groups, of poly-hydr;c alcohols w;th polyisocyanates, for example the reaction product of 1 mol of trimethylolpropane w;th 3 mol of toluylene diisocyanate, and also the polymer;zed poly;socyanates, such as the d;mer of tolylene di;socya nate and the like, or tr;meriied or polymer;zed ;socya-nates such as are descr;bed, for ;nstance~ ;n German Patent 951,168. Addit;onally, a react;on product formed from 1 mol of ~ater and 3 mol of hexamethylene d;;socya-nate hav;ng an NC0 content of 16-17% by weight is also suitable. The last-mentioned react;on product formed from water and hexamethylene diisocyanate is part;cularly preferred. The NC0 content of the react;on product app-l;es to a 75% strength by we;ght solut;on in xylene/ethyleneglycol acetate.
Amine resins are also suitable for curing the polymers according to the invention. Amine-aldehyde resins, i.e~ aldehyde condensation products of melamine, urea, aceto-guanamine or similar compounds may be mentioned as an example. Preferred aldehyde condensation products of melam;ne ;nclude hexamethoxy~ethylmelam;ne, hexakis-(methoxymethyl)melamine, ethoxymethoxy~ethylmelamine, hexamethylated methylolmelamine and the like and aLso benzyl urea and benzoguanamine.
The amount of crossl;nking agent employed depends on the OH number of the copolymers according to the invention.
In general, equimolar amounts are employed.
Curing is generally carr;ed out at a tempera~ure between O and 260C, preferably 20 to 150C. The temperature is dependent on the curing time. However, it is preferable to carry out the reaction at lou temperatures.
~y virtue of their va,ious functional groups, the copoly-mers prepared in accordance ~ith the invention have excel-lent properties. They exhibit, surprisingly, a very good resistance to chemicals at a relatively low hydroxyl num-ber~ for example resistance against gasoline, whereas theknown polyacryl;c resins in general only reach an adequate resistance to chemicals at OH numbers of at least 1ZO.
Furthermore, the copolymers according to the invention possess a high flexibility, toughness and elasticity anrJ
a good adhesion, so that they can, if desired, also be employed in mixtures of adhesives.
The copolymers according to the invention can be used in industry in a versatile manner, for example for the pre-paration of shaped articles and/or coatings. As a resultof the presence of urethane groups, they produce a very good adhesion on substrates. For this reason they are suitable, for example, for linings and coatings, for ex-ample for vessels used in the chemical industry and for articles exposed to weathering. They are employed as paints and coatings above all for vehicle components, par-ticularly for motor vehicles, industrial paints, house-hold equipment, furniture and in the building industry or the like. It is also possible to add pigments and other _ 9 _ customary additives to the coat;ng mater;als. Thus they are used, for example, as b;nders for p;gmented and clear prim;ng pa;nts andtor f;n;shing paints; they can also be employed in ;ntegrated plast;cs/metal coatings.
In the examples ~hich follow, p denotes parts by ~eight and X denotes percent by ~e;~ht.
Examples Starting materials The preparation of the carbamoyloxyalkyld;carboxylic 1~ ac;d esters~ carry;ng hydroxyl groupsr ~hich are used as the start;ng material and which are shown in Ta~le 1 can be carried out in accsrdance with d;rections such as are described in Canadian Patent Application Serial No. 501,331 already mentioned~
Table 1 Compound ~o_ ~ -CH2~ e A /~_~O_C~2_ ~ -OLC-~CH-C-0-GE
~0. ~ _ ~
~ ~ e IOH
B ~ ( ~ )3-C~ H-G~ ~ - ~ -O-C-~ ~ C-O~ ~ -CH-C~3-C~2 0 C C~( ~ )3-~-C~-N~ ~ ~ = ~ 0-GE
8~
Table 1 (contd~
- trtmpound O O
O O O' O
E ~ CH2~ 6 ~2 2 O O O 0 0~1 ~~ ~ - ~ -0-C-~H~ 6~ ~ c-c-cH=
GE = glycidyl ester The compounds Listed in Table 1 ~ere polymeri~ed, under nitrogen and ~;th st;rr;ng, ~ith the monomers l;sted ;n Table 2 in a solvent mixture co~posed of xylene, an aro-matic mixture of hydrocarbons having a boiling po;nt of 154 to 178C and butyl acetate t2~ Th;s ~as effected~ on the one hand, by initially taking the compounds of Table 1 together uith the solvent mixture and heating to 14~C, after ~hich the added monomer mixture 1 ~as metered in in the course of three hours at a rate determined by the exo-thermic reaction. The first stage of the copolymeriza-tion can also be carried out by initially taking part of ehe soLvent mixture, and the monomer mixture 1 is composed of the rest of the solvent, monomers and compounds of TabLe 1 and further additives (Example 3). In this case too, the monomer mixture 1 ;s added dropwise to the soL-vent mixture which has been heated to 140C.
After the total amount of the monomer mixture 1 had been ~dded, the monomer m;xture 2 was added in the course of four hours ~t 140C and~ ~hen the addition ~as co~plete, the ~ixture ~as allowed to stand at 140C for one hour.
Details of the resulting copolymers in respect of OH num-5 ber, acid number, solids con~ent and viscosity at 20C
t50X strength solution in xylene) are given ;n Table 2.
- 8 and 9 _.
The procedure of Ex~mples 1 to 7 was carried out using eompounds E and F from Table 1, ~i~h the difference that the copolymerization temperature was 150C and the sol-vent employed ~as ethylglycol acetate. Details relating to the monomers used, the proportions of ingred;ents and the physicaL data of the resulting copolymers are given in Tahle 2.
Table Z
Solvent P 1200 . 200 . ~3~ ~200 Compound from Tab. 1 A B C C
amount P 644 217 305 644 Monomer mixture 2n Solvent P - 100 167 Styr~ne P 57.2 22,2 27 57.2 DTDBP p 9~2 2.25 3.75 9.2 DDM P 6.0 1.35 2.25 6.0 ZS Monomer mixture Styrene 696 200 269 696 MMA P 272 28.4 116 272 HEMA P 80 34.5 34 8.0 30 DTD0P P g.2 2.253.75 g.2 DDM ~ 6.~ l ~52.25 ~.Q
'~
. - 12 -Table 2 (contd.) OH number 123100 60 60 Ac;d number 5-32.0 5,0 9 Sol;ds content (1hr/125C)60 60 59.6 59.3 5 Viscosity (20, 4902300 454 1053 5QX solution in xylene, mPa.s) DTD8P = di-tertO-d;butyl peroxide DDM - dodecyl mercaptan MMA = methyL methacrylate HEMA = hydroxyethyl methacrylate EGA = ethylglycol acetate Table 2 (contd.) Solvent P 500 500 lOOO 233 113 Co~pound from Tab. 1 B B C ~ ~
amount P 197 281 473 185 49 Monomer mixture Solvent P - - 200 lOO 66 Styrene P 31,6 151 7617.5 5 10 DTDBP P 3,75 3,75 9 2.5 1.5 DDM P 2.25 2.25 5.4 I.5 0.9 .
Monomer m;xture Styrene P 348 46 835 65 138 DTD8P P 3 75 3 75 9 2.5 1.5 DDM P 2.25 2.25 ~,4 1.5 0.4 OH number 60 lOO 51 140 71 2Q Acid number 4.8 4.6 3.1 8,1 3.C
Solids content (1hr/125C) 59.8 58.2 59.9 53 60 Viscosity (20, 842 1310 575 - 965 50% solution in (in ~A) xy(ene, mPa.s) 21 DTDBP = di-tert.-dibutyl peroxide DDM = dodecyl mercaptan MMA = methyl methacrylate HEMA = hydroxyethyL methacrylate EGA = ethylglycol acetate
Claims (18)
1. A curable copolymer based on A) 5-95% by weight of at least one polymerizable carbamoyloxyalkyldicarboxylic acid ester, carrying hydroxyl groups, of the formula I
(I) in which R1 represents hydrogen or alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, R2 represents alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, or the ra-dical subject to the proviso that R1 is hydrogen and x is an integer from 2 to 10, R3 represents linear or branched alkylene having 2 to 5 carbon atoms, R4 represents hydrogen or methyl and R5 represents hydroxyalkyl or hydroxyaminoalkyl having in each case 2 to 20 carbon atoms in the alkyl radi-cal, or an alkyl radical of this type which also con-tains ester and/or ether groups, and B) 5-95% by weight of a copolymerizable monomer belong-ing to the group comprising a) an .alpha.,.beta.-olefinically unsaturated monocarboxylic acid and alkyl and hydroxyalkyl esters thereof having in each case 1 to 18 carbon atoms in the alkyl radical, and amides and nitriles thereof, and also monoalkyl and dialkyl esters of .alpha.,.beta.-olefinically unsaturated dicar-boxylic acids having 1 to 18 carbon atoms in the alkyl radical, b) vinyl-aromatic monomers, c) vinyl esters of organic monocarboxylic acids having 1 to 18 earbon atoms in the carboxylic acid radical, and d) glycidyl esters of unsaturated monocarboxylic and/or dicarboxylic acids, the sum of the components A)and B) being in all cases 100% by weight, in the presence of C) polymerization catalysts and, if appropriate, D) molecular weight regulators.
(I) in which R1 represents hydrogen or alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, R2 represents alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, or the ra-dical subject to the proviso that R1 is hydrogen and x is an integer from 2 to 10, R3 represents linear or branched alkylene having 2 to 5 carbon atoms, R4 represents hydrogen or methyl and R5 represents hydroxyalkyl or hydroxyaminoalkyl having in each case 2 to 20 carbon atoms in the alkyl radi-cal, or an alkyl radical of this type which also con-tains ester and/or ether groups, and B) 5-95% by weight of a copolymerizable monomer belong-ing to the group comprising a) an .alpha.,.beta.-olefinically unsaturated monocarboxylic acid and alkyl and hydroxyalkyl esters thereof having in each case 1 to 18 carbon atoms in the alkyl radical, and amides and nitriles thereof, and also monoalkyl and dialkyl esters of .alpha.,.beta.-olefinically unsaturated dicar-boxylic acids having 1 to 18 carbon atoms in the alkyl radical, b) vinyl-aromatic monomers, c) vinyl esters of organic monocarboxylic acids having 1 to 18 earbon atoms in the carboxylic acid radical, and d) glycidyl esters of unsaturated monocarboxylic and/or dicarboxylic acids, the sum of the components A)and B) being in all cases 100% by weight, in the presence of C) polymerization catalysts and, if appropriate, D) molecular weight regulators.
2. Copolymer as claimed in claim 1, wherein in the pro-portion of the component A) is 10 to 70% by weight and that of the component B) is 30 to 90% by weight.
3. Copolymer as claimed in claim 1, wherein the copolymers have OH numbers from 30 to 200 and the viscosity, as a 50%
strength solution, is 200 to 3,000, mPa?s.
strength solution, is 200 to 3,000, mPa?s.
4. Copolymer as claimed in claims 1 or 2 or 3, wherein the monomers of component B) are composed of 0 to 95% by weight of the monomers a), 5 to 100% by weight of the monomers b), 0 to 95% by weight of the monomers c) and 0 to 50% by weight of the monomers d), the sum of the monomers geing in all cases 100% by weight.
5. Compound as claimed in claims 1 or 2 or 3, wherein the component A) is a compound of the formula I in which R1 denotes hydrogen or alkyl or hydroxyalkyl having in each case 2 to 20 carbon atoms in the alkyl radical, R2 denotes alkyl or hydroxyalkyl having in each case 2 to 20 carbon atoms in the alkyl radical, or the radical subject to the proviso that R1 is hydrogen and x is an integer from 2 to 6, R3 denotes alkylene having 2 to 3 carbon atoms, R4 denotes hydrogen or methyl and R5 denotes a hydroxyalkyl ester radical of a branched, saturated fatty acid having 9 to 11 carbon atoms in the acid radical, or hydroxyalkyl, each having 2 to 14 carbon atoms in the alkyl group.
6. Copolymer as claimed in claims 1 or 2 or 3, wherein the component B) is composed of at least one copolymerizable monomer a) an .alpha.,.beta.-olefinically unsaturated monocarboxylic acid and alkyl and hydroxyal-kyl esters thereof having in each case 1 to 8 carbon atoms in the alkyl radical or monoalkyl or dialkyl esters of ?,.beta.-olefini-cally unsaturated dicarboxylic acids having 1 to 8 carbon atoms in the alkyl radical, b) at least one vinyl-aromatic monomer and c) at least one vinyl ester of organic mono-carboxylic acids having 2 to 11 carbon atoms in the acid component.
7. Copolymer as claimed in claims 1 or 2 or 3, wherein the component B) is composed of at least one copolymerizable compound select-ed from the group consisting of acrylic acid, 2-ethylhexyl-acrylate, methylmethacrylate, hydroxyethylmethacrylate, styrene, vinyl acetate and the vinyl ester of Versatic acid.
8. Process for the preparation of curable copolymers, which comprises copolymerizing A) 5-95% by weight of at least one polymerizable carbamoyloxyalkyldi-carboxylic acid ester, carrying hydroxyl groups, of the formula (I) (I) in which R1 represents hydrogen or alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, R2 represents alkyl or hydroxyalkyl having in each case 1 to 30 carbon atoms in the alkyl radical, or the ra-dical subject to the proviso that R1 is hydrogen and x is an integer from 2 to 10, R3 represents linear or branched alkylene having 2 to 5 carbon atoms, R4 represents hydrogen or methyl and R5 represents hydroxyalkyl or hydroxyaminoalkyl having in each case 2 to 20 carbon atoms in the alkyl radical, or an alkyl radical of this type which also contains ester groups or ether groups or both, and B) 5-95% by weight of at least one copolymerizable monomer selected from the group consisting of a) an .alpha.,.beta.-olefinically unsaturated monocarboxylic acid and alkyl and hydroxy alkyl esters thereof having in each case 1 to 18, preferably 1 to 8, carbon atoms in the alkyl radical, and amides and nitriles thereof, and also monoalkyl and dialkyl esters of .alpha.,.beta.-olefinically unsaturated dicarboxylic acids having 1 to 18 carbon atoms in the alkyl radical, b) vinyl-aromatic monomers, c) vinyl esters of organic monocarboxylic acids having 1 to 18 carbon atoms in the carboxylic acid radical, and d) glycidyl esters of unsaturated monocarboxylic or dicarboxylic acids or both, the sum of the components A)and B)being in all cases 100% by weight, in the presence of C) polymerization catalysts alone or together with D) molecular weight regulators.
9. Process as claimed in claim 8, wherein the polymeriza-tion temperature is 20 to 270°C.
10.Process as claimed in claim 8, wherein the polymeriza-tion catalysts are employed in amounts of 0.01 to 5% by weight and molecular weight regulators D) are employed in amounts of 0.01 to 2% by weight.
11. Process as claimed in claims 8 or 9 or 10, wherein the proportion of the component A) is 10 to 70% by weight and that of the component B) is 30 to 90% by weight.
12. Process as claimed in claims 8 or 9 or 10, wherein the monomers of component B) are composed of 0 to 95% by weight of the monomers a), 5 to 100% by weight of the monomers b), 0 to 95% by weight of the monomers c) and 0 to 50% by weight of the monomers d), the sum of the monomers being in all cases 100% by weight.
13. Process as claimed in claims 8 or 9 or 10, wherein the component A) is a compound of the formula I in which R1 denotes hydrogen or alkyl or hydroxyalkyl having in each case 2 to 20 carbon atoms in the alkyl radical, R2 denotes alkyl or hydroxyalkyl having in each case 2 to 20 carban atoms in the alkyl radical, or the radical subject to the proviso that R1 is hydrogen and x is an integer from 2 to 6, R3 denotes alkylene having 2 to 3 carbon atoms, R4 denotes hydrogen or methyl and R5 denotes a hydroxyalkyl ester radical of a branched, saturated fatty acid having 9 to 11 carbon atoms in the acid radical, or hydroxyalkyl, each having 2 to 14 car-bon atoms in the alkyl group.
14.Process as claimed in claims 8 or 9 or 10, wherein the component B) is composed of at least one copolymerizable monomer a) an .alpha.,.beta.-olefini-cally unsaturated monocarboxylic acid and alkyl and hydroxyalkyl esters thereof having in each case 1 to 8 carbon atoms in the alkyl radical or monoalkyl or dialkyl esters of .alpha.,.beta.-olefini-cally unsaturated dicarboxylic acids having 1 to 8 carbon atoms in the alkyl radical, b) at least one vinyl-aromatic monomer and c) at least one vinyl ester of organic mono-carboxylic acids having 2 to 11 carbon atoms in the acid component.
15. Process as claimed in claims 8 or 9 or 10, wherein the componerit B) is composed of at least one copolymerizable compound selected from the group consisting of acrylic acid, 2-ethylhexylacrylate, methylmethacrylate, hydroxyethylmeth-acrylate, styrene, vinyl acetate and the vinyl ester of Versatic acid.
16. Process as claimed in claims 8 or 9 or 10, wherein the copolymers have OH numbers from 30 to 200, and the vis-cosity, as a 50% strength solution, is 200 to 3,000 mPa.s.
17. Shaped articles and coatings, prepared from copolymers as claimed in claim 1.
18. Coatings as claimed in claim 17 as vehicle lacquers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3504337.7 | 1985-02-08 | ||
| DE19853504337 DE3504337A1 (en) | 1985-02-08 | 1985-02-08 | CURABLE COPOLYMERISATE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1244183A true CA1244183A (en) | 1988-11-01 |
Family
ID=6262024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000501325A Expired CA1244183A (en) | 1985-02-08 | 1986-02-07 | Curable copolymers, a process for their preparation and their use |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4704442A (en) |
| EP (1) | EP0190653B1 (en) |
| AT (1) | ATE57385T1 (en) |
| AU (1) | AU578876B2 (en) |
| CA (1) | CA1244183A (en) |
| DE (2) | DE3504337A1 (en) |
| ES (1) | ES8701799A1 (en) |
| PT (1) | PT81994B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199087B2 (en) * | 1985-03-29 | 1993-11-10 | Akzo N.V. | A liquid coating composition and a process for coating a substrate with such coating composition |
| JPS63154713A (en) * | 1986-12-17 | 1988-06-28 | Shin Etsu Chem Co Ltd | Production of vinyl chloride copolymer |
| US6235858B1 (en) | 1992-10-30 | 2001-05-22 | Ppg Industries Ohio, Inc. | Aminoplast curable film-forming compositions providing films having resistance to acid etching |
| KR0179461B1 (en) * | 1992-10-30 | 1999-05-15 | 리타 버그스트롬 | Aqueous aminoplast-curable film-forming compositions providing films having resistance to acid etching |
| US5804641A (en) * | 1995-04-12 | 1998-09-08 | Nippon Eisei Center Co., Ltd. | Foamable composition for creating a barrier to prevent attack of humidity, fungi and insects |
| US7232863B2 (en) * | 2002-10-31 | 2007-06-19 | Basf Corporation | Functional addition polymers and a method for their preparation |
| US7342075B2 (en) * | 2002-10-31 | 2008-03-11 | Basf Corporation | Carbamate functional addition polymers and method for their preparation |
| US20040087728A1 (en) * | 2002-10-31 | 2004-05-06 | Donald Campbell | Carbamate functional addition polymers and a method for their preparation |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT314697B (en) * | 1972-07-24 | 1974-04-25 | Vianova Kunstharz Ag | Process for the production of coating agents based on isocyanate-crosslinkable copolymers |
| DE2422170C2 (en) * | 1974-05-08 | 1982-09-23 | Bayer Ag, 5090 Leverkusen | Polymerizable N, N-disubstituted carbamoyloxyalkylcarboxylic acid esters, process for their preparation and their use |
| US4126747A (en) * | 1976-12-28 | 1978-11-21 | Union Carbide Corporation | Carbamoyloxy acrylate compounds |
| DE2907997C2 (en) * | 1979-03-01 | 1982-04-15 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of curable copolymers |
| DE3020524C2 (en) * | 1980-05-30 | 1983-10-27 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of curable copolymers |
| DE3031655A1 (en) * | 1980-08-22 | 1982-04-08 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING CURABLE COPOLYMERS |
| CA1217195A (en) * | 1983-03-10 | 1987-01-27 | Carmine P. Iovine | Polymerizable imidazolidinones and polymers thereof useful as nonwoven binders |
| US4507188A (en) * | 1983-12-21 | 1985-03-26 | Thiokol Corporation | Ultraviolet curable formulations containing urethane acrylate monomers |
-
1985
- 1985-02-08 DE DE19853504337 patent/DE3504337A1/en not_active Withdrawn
-
1986
- 1986-01-29 EP EP86101136A patent/EP0190653B1/en not_active Expired - Lifetime
- 1986-01-29 DE DE8686101136T patent/DE3674810D1/en not_active Expired - Fee Related
- 1986-01-29 AT AT86101136T patent/ATE57385T1/en active
- 1986-02-06 US US06/826,789 patent/US4704442A/en not_active Expired - Fee Related
- 1986-02-06 ES ES551707A patent/ES8701799A1/en not_active Expired
- 1986-02-07 CA CA000501325A patent/CA1244183A/en not_active Expired
- 1986-02-07 AU AU53318/86A patent/AU578876B2/en not_active Ceased
- 1986-02-07 PT PT81994A patent/PT81994B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AU5331886A (en) | 1986-08-14 |
| US4704442A (en) | 1987-11-03 |
| PT81994B (en) | 1988-07-01 |
| EP0190653B1 (en) | 1990-10-10 |
| ES8701799A1 (en) | 1987-01-01 |
| ES551707A0 (en) | 1987-01-01 |
| PT81994A (en) | 1986-03-01 |
| DE3504337A1 (en) | 1986-08-14 |
| EP0190653A3 (en) | 1989-01-04 |
| EP0190653A2 (en) | 1986-08-13 |
| AU578876B2 (en) | 1988-11-03 |
| DE3674810D1 (en) | 1990-11-15 |
| ATE57385T1 (en) | 1990-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4170582A (en) | Process for preparing a polymer resin aqueous dispersion | |
| KR100250097B1 (en) | An improved process of polymerization in an aqueous system | |
| CA1255440A (en) | Bulk polymerization process for preparing high solids and uniform copolymers | |
| US3382297A (en) | Polymer dispersions | |
| CA1244183A (en) | Curable copolymers, a process for their preparation and their use | |
| US4276432A (en) | Low molecular weight acrylates or methacrylates and methods for their preparation | |
| EP0103199B1 (en) | Humidity resistant coatings employing branched polymers of t-butyl acrylate | |
| US3370050A (en) | Preparation of interpolymers of hydroxyl-containing monomers in an organic solvent using hydrogen plroxide as catalyst | |
| US4732941A (en) | Process for preparing a stable dispersion of vinyl polymer | |
| KR930019717A (en) | Method for preparing hydroxy functional copolymer | |
| US5929158A (en) | Non-aqueous polymer dispersion and curable compositions | |
| US4605720A (en) | Preparation of nonaqueous dispersions with the use of monofunctional stabilizer | |
| EP0295784A2 (en) | Polymers prepared by polymerizing alpha, beta-ethylenically unsaturated acids and epoxy compounds and curable coating compositions containing same | |
| EP0103118A1 (en) | High solids primer-guidecoats based on t-butyl acrylate and styrene | |
| US4530957A (en) | Non-aqueous dispersions based on capped stabilizers and reactants comprising polyfunctional monomers I | |
| US4748211A (en) | Hydroxyl functional graft copolymers | |
| EP0384338B1 (en) | Self-curing aqueous resin dispersion | |
| US4542180A (en) | Composite low temperature cure latexes | |
| US2635086A (en) | Emulsion polymerization process | |
| KR100293586B1 (en) | Monomers comprising at least one isocyanate functional group and one unsaturated group, a process for their synthesis and a (co) polymer obtained therefrom | |
| KR910002081B1 (en) | Thermosetting compositions comprising acrylic polymers | |
| CA1139031A (en) | Process for the production of aqueous polymer dispersions | |
| KR970062000A (en) | High Solid Acrylic Polyol Resin Composition and Manufacturing Method Thereof | |
| US4801653A (en) | Coating compositions prepared from hydroxyl functional graft copolymers | |
| GB2173808A (en) | Free radical initiated polymerization of polymerizable ethylenically unsaturated monomer component in the presence of hydrogen peroxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |