CA1281494C - Reaction product of olefinically unsaturated compounds with compounds containing active hydrogen, processes for their preparation and 2-component lacquers based thereon - Google Patents

Abstract

Abstract of the disclosure:

Reaction products of A) compounds containing at least two R1R2C=CR3-X groups (I) with B) compounds which contain:
a) at least two active H atoms or b) at least two groups having active H atoms of the type -AH- (II) or c) at least one active H atom and at least one group of the type (II), or which form the corresponding amount of this group (II), in which, in formula (I), X denotes -CO- which is attached to a further R1R2C=
CR3-X group either directly or via the radical of a poly-hydric alcohol or of an amine, R1 denotes hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms, R2 denotes hydrogen, a hydrocarbon radical having 1 to 10 carbon atoms, an ester group containing the radical R4 of a monohydric alcohol having up to 12 carbon atoms, -CN, -NO2 or a CO-NHR1 or CO-R1 group, R3 has the same meaning as R2, and in formula (II), -AH- denotes one of the groupings -CH-, -NH- and -SH.
These compounds are prepared with the use of specific catalysts and can be employed in the form of 2-component systems as binders for coatings which cure rapidly at room temperature and at elevated temperatures.

Description

- ;2 -HOE ~5/F 036J

It is known to reac~ unsaturated compounds, such as cinnamic acid esters, ~ith H-active compounds, for example malonic acid ester or acetoacetic ester, by a Michael addit1on reaction ~ith the formation of subst;tu-ted compounds, for example substituted malonic acidesters (Krauch-Kunz "Namensreaktionen der organischen Chemie" C"Named Reactions of Organic Chemistry"], 5th edition 1976, page 42).
It is also known to use an acrylic resin contain-ing OH groups or an ~-caprolactone-modified acrylic resin mixed with polyisocyanates as two-component lac-quers (German Patent Nos. 3,005,945, 3,027,776 and 3,148,022). A further publication describes the reaction of acrylate copolymers containing epoxide groups with a partially masked isocyanate, and the use of the reaction product as a lacquer binder (German Offenlegungsschrift 3,130,545).
The known products have in some cases proved suc-cessful. However, attempts have already been made to prepare products more acceptable to the environment by starting from systems not containing free isocyanate.
Thus an acrylic resin which contains oxazol;dine and uses water or atmospher;c moisture as the cur-ng agent is descr;bed in another publication tEP Laid-Open 25 Specif;cation 34,720). This system has the d;sadvantage that the cured surface res;sts the deeper penetration of water into the lower layers of the coating and thus pre-vents complete curing through the whole thickness of the film.
A two-component system which reacts in the absence of isocyanate is also known. This comprises an acrylic resin containing epoxide groups which can be cured by means of another acrylic resin containing tertiary amino - groups. In the case of the product prepared by this .

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process, -the excessively low degree of crosslinking results in inadequate resistance to chemicals, so that the coatings prepared usiny this system are only suitable for a limited field of applications.
U.S. Patent No. 4,408,018 describes acrylic polymers into which acetoacetate groupings have been introduced and which can be crosslinked with ~,~-olefinically unsaturated esters in the presence of strong bases via the Michael addition reaction. The introduction of the acetoacetate group is effected via the aceto-acetic esters of hydroxymethyl acrylates or methacrylates andsubsequent copolymerization with further copolymerizable monomers, or by reacting polymers containing OH groups with the precursor of the acetoacetic ester component, diketene. Polyacrylates contain-ing more than two acrylate groups, reaction products of polyiso-cyanates with acrylic acid esters containing hydroxyl groups and reaction products of epoxide resins with acrylic acid are men-tioned as organic components which can be crosslinked with the polymers containing the acetoacetate groups. These compounds, however, have the disadvantage that the strong bases acting as catalysts, such as alkali metal hydroxides or alcoholates, result in considerable yellowing and cloudiness in the lacquer.
The invention is therefore based on the object of enlarging the supply of lacquer binders available on the market by means of a system which requires no free isocyanates for curing, and is therefore acceptable to the environment. This system employs catalysts which do not shorten the pot life or produce any yellowing in the lacquer film and which produce, with the use of L49~

small amounts of cata.lyst, coatings which meet the high require-ments in respect of curing properties and resistance to chemicals.
The present invention therefore relates to a reaction product of A) compounds containing at least two RlR2C=CR3-X
groups (I) in which formula (I) X denotes -CO- which is attached to a further RlR2C=CR3 group either directly or via the radical of a polyhydric alcohol or of an amine, Rl denotes hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms, R2 denotes hydrogen, a hydrocarbon radical having 1 to 10 carbon atoms, an ester group containing the radical R4 of a monohydric alcohol .
having up to 12 carbon atoms, -CN, -NO2 or a CO-NHRl or CO-Rl group, and R3 has the same meaning as R2 and is identical with different from the latter, with B) compounds which contain a) at least two active H atoms or b) at least two groups containing active H atoms of the type -AH- (II) or c) at least one active H
atom and at least one group of the type (II), or which form the corresponding amount of this group (II) in which formula (II) -AH-denotes one of the groupings -CH- and -SH, subject to the proviso that reaction products of A) polyacrylates containing at least two free acrylic acid groups, reaction products of polyisocyanates with acrylic acid esters containing OH-groups or reaction products of epoxy resins with acrylic acid, with B) diketene or acetoacetic acid esters of hydroxyethyl acryla~e or methacrylate are excluded, wherein the reaction product is obtained via Michael reaction in the presence of at least one catalyst selected from the group consisting of diazabicyclooctane (DABCO), halides of quaternary 4~
- 4a - 23221-4184 ammonium compounds, on their own or as a mixture with alkyl silicates, amidines, organic phosphonium salts having 1 to 20 carbon atoms in the alkyl radical or aryl radical or both, ter-tiary phosphanes of the general formula P(CH2-Y)3 in which the Ys r~ or . ~ are identical ~ different and denote the radical -OH, CH2CN or -N(Z)2 in which Z is an alkyl radical having 1 to 5 carbon atoms, tertiary phosphanes of the general formula P(R4,R5,R6) in which the radicals R4, R5 and R6 denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substi-tuted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R~, R5,. R6 are identical or different, but at least one of the radicals represent a phenyl radical, and aminophosphoranes of the yeneral formula (R7,R8,R9)~=N-C(R10,Rll,R12) in which R7, R8 and R9 are identical or different and denote an alkyl radical having l to 12 carbon atoms or a phenyl radical which is unsubstituted or sub-stituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R10, Rll and R12 are identical or different and each represents an alkyl radical having 1 to 5 carbon atoms or phenyl radical.
The invention also relates to a reaction product of A) compounds containing at least two RlR2C=CR3-X groups (I), in which formula (I) the radicals Rl to R3 and X have the meaning as defined above, with B) compounds which contain a) at least two groups containing active H atoms of the type -~H- (II) or b) at least one active H atom and at least one group of this type (II) or which form the corresponding amount of this group (II).

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- 4b - 23221-4184 The present invention further provides a reaction product of A) compounds containing at least two RlR2C=CR3-X
groups (I), in which formula (I) the radicals Rl to P~3 and X have the meaning as defined above, with B) compounds which contain a) at least two groups containing active H atoms of the type -CH-(II) derived from unsubstituted or mono alkyl substituted malonic acid moieties or from the grouping ~C-CHRl-CO-, NC-CH2-CN, =P0-CHRl-C0-, =P0-CHRl-CN, =P0-CHRl-CN, =P0-CHRl-P0=, or -C0-CHRl-N02, b) at least one active H atom and at least one group of this type (II), or which form the corresponding amount of this group (II).
Also provided isaprocess for the preparation of reac-tion products which comprises reacting compounds A) containing at least two RlR2C=CR3-X groups (I) in which formula (I) the radicals Rl to R3 and X have the meaning as defined above, with B) com-pounds of the type as defined above under the formation of an oligomeric or polymeric reaction product, the reaction being carried out, in the event that -AH- represents one of the groups -CH- or -SH, in the presence of at least one catalyst selected from the group consisting of diazabicyclooctane (DABC0), halides of quaternary ammonium compounds, on their own or as a mixture with alkyl silicates, amidines, organic phosphonium salts having 1 to 20 carbon atoms in the alkyl radical or aryl radical or both, tertiary phosphanes of the general formula P(CH2-Y)3 in which t'ne Ys are identical or different and denote the radical -OH, CH2CN or -N(Z)2 in which ~ is an alkyl radical having 1 to 5 carbon atoms, tertiary phosphanes of the general formula P(R4,R5,R6) in which D

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- 4c - 23221-4184 the radicals R4, R5 and R6 denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substi-tuted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R4, R5, R6 are identical or different, but at least one of the radicals represent a phenyl radical, and aminophosphoranes of the general E formula (R7,R8,R9)~=N-C(R10,Rll,Rl2) in which R7, R8 and R9 are identical or different and denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or sub-stituted by at least one alkyl, alkoxy or dialkylamino group eachof which has 1 to 4 carbon atoms in the alkyl radical, and R10, Rll and R12 are identical or different and each represents an alkyl radical having 1 to 5 carbon atoms or phenyl radical.
The product according to the invention has the advantage that it is prepared from components which contain no toxic con-stituents and can there.fore be used without special precautionary measures.
Although, in the reaction of compounds A) containing in each case two groups (I) with compounds B) containing two active H
atoms or two groups (II), even if the latter only contain one H
atom, it would be expected, on the basis of the bifunctionality on each side, that a lengthening of the chain would be the sole result, surprisingly, the cured, crosslinked reaction products D

according to the invention are obtained. The active groups of the compounds A) and ~ can also be present in a s;ngle molecule, so that systems are available which can be cured by intermolecular rrosslinking and are self-crosslinking.
If a higher degree of reactivity and thus greater crosslinking of the product is desired, it can be advan-tageous to employ a procedure such that three or more groups of the type tI) or active H atoms and/or groupings of the type (II) are present in at least one of the com-pounds A) and 3).
In one embodirent of the invention the radisal R1R2C=CR3-X (I) can be derived from a monounsaturated or polyunsaturated carboxylic acid of a basicity not higher than 2, for example a monocarboxylic and/or dicarboxylic acid hav;ng 2 to 10, preferably 3 to 6, carbon atoms, such as cinnamic acld, croton;c acid, citraconic acid or the anhydride thereof, mesaconic acid, fumaric acid~
dehydrolevulin;c acid or sorbic acid, but preferably acrylic acid, methacrylic acid and/or maleic acid or the anhydride thereof, and can also be derived from unsatura-ted ketones, such as d;vinyl ketone or dibenzalacetone;
and also from unsaturated nitriles, such as maleic acid mononitrile-monoesters of poLyhydric alcohols~ from cyano-acrylic acid esters of the formula H2C=C(CN)-COOR, from nitrites of the formula RooC-R3C=CH-No2, from alkylidene-malonic acid esters of the formula RooC-C(CooR4)=cR1R2 or alkYlideneacetoacetic esters of the formula ROOC-C(CO-CH3)=CR1R2 or the corresponding nitriles, or 3D the like, R in the above formulae being the radical of a polyhydric alcohol and R1 and R2 being hydrogen or alkyl.
As a rule, the~radicals (I) are present attached ;n the form of an ester or amide. They can be attached to the radical of a polyhydric alcohol or a compound containing NH groups, such as a polyamine, polyamide or polyimino-amide~ or a polyhydric phenol, preferably an oligomer -or polymer. Thus the compound A) can be derived, for example, from saturated and/or unsaturated poLyethers or polyesters containing OH groups, for example those based ~ 6 -on maleic acid or phthalic acid and diols; acrylic resins containing OH groups; aliphatic~ or preferably aromatic, epoxide resins containing, if appropriate, OH groups, for example those based on diphenylolpropane and/or diphenylol-methane, hydantoin and/or amine resins. The radical (I)which is attached in the form of an ester can, for example, have been produced by an addition reaction bet-ween acrylic or methacrylic acid and the epoxide group.
Examples of polyhydric alcohols ~hich are suitable as starting substances for A) are alkanediols and alkane-triols, such as ethanediol, the various propanediols, butanediols, hexalnediols or octanediols or homologs thereof, the corresponding oligomeric ethers, and also glycerol, trimethylolethane, trimethylolpropane, hexane-triol, pentaerythritol, d;pentaerythritol, sorbitol,polyvinyl alcohol or the like.
The following are mentioned as examples of start-ing compounds, cc,ntaining NH groups, for the compounds A:
alkylenediamines and oligomers thereof, such as ethylene-diamine, propylenediamine, butylenediamine, diethylene-tr;am;ne, tetram;nes and higher homologs of these amines, and also aminoalcohols, such as diethanolamine or the like.
Aminocarboxylic acid esters of polyhydric alcohols are ; also exampLes of suitable amines. Examples of suitable compounds containing N~ groups are polyamides of acrylic or methacrylic acid, and also polyurethanes, for example polyisocyanates ~Ihich have been masked in the form of polyurethane groups, such as those obtained by reacting hydroxyethyl acrylate ~ith polyisocyanates, amine resins, such as methylolmelamines, preferably hexamethylolmel-amine, and urea resins, the radical (I) being attached as an amide to the amine groups of these compounds by means of the grouping -CO-. If these amine compounds contain OH groups; or alkylol groups, it is also possible for the radical ~I) to be directly attached to these resins via an ester group (formula III, see formula sheet) or indirectly via an ether group (formula IV, see formula sheet). It is thus possible to start from a hydroxyalkyl ester or a hydroxyalkyl amide of an unsaturated acid, such 128~L~L9~

as acrylic acid, for the ether linkage of the radical (I).
The same applies to a corresponding link to polyhydroxy compounds.
The grouping -AH- ~II) in the compound B) is derived:
aa~ when it denotes -CH- from a compound containing ~he grouping -C0-CHR1-C0-, NC-CHR1-C0-, NC-CH2-CN, =P0-CHR1-C0-l, =P0-CHR1-CN, =PQ-CHR1-P0=, or -C0-CHR1-N02 in which R1 is preferably hydrogen, bb) ~hen it denotes -NH-, ~hich also embraces NH2, from a primary and~or secondary amine, and cc) when it denotes -SH, from a thioalcohol acid ester or amide andlor a mercaptan.
~-Dioxo compounds are preferred.
Examples of suitable compounds B) of the type aa) are ketones, such as acetylacetone, benzoylacetone or acetyldibenzoylmethane, and also esters of an optionally alkyl-substituted acetoacetic acid, such as ~-methyl-acetoacetic and/or~-methylacetoacetic acid, or of acetonedicarboxylic acid~ malonic acid units, attached by an ester linkage, of malonic acid and monoalkyl deriva-tives thereof, linear or branched and having 1 to 6 car-bon atoms in the alkyl radical, for example methyl, ethyl and n-butyl, or phenyl, or esters of cyanoacetic acid ~ith monohydric to hexahydric alcohols containing 1 to 10 carbon atoms. The alkyl-substituted esters, for example ~-methylacetoacetic esters or~ ,~-dimethylacetoacetic esters, contain snly one active H atom and are therefore preferably employed in the form of diesters or polyesters of polyhydric alcohols, in order to make available a suf-- fic;ent number of reactive groups. Examples of alcohols which are suitable for the esterification of the above acids are methanol, ethanol, butanol and octanol and/or, ~hich is preferable, polyhydric alcohols or polyhydroxy compounds such as those mentioned as starting substances for A). Further examples of compounds B) are acetoacetic esters, ethanediol bisacetoacetate, glycerol trismalonate, trimethylolpropane trisacetoacetate, partial esters of these acids uith polyhydric alcohols, also the .i .

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corresponding esters of acrylic resins containing OH
groups, polyesters, polyethers, polyester-amides, poly-ester-imides and polyhydroxylamines, and also nitriles of these acids insofar as these exist, for example malonic acid mononitrile or dinitrile, alkoxycarbonylmethanephos-phonic acid esters and the corresponding bismethanephos-phonic acid esters (formuLa VII, see formula sheet). The acids mentioned above can also be attached, in the form of amides, to amines, preferably polyam;nes, for example to those mentioned above in connection with compound A), ~hich also embrace oligomers and/or polymers, including amine res;ns, aliphatic amines being preferred.
Reactive nitro compounds, for example nitroacetic acid derivatives, such as glycerol tris-tnitroacetate~
or trimethylolpropane nitroacetate, are also suitable as compounds aa).
Examples o~F suitable compounds bb) are primary and/or secondary polyaminesO in particular aliphatic diamines, triamines and higher amines, for example homo-logs, oligomers and/or polymers thereof, including amineresins, such as have been described earlier in the text, urea and derivatives thereof, and also cyclic polyamines, for example aromatic polyamines, such as phenylenediamine or the like, or mixtures of aliphatic and aromatic amines, it being preferable in this case too to employ aliphatic amines.
Examples of suitable compounds E) containing a grouping -SH oF the type cc) are thioglycolic, ~-mer-captopropionic or thiosalicylic acid esters of polyhydric alcohols, and thioalcohol ethers and esters, mercaptans, for example ethyl mercaptan and propyl mercaptan and homologs thereof or ethers thereof, for example thiogly-cerol, and substitution products of cyclic amines with thioalkanols or the like.
Under compounds ~) which form groups of the type (II), examples which should be mentioned are diketene and its~ -monoalkyl-substitution products, and also tetra~
hydrodioxin; t~,ese can react with suitable components ~o form acetoacetic ester or amide groups.

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g The reaction component ~) can be attached to at least one polyfunctional compound of the group comprising monohydric or polyhydric alcohols, polymers containing OH groups, for example those mentioned earlier in the text, polyamines and polymercaPtans~ and, in respect of the CH group, is polyfunctional. Thus it can have been prepared, for example, by esterifying a polyepoxide with a carboxylic acid which forms the grouping -AH- (II), for example cyanoacetic acid ~equation V, see formula sheet).
A component ~) having two active H atoms per epoxide group is obtained in this way. Aromatic or aliphatic polyepox;des, for examPle those mentioned above, can be employed in this reaction.
If polyamines are used as the starting materials, it is possible to prepare compounds 8) both of the type aa), in the form of amides, and of the type bb). If the grouping -AH- has the meaning -CH-~ it is possible, for example, to use as starting material 1 mole of an alkyl-enediamine, which is reacted with 2 moles of acetoacetic ester, with the formation of the compound VI (see formula :heet), uhich also contains four H atoms activated by amide groups. The polyamines as such are themselves suf-ficient as compounds B) in which the group ~II) denotes -NH-. For example, it is possible to react 1 mole of trimethylolpropan~ trisacrylate in this ~ay ~ith 3 moles of ethylenediamine, and the free amine groups in the pro-duct can also react with further active acrylate double bonds to produce crosslinking.
The inven1:ion also embraces a process for the preparation of reaction products of A) compounds contain-ing at least two R1R2C=CR3-X groups (I~ with ~ com-pounds ~hich contain:
a) at least two active H atoms or b) at least two 91'0UpS having active H atoms of the type -AH- (II) or c) at least one active H atom and at least one group of the type (II), or which form the corresponding amount of this group (II), in which, in formuLa (I), ~8i~L9 - 10 ~
Y~~-d~e~n~otes -CO- which is attached to a further R1R2C=CR3 group either directly or via the radical of a ~olyhydric alcohol or of an amine, R1 denotes hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms, R2 denotes hydro~3en, a hydrocarbon radical having 1 to 10 carbon atoms, an ester group containing the radical R4 of a monohydr'ic alcohol having up to 12 carbon atoms, -CN, -N02 or CO-~HR1 or CO-R1 grou R3 has the same meaning as R2, and, in formula ~II), -AH- denotes one of the groupings -CH-, -NH- and -SH, which comprises reacting the compounds A) and B) with the formation of an ol;gomeric and/or polymeric reaction pro-duct, the reaction being carried out, in the event that-AH- represents one of the groups -C~- or -SH, in the presence of at least one catalyst from the group compris-ing diazab;cyclooctane tDABCO), halides of quaternary ammonium compounds, on their own or as a mixture with alkyl sil;cates, amidines, organic phosphonium salts hav-ing 1 to 20 carbon atoms in the alkyl radical and/or aryl radical, tert;ar~ phosphanes of the general formula P(CH2-Y)3 in uhich the Ys are identical or different and denote the radical -OH, CH2CN or -NtZ)2 in uhich Z is an alkyl radical ha~;ng 1 to 5 carbon atoms, tertiary phos-: phanes of the general formula P(R4,R5,R6) in ~hich the radicals R4, R5 and R6 denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubsti-; tuted or substitLIted by at least one alkyl, alkoxy or 3~ dialkylam;no group each of wh;ch has 1 to 4 carbon atoms in the alkyl radical, and R4, R5 and R6 are identical or different, but at least one of the rad;cals represents a phenyl radical, and aminophosphoranes of the general for-mula (R7 R8 R9~p=N_C(R10,R11,R12) ;n wh;ch R7, R8 and R9 are ;dent;cal or different and denote an alkyl radi-cal having 1 to 12 carbon atoms or a phenyl radical which ;s unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of ~h;ch has 1 to 4 carbon atoms in the alkyl rad;cal, and R10, R11 and R12 ~Z8~9~

are identical or different and each represents an alkyl radical having 1 5 carbon atoms or a phenyl radical.
The invention also embraces a process for the preparation of the reaction products mentioned in claim 1, the reartion being effected, in the event that -AH-rePresents one o1 the groups -CH- or -SH, in the pre-sence of at l~ast one quaternary ammonium compound Gr an alkali metal alcoholate as a catalyst.
These processes take place very smoothly. Since the starting materials used are preferably oligomeric and/or polymeric corpounds A and B, oligomeric and/or polymer;c reaction products are also obtained. In gene~
ral, the reaction is carried out at -10 to 180, prefer-ably O to 100 ancl especially 20 to 80C. For example, 1~ products of good hardness are obtained at room tempera-ture after 2 to 24 hours or at 60C after 10 to 40 minutes.
The reactTon of compounds B) in which the group-ing (lI) is -NH- or -NH2 can be carried out in the absence of a catalyst. On the other hand, one or more catalysts are used, as a rule, if the grouping -AH- rep-resents a -CH- group ~the preferred form) or an -SH
group. Examples of catalysts suitable for the Michael addition reaction are those belonging to the group com-prising diazabicyclooctane tDABCO), halides of quater-nary ammonium compounds, such as alkylammonium, aryl-ammonium and/or benzyLammonium bromides, chlorides and, in particular, flworides, the halides being optionally employed ;n combination with alkyl silicates in order 3~ to improve the activity of the catalyst further. Speci-fic examples ~hich should be mentioned are alkyLbenzyl-dimethYlammonium halides (alkyl = C16-C723, benzyltri-methylammonium halides and tetrabutylammonium halides, in each case especially the fluorides, and also copoly-merized triphenylvinylphosphonium fluoride. Furthersuitable catalysts are the organic phosphonium salts, corresponding to the above ammonium halides and having 1 to 20 carbon atoms in the alkyl radical and/or aryL
; radical, for example trimethylbenzylphosphonium halides, 9~

tributylhexadecylphosphonium bromide, amides, such as tetramethylguanidine, diazabicycloundecene, diazabicyclo-nonene and others.
Further suitable catalysts for the process for the preparation of Michael adducts are the phosphanes (formerly known as phosphines), for example a) tertiary phospha~nes P(CH2-Y)3, such as tris-2-cyanoethylphos-phane, trisdiethylaminome~hylphosphane, preferably tris-hydroxymethylphosphane and trisdimethylaminomethylphos-phane, b) tertiary phosphanes P~4, R5, R6), such astriphenylphosphane, tris-p-tolylphosphane, tris-o-anisyl-phosphane, tr;s-p~dimethylaminophenylphosphane, phenyl-di-p-anisylphosphane, phenyldi-o-anisylphosphane, diphenyl-p-anisylphosphane, diphenyl-o-anisylphosphane, diphenyl-p-d;methylam;nophenylphosphane, butyldiphenyl-phosphane, methylditolylphosphane, ethyldi-p-anisyl-phosphane, (diethylaminomethyl)-diphenylphosphane, pre-ferably tris-p-anisylphosphane, methyldiphenylphosphane and methyldi-p-anisylphosphane, and c) iminophosphoranes ~R7, R8, R9) P=N-C (R10, R11, R12), such as ~,~-dimethyl-benzylimino-tris-~dimethylamino)-phosphorane, ~ ,~-di-methylbenzyliminomethyldiphenylphosphorane, t.-butyl-iminotriphenylphosphorane or preferably~ ,~-dimethyl-benzyliminotributylphosphorane.
Examples of catalysts for the M;chael addition reaction ~hich can also be employed for the preparation of specific reaction products are those belonging to the group comprising alkali metal alcoholates, such as lithium butylate, sodium methylate or potassium methy-late, or quaternary ammonium compounds, such as alkyl-ammonium, arylammonium and/or benzylammonium hydroxides or carbonates. Specif;c examples ~hich may be mentioned are alkylbenzyldimethylammonium hydroxide (alkyl =
C16-C22), benzyltrimethylammonium hydroxide and tetra-butylammonium hydroxide. The catalysts or catalyst mix-tures mentioned can be used in the presence of tertiary aliphatic amines ~hich in themselves are not active at room temperature, such as, for example, triethylamine, N-methyldiethanolamine, N-methyldiisopropanolamine or : . - . .. - ~ ,. - ~ - - . .

N-butyldiethanolamine. These auxiliaries can be present in an amount of D.1 - 5, preferably 0.1 - 1X by weight.
The amount of catalyst is, in general, 0.01 to 5, preferably 0.02 to 2X by weight, relative to the total solids content of the starting material. It can be varied depending on the reactivity of the compounds A) and B) and the intended mode of carrying out the pro-cess. ~he catalyst can also be added in portions, i.e~
in several stages.
In one embodiment of the invention, the com-pounds A) are reacted as a mixture containing a minor proportion of compounds A) ~hich contain only one group of the formula I, or the compounds B) are reacted as a mixture containing a minor proportion of compounds B) which conta;n only one active H atom or only one group of the formula (II) . This alternative will, however, only be made use of if it is desired to reduce the den-sity of crosslinking and to vary the associated proper-ties of the product correspondingly. This is parti-cularly the case when at least one of the componentsA) and B) effects a particularly high degree of cross-linking, as the result of a relatively high proportion of reactive groups, for example if a monomolecular hexaacrylic acid ester is used, so that an undesirable stiffening of the reaction product, and hence the risk of possible embrittlement, must be expected ;n a given case. In this embodiment, the proportion of compounds containing only one group tI) or (II) wi ll not be more than 20, preferably not more than 10 and particularly up to 5X by weight, relative to the particular analogous compound A) or B). By making an addition of this type it ;s possible to control the hardness and elasticity of the reaction product to a certain extent. Examples of compounds A) containing only one reactive group tI) ~hich should be employed for this varian~ are the esters or amines of the unsaturated carboxylic acids which have been enumerated for A), but which have been esterified, or reacted with the formation of amides, only with mono-hydric alcohols or monoamines.
.

. i . .

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Examples of compounds ~) ~hich are suitable for this embodiment are those containing the groupings men tioned above under aa) in which R1 has a meaning other than hydrogen, for example the 3 lkyl-substitution pro ducts of acetoacetic acid and malonic acid which have been esterified onLy with a monohydric alcohol or reacted only with a monoamine. Compounds 8) of the type bb~ are amines having only one active H atom on the amino group~
such as secondary monoamines, for example diethylamine, and those of type cc) are alkanol-mercaptans containing only one mercaptan group, for example ethyl mercaptan.
The process according to the invention can be carr;ed out in one or more stages. As a rule, however, for reasons of economy of labor, the single-stage pro-cess will be preferred, for example by carrying out thereaction uith equivalent proportions of components con-taining in each case two active groups or H atoms (equa-tion XII, see formula sheet and underlined H atoms).
The choice of process stages and of the pot life and properties of the product therefore depends on the pro-cess conditions, i.e. on the nature and amount of the starting materials~ the metering in of the catalyst and tne temperature profile. Thus, the elasticity of the crosslinked product can be controlled within a tolerance range~ for example by means of the chain length of the oligomers and/or polymers employed for A) or ~).
Although the process according to the invention is operated discontinuously as a rule, it is also within the scope of the invention to carry out the mixing of the components and the progress of the reaction continu-ously, for example by means of an automatic lacquering device.
If the process is carried out in several stages, one or more of the components can be added in portions.
For example~ in the first stage 1 mole of butanediol bisacrylate can be reacted with 2 moles of malonic acid d;amide (equation XI, see formula sheet), with the for-mation of a product containing two groups (II) each of which has an active tunderlined) H atom. This product 9~

can be reacted in at least one further stage with further molecules of a compound A), with lengthening of the cha;n and crosslinking. Analogously, it is possible, for example, to react one mole of trimethylolpropane trisacrylate or trismethacryla~e in the first stage with three moles of acetylacetone.
The crosslinking in the second stage and, if appropriate, further subsequent stages, can be effected, for example, by the addition of a catalyst. The procedure employed can be such that the reaction in the first stage is carried out with only a relatively small amount of catalyst, for example less than 2X, or with a cata-lyst of relat;vely low activitY. If the second or sub-sequent stages are carried out relatively soon after the preParation of the precursor, it is not necessary to remove the catalyst ~hich may have been employed in the first stage. Either a higher dose of the same catalyst and/or another catalyst can be used in the second stage.
It ;s also possible to prepare, in the first stage, a ; 20 precursor which is stable on storage for a prolonged period of time and can thus be despatched to the pro-cessor. In this case, it will be advantageous to remove the catalyst, for example by neutralization or distil-lat;on, or to employ a catalyst which is either attached from the outset to a polymer, such as polymerized tri-phenylvinylphosphonium fluoride, or which becomes attached to a polymer dur;ng the reaction. Before ulti-mate application, the crosslinking reaction ~ill be set in progress by a further addition of an adequate amount ; 30 of catalyst.
- The process according to the invention can be carried out in the presence or absence of organic sol-vents which, in a given case, also exert an effect on the activity of the catalysts. Examples of suitable solvents are aromatic and aliphatic hydrocarbons, such as toluene, the various xylenes, mixtures of aliphatic and/or aromat;c hydrocarbons, mineral oil fract;ons, ; esters, ethers~ alcohols or the like.
All the reactants can be employed on their own ~L2~ 4~4 ., o-r--as- 3 mixture, insofar as they are compatible with one another.
Although the process according to the invention is usually carried out under normal pressure, i~ can be S desirable ;n individual cases also to ~rork under an ele-vated pressure in order to increase the rate of curing.
The ratio of the amounts of reactants A) and 8) to one another depends on the number of unsaturated groups (I) in compound i~ and the sum of the active H atoms in compound B), that is to say including those in the groups tII) ~referred to in brief below as "active double bonds:
active H atoms"). If the process is carried out in several stages, this ratio can be varied within a wide range for the pr~?paration of the precursors. For the preparation of the crossl;nked end product, however, the said ratio of acl:ive double bonds:active H atoms is generally about 2.4:0.8 to 0.8:2.4, preferably about 2:1 to 1:2 and particularly about (0.8 to 1.2):1 to 1:(0.8 to 1.2). Therefore, because of the two active H atoms in the acetoacet~c ester, only about 0.8 to 1.2 moles of acetoacetic ester ~ill, for example be used for one mole of ethanediol bisacrylate. If, on the other hand, it is desired to react only one H atom in the aceto-acetic ester, it is also possible to employ 2 x (0.8 to 1.2) moles of acetoacetic ester (formula XII, see for-nrula sheet). As can be seen from this formula, the reaction product still contains one reactive group (see ~he underlined H atom~, so that it can crosslink further either with other molecules or ~rith itself. The ratio of active double bonds:active H atoms is then 1:1. On the other hand, ~t is also possible to employ a mixture of the components; A on the one hand and/or B on the other hand, with a different functionality in each case, in order to control the degree of crosslinking in the end products.
The reac1ion mixture according to the invention is a 2-component system which exhibits pot lives varying bet~reen 5 minutes; and about 12 hours, depending on the choice of the conrpounds A) and B) and on the nature and ,:

~8~99L

amount of the catalyst or combination of catalysts.
This ensures a high degree of reliabiLity in processing.
Because of this advantageous property of the product, ;n conjunction with its rapid and fault-~ree curing at room temperature or elevated temperatures and its resistance to chemicals, it is excellently suitable for use as a binder for coatings.
The 2-component systems can be applied as coat-ings to many kinds of substrates, for example to substrates of an organic or inorganic nature, such as uood, wood fiber materials, for example for sealing wood, textiles of natural or synthetic origin, Plastics, glass, ceramics, building materials, such as concrete, fiberboards or artific;aL stone, but particularly to metal. The coatings can also be employed for domestic and industr;al articles and equipment, for example refrigeration equipment, ~ashing machines, electrical equipment, w;ndows, doors, furniture or the like. The preferred use ;s, however, for motor vehicles. Applica-tion can be carried out by brushing, spraying, dippingor electrostatic means. The 2-component systems can, of course, also contain the customary additives, such as dyestuffs, pigments, fillers, plasticizers, stabi-lizers, leveling agents, neutral;zing substances, such as tertiary amines, and catalysts, and these can be used in the customary amounts. These substances can be added to the individual components and/or to the total mixture.
The follo~ing are mentioned as examples of dye-stuffs or pigments, which can have an inorganic or 3û organic nature: titanium dioxide, graphite, carbon black, zinc chromate, strontium chromate, barium chro-mate, lead chromate, lead cyanamide, lead silicochromate, calcium molybdate, manganese phosphate~ zinc oxide, cad-mium sulfide, chromic oxide, zinc sulfide, nickel titanium yellow, chromium titanium yellow, red oxide of iron, black oxide of iron, ultramarine blue, phthalocya-nine complexes, naphthol red or the like.
Examples of suitable fillers are talc, mica, kaolin, chalk, powdered quartz, powdered asbestos, s.

powdered slate, barium sulfate, various grades of silica, silicates or the like.
The customary solvents are used for the fiLlers, for example aliphat;c and aromatic hydro-carbons, ethers, esters, glycol ethers and estersthereof, ketones, chlorinated hydrocarbons, terpene derivatives, such as toluene or xylene, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether-acetate, ethylene glycol monobutyl ether-acetate, ethylene glycol dimethyl ether, cliethylene glycol dimethyl ether, cyclo-hexanone, methyl ethyl ketone, acetone, isophorone or mixtures thereof~
The scope of the invention therefore also includes 2-component systems which are suitable for the production of coaltings, preferably motor vehicle lac-quers and especially automobile refinishing paints. The resistance to xylene and hence, at the same time, good resistance to premium grade gasoline is of particular ;nterest in this respect~ The use, according to the invention, of the reaction products is therefore particu-larly advantageous. Since the 2-component system in accordance with a preferred embodiment of the invention can cure of itself at room temperature ~ithin a rela~
tively short time, without environmentally polluting substances being liberated, its use as an automobile - refinishing paint is of considerable practical importance.
In the instructions and Examples below, X
denotes in each case X by weight and parts denote in each case parts by ~eight. Vacuum is to be understood in each case as Ineaning a waterpump vacuum.
Examples I Preparation of the component A (MichaeL accePtOr) A 1) 400 parts of acrylic acid, 200 parts of toluene, 3 parts of hydroquinone monomethyl ether and 3 parts of p-toluenesulfonic acid were added to 400 parts of a sol-vent-free acrylir resin (R)Macrynal SM 510 made by Hoechst AG) ~OH No. 150). The mixture was hea~ed under a water separator, while air was passed through ;t, until :
' 9~
_ ~9 the evolution of ~2 was complete. After the mixture had been cooled to room temperature and washed with water, the excess acrylic acid was removed. The organic phase was freed from the solvent by vacuum distillation and ~as diluted to a solids content of 60X. C=C equivalent weight 864.
A 2) 500 parts of methyl acrylate, 3 partQ of hydro-quinone monomethyl ether and 6 parts of dibutyltin oxide ~ere added to 510 parts of the acrylic resin mentioned under A 1. 26 parts of methanol were distilled off through a Vigreux column at an internal termperature of 80 to 90C in the course of 30 hours. The excess methyl acrylate was removed by vacuum distillation. The residue was d;luted with xylene to a solids content of 60%. C~C
1~ equivalent weight 1,083.
A 3) 1,000 parts of an acrylic resin containing glycidyl groups, prepared from styrene, glycidyl methacrylate and d;methyl maleate ~epoxide equivalent weight 510) were dis-solved in b60 parts of xylene at 70C. 127 parts of acrylic acid and 1 part of tetraethylammonium bromide were added at 7ûC. The mixture uas subsequently stir-red at 80C, while air was passed through it, until an acid number of 1 ~as reached. The pale yello~ solution was diluted with 17 parts of xylene. Solids content 62.5%, C=C equivalent weight 1,022.
A 4) 0.1 part of dibutyltin dilaurate and S0 parts of n-butyl isocyanate were added to 570 parts of the resin solution from Example A 3. The mixture was subsequently stirred for 4 hours at 60C (NC0 value 0.2X). Solids content 65X; C=C equivalent weight 1,112.
A ~) 296 parts of tri~ethylolpropane trisacrylate ~ere initially placed in a 1 l flask equipped with a stirrer, a reflux condenser and a gas inlet, and 200 parts of iso-propanol and 1.5 parts of triethylamine ~ere added. 17 parts of hydrogen sulfide were absorbed at room tempera-ture. The ~ixture was stirred for a further hour at 30C.
The heavier product phase formed ~as then separated off as a nearly colorless liquid. Solids content 88%; C=C
equivalent weight 172.

~2~ L94 A 6) 657 parts of a melamine resin of the hexamethoxy-methyl melamine type (molecular ~eight 399), 1,053 parts of 2-hydroxyethyl acrylate, 3.3 parts of hydroquinone monomethyl ether and 1.65 parts of sulfuric acid ~ere initially placed in a three-necked flask equ;pped wi~h a stirrer, a thermometer and a distillation column fitted ~ith a descending condenser. The mixture ~as warmed to 75C in vacuo and was heated at 95C for 4 hours.
After being cooled to room temperature, it was neutrali-zed w;th 10 parts of a 10X strength methanolic potassium ~ hydroxide solution and filtered. This gave 141 parts of a clear resin solution of low viscosity. C=C equivalent weight 175.
A 7) 1 part of dibutyltin dilaurate was added to 220 parts of isophorone diisocyanate, and the mixture waswarmed to 50C. 2 parts of hydroquinone monomethyl ether, dissolved in 232 parts of hydroxyethyl acrylate, were added dropuise in the course of one hour at the same temperature. The mixture ~as then stirred until the N=C=0 content was less than 0.5. After 7 parts of a glycidyl ester of a saturated C9_11 fatty acid, branched in the ~ -position, tepoxide equivalent weight 260) and 0.5 part of chromium-III octoate had been added, the mix-ture was stirred for 5 hours at 80C, and 115 parts of xylene were then added~ Solids content 80X; C=C
equivalent weight 289.
II Preparation of the component a tMichael donor) 3 1) 312 parts of neopentylglycol and 706 parts of methyl acetoacetate were heated to 130 to 160C under N2 as a protective gas in a 2 l glass flask, equipped with a distillation bridge, a stirrer and an electrical thermometer. When the removal of methanol by distilla-tion ~as complete ~after approx. 7 hours), the mixture was cooled to 120C. The excess methyl acetoacetate was removed by vacuum distillation. This left a residue of 819 parts of a clear, pale liquid. C-H equivalent weight 70.
~ 2) 670 parts of trimethylolpropane and 1,972 parts of methyl acetoacetate were heated from 130 to 180C in ~......... ... , .; ~: - -the course of ~ hours in a 4 l apparatus analogous to that of a 1. When the distlllation ~as complete, the receiver contained 465 parts of methanol. The mixture was cooled to 150C, and the low-boiling fraction was removed by vacuum distlllation. This left a residue of 1,95û parts cf a colorless liquid. C-H equivalent weight 64.
B 3) 335 parts of trimethylolpropane and 2,400 parts of diethyl malonate were heated to 150 to 170C under N2 as a protective gas in the same apparatus as that of 8 1. When the removal of the ethanol by dis~illation was complete, the excess diethyl malonate was removed by vacuum distillation at 150 to 160C. This left a resi-due of 1,2û1 parts of a colorLess liquid. C-H equivalent weight 79.
B 4~ 92 parts of glycerol and 426 parts of 2,2,6-tri-methyl-4-oxo-4H-1,3-dioxin were initially placed in an apparatus as described in 8 1. 160 parts of acetone were removed by distillation at 180C, with stirring, in the course of 5 hours. The residue was then freed from low-boiLing constituents at 120C in vacuo. This left 348 parts of a yellow liquid of low viscosity. C-H
equivalent weight 58.
8 5) 300 parts of ethyl acetoacetate, 3 parts of potas-sium hydroxide solution and 4 parts of hydroquinone mono-methyl ether were initially placed in a 1 l three-necked flask equipped with a stirrer, a reflux condenser and an electrical thermometer, and were heated to 130C with stirring. 1~8 parts of butanediol diacrylate were metered in in the course of one hour. After a further 2 hours the double bond content was less than 0.2X. The potassium hydroxide solution was then neutralized with methanolic ; hydrochloric acid. The low-boiling constituents were removed by applying a high vacuum at 100C. This left 35 464 parts of a pale yellow, viscous liquid. C-H equiva-lent weight 232.
8 6) 250 parts of a polyethylene glycol diamine (amine number 243), dissolved in 166 parts of diethylene glycol dimethyl ether~ were added dropwise at -20C to a solution s~

o-f--1-90 parts of diketene in 134 parts of diethylene glycol dimethyl ether. After being st;rred for 1 1/2 hours at -28C, the m;xture was warmed to +10C and was then stirred until an amine number less than 1 had been reached.
After 10 parts of ethanol had been added, the m;xture was heated at 90C for 40 minutes. The solvent was then removed by vacuum distillation. The residue was taken up in 100 parts of dimethoxyethane. This gave a clear, pale yellow solution. Solids content 81X; C-H equivalent weight 1Z2.
B 7) 134 parts of trimethylolpropane and 327 parts of methyl cyanoacetate were heated with 4 parts of titanium acetylacetonate from 100 to 180C with removal of methanol by d;stillation. After 4 hours, the mixture was cooled to 140C, and the low-boiling fraction was removed by vacuum distillation. This left 341 parts of a yellow liquid. C-H equivalent weight 57.
B 8) 750 parts of the acrylic resin mentioned under A 1 tOH number 150) and 260 parts of ethyl acetoacetate ZO were heated to 15ûC in a distillation apparatus. The mixture uas heated to 170C in the course of 2 hours.
When the removal of the ethanol by distillation was com-plete, the low-boiling fraction was removed by applying a vacuum. After the mixture had been cooled to 100C, 306 parts of xylene were added. This gave a clear, pale yellow liquid. Solids content 75X; C-H equivalent weight 310.
~ 9) 510 parts of a polyester (OH number 110) prepared from trimethylolpropane, terephthalic acid, adipic acid and neopentylglycol were heated to 140C with 130 parts of ethyl acetoacetate. The mixture was heated to 170C
jn the course of 3 hours while volatile constituents were continuously removed by d;stillation. After the residue had been cooled to 140C, the low-boiling fraction ~as removed by vacuum distillation. The residue was then diluted with 198 parts of xylene. This gave a clear, pale yellow solution~ Solids content 75X; C-U equivalent weight 402.
B 10) 300 parts of the acrylic resin, containing OH

.. .. ..

12 ~3iL49~
~ Z3 -groups, mentioned under A 1 ~ere dissolved in 200 parts of xylene at 70Ca ~hen the solution had been cooled to room temperature, 0.025 part of dimethylaminopyridine was added. 60 parts of d;ketene were added dropwise in the course of 6 hours. Af~er a further 12 hours the con-tent of free diketene was 0.2Z. Solids content 65X; C~H
equivalent we;ght 392.
B 113 440 parts of coconut oil fatty ac;d methyl ester ~saponificat;on number 255) and 268 parts of trimethylol-propane and 1 part of butyl t;tanate were heated to 180C;n a d;st;llation apparatus. The temperature was slowly ;ncreased to 250C ;n the course of 7 hours, with contin-uous removal of methanol by d;stillation. After a total of 59 parts of methanol had been distilled off, the mix ture was cooled to 100C, and 585 parts of ethyl aceto-acetate were added~ After the mixture had been warmed to 140C, ;t ~as heated to 175C in the course of 3 hours, w;th cont;nuous d;stillation. In total, a further 175 parts of distillate were obtainsd. After the mixture had been cooled to 150C~ the low-boiling fraction ~as re-moved ;n vacuo. This gave 992 parts of a v;scous, pale yello~ liquid. C-H equivalent ~eight 124.
B 12) 200 parts of acetylacetone and 0.5 part of tri-methylbenzylammonium hydrox;de were warmed to 40C.
170 parts of trimethylolpropane trisacrylate were added droP~ise in the course of 2 hours. The mixture ~as then stirred until it had a double bond content of less than 0.5Z. A pale yellow, viscous liqu;d was obtained. C-H
equ;valent we;ght 162. 0 III) Preparation of a self-crosslinking reaction product ;n accordance with the invent;on C) ~Example 17) 924 parts of a 70X strength solut;on in xylene of an acrylic resin (OH number 130) (carrier sub-stance) prepared by free radical polymerization of sty-rene, hydroxyethyl methacrylate and methyl methacrylatewere reacted, at 40C, with 258 parts of a 70X strength solution in xylene of a toluylene diisocyanate, half-masked with hydroxyethyl acrylate (N=C=O content 9.8%, C=C equivalent weight 290) (component A), in the presence .49~

of 5 parts of dibutyltin diLaurate, until an isocyanate content of less than 0.3~ had been reached. 2 parts of dimethylaminopyridine were then added and 25 parts of diketene ~component ~) were added dropwise at room tem-perature, w;th stirring. After stirring at room tempera-ture for 24 hours, free diketene could no longer be detected. Solids content 71X; C=C equivalent weight 2,022;
C-H equivalent weight 2,020- The equivalent amount of acetoacetic ester can also be reacted instead of diketene, a product with the same characteristic data being obtained.
IV) ~
Examples 1 to 51 according to the invention are summarized in Tables 1 and 2. In addition, four compari-son tssts V 1 to 4 using commercially available products are also described.
The amounts by weight of the components A and B
indicated in Tables 1 and 2 below were mixed. The compari-son substance used was a copolymer prepared from 31 parts of glycidyl methacrylate, 15 parts of dimethyl maleate 2~ and 54 parts of styrene. The curing agent used for th;s system was diethylene triam;ne. In the case of the pig-mented coatings, the amount of titan;um d;oxide corres-ponding to the desired degree of pigmentation was mixed in, and the mixture was ground on a bead mill. The result-ing coating material, as such or, if necessary, afterthe catalyst indicated had been mixed in, was applied to glass sheets in a wet film thickness of 100 ~m by means of a doctor-blade, and was cured at a~bient ~rature or at 80C (30 minutes).
The abbreviat;ons used in the Tables below denote as follows:
ABAH : Alkylbenzyldimethylammonium hydroxide (alkyl =
C1 6-C22) ~TAH : Benzyltrimethylammonium hydroxide DETA : Diethylenetriamine HC : Hot curing = 30 minutes at 80C
RT : Room temperature T~AF : Tetrabutylammonium fluoride TBAH : Tetrabutylammonium hydroxide ~.Z~ 9~

TMPSG : Trimethylolpropane trithioglycolate TMPTA : Trimethylolpropane trisacrylate TPTP : Tris-p-tolylphosphane MDPP : Methyl diphenylphosphane PDOAP : Phenyl di-o-anisylphosphane DPOAP : D;phenyl o-anisylphosphane TPAP ~ Tris-p-anisylphosphane MDPAP : Methyl di-p-anisylphosphane DPPDAPP : D;phenyl-p-dimethylaminophenylpnosphane THMP : Trishydroxymethylphosphane TCEP : Tris-2-cyanoethylphosphane TDAMP : Tris diethylaminomethylphosphane TDAIP : Tris dimethylamino-1,1-dimethylbenzylimino-phosphorane TBIP : Tributyl-1,1-dimethylbenzyliminophosphorane TPP : Triphenylphosphane DBU : 1,8-D;azabicyclo-~5.4.0]-undec-7-ene DBN : 1,5-Diazabicyclo-~4.3.0]-non-5-ene TM~ : N,N,N',N'-tetramethylguanidine DAB~O : 1,4-diazabicyclo-~2.2.2]-octane , - 2 6 - ~L28149~

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V) Discussion of the results As can be seen from Table 1, the products of Ex-amples 1 to 38 display a high resistance to chemicals and a high degree of hardness, i.e. they are compLetely cross-linked although curing has been carried out in some casesonly at room temperature. On the other hand, they also have advantageous pot lives, cf. in particular, Examples 6 to 9, 16 - 18, 22, 23, 27 and 30. The last-mentioned Examples show that a pot l;fe within the range from 5 to approx. 20 hours can be achieved by suitable choice of catalysts. It is evident from Examples 11 to 13 and also 16, 19 - 21, 24, 28 and 33 to 37 that high values of hardness are obtained even after 1 day if forced drying is employed (hot curing for 30 minutes at 80C).
In comparison with Table 1, Table 2 shows that the pot lives of the pigmented systems are somewhat shorter, but that they are nevertheless adequate for reliable pro-cessing. As can be seen from Examples 39 to 49, the films cure completely even at room temperature. The resistance to chemicals of the products according to Table 2 is on average higher than that of the unpigmented systems of Table 1.
Examples 12, 13, 50 and 51 sho~ that the amine and mercapto compounds, as component ~, also produce complete curing and good resistance to chemicals in the products, the reaction even being carried out without a catalyst in the case of Examples 13 and 51. The physical data of comparison tests V 1 to V 4 show a low resistance to xylene and also a less pronouced degree of curing. The products according to the invention are therefore superior to the comparison samples.

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~Alkyl 0), PO - CH2 - COOR IVII) (CH~ ) l -CH2 -CO-O- (CH" a -O-CO-C~, -P ~OCH, ), (VIII ) P
NCCH2-P-O-CH~-C (CH, ), -CH2-O- I -CH2-CN (IX) R, R
(R60), - I (CH2 ) 2 ~ (CH2 ) 2 ~ (CH2 ) 2~ (CH, ) 2 ICH-~ (0~6 ), O=P (ORS ) 2 o=P (OF~ ) 2 R6 = C1 5-Alkyl (X) H, C~CH-CO-O- (CE~2 ) 4-O-C~CH=CH2 2 CH2 (CO~2) 2 (H2 NOC), CH-C~2 -CH2 -COO- (CH2 ) 4-OOC- (CH2 ) 2 -C~l (CONH, ) ,.
(XI ) 2 H, C~C~-COO- (CH~ OOC-CY=CH, ~2 CH, -CO-C~1 -COOR
co - eH~
H, C~CH-COO- (CH, 3, -OOC-CH2 -C~C - COOR
ROOC ~-CB,-CH2-COO- ~CH2 ),-O~C-CH2-CH, ~XII) ~1 `:~

Claims (54)

1. A reaction product of A) compounds containing at least two R1R2C=CR3-X groups (I) in which formula (I) X denotes -CO- which is attached to a further R1R2C=CR3 group either directly or via the radical of a polyhydric alcohol or of an amine, R1 denotes hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms, R2 denotes hydrogen, a hydrocarbon radical having 1 to 10 carbon atoms, an ester group containing the radical R4 of a monohydric alcohol having up to 12 carbon atoms, -CN, -NO2 or a CO-NHR1 or CO-R1 group, and R3 has the same meaning as R2 and is identical with or different from the latter, with B) compounds which contain a) at least two active H atoms or b) at least two groups containing active H atoms of the type -AH- (II) or c) at least one active H atom and at least one group of the type (II), or which form the corresponding amount of this group (II) in which formula (II) -AH- denotes one of the groupings -?H- and -SH, subject to the proviso that reaction products of A) poly-acrylates containing at least two free acrylic acid groups, reaction products of polyisocyanates with acrylic acid esters containing OH-groups or reaction products of epoxy resins with acrylic acid, with B) diketene or acetoacetic acid esters of hydroxyethyl acrylate or methacrylate are excluded, wherein the reaction product is obtained via Michael reaction in the presence of at least one catalyst selected from the group consisting of diazabicyclooctane (DABCO), halides of quaternary ammonium compounds, on their own or as a mixture with alkyl silicates, amidines, organic phosphonium salts having 1 to 20 carbon atoms in the alkyl radical or aryl radical or both, tertiary phosphanes of the general formula P(CH2-Y)3 in which the Ys are identical or different and denote the radical -OH, CH2CN or -N(Z)2 in which Z is an alkyl radical having 1 to 5 carbon atoms, tertiary phosphanes of the general formula P(R4,R5,R6) in which the radicals R4, R5 and R6 denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R4, R5, R6 are identical or different, but at least one of the radicals represent a phenyl radical, and aminophosphoranes of the general formula (R7,R8,R9)P=N-C(R10,R11,R12) in which R7, R8 and R9 are identical or different and denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R10, R11 and R12 are identical or different and each represents an alkyl radical having 1 to 5 car-bon atoms or phenyl radical.

2. A reaction product of A) compounds containing at least two R1R2C=CR3-X groups (I), in which formula (I) the radicals R1 to R3 and X have the meaning as defined in claim 1, with B) compounds which contain a) at least two groups containing active H atoms of the type -CH- (II) derived from unsubstituted or mono alkyl substituted malonic acid moieties or from the grouping NC-CHR1-CO-, NC-CH2-CN, =PO-CHR1-CO-, =PO-CHR1-CN, =PO-CHR1-PO=, or -CO-CHR1-NO2 b) at least one active H atom and at least one group of this type (II), or which form the corresponding amount of this group (II).

3. Reaction product as claimed in claim 1 wherein the groups (I) in the compounds A) are attached to an oligomer or polymer.

4. Reaction product as claimed in claim 2 wherein the groups (I) in the compounds A) are attached to an oligomer or polymer.

5. Reaction product as claimed in claim 1 wherein the group -AH- (II) of the compound B) is derived:

aa) when it denotes -?H-, from a compound containing the grouping -CO-CHR1-CO-, NC-CHR1-CO-, NC-CH2-CN, =PO-CHR1-CO-, =PO-CHR1-CN, =PO-CHR1-PO=, or -CO-CHR1-NO2, and bb) when it denotes -SH, from at least one component selected from the group consisting of thioalcohol acid ester, amide and a mercaptan.

6. Reaction product as claimed in claim 5 wherein the groups (I) in the compounds A) are attached to an oligomer or polymer.

7. Reaction product as claimed in claim 1 wherein the radical R1R2C=CR3-X (I) in the compound A) is derived from at least one acid selected from the groups consisting of acrylic acid, methacrylic acid, maleic acid and its anhydride and the compound B) contains malonic acid moieties attached by an ester linkage.

8. Reaction product as claimed in claim 2 wherein the radical R1R2C=CR3-X (I) in the compound A) is derived from at least one acid selected from the groups consisting of acrylic acid, methacrylic acid, maleic acid and its anhydride and the compound B) contains malonic acid moieties attached by an ester linkage.

9. Reaction product as claimed in claim 3 or 5 wherein the radical R1R2C=CR3-X (I) in the compound A) is derived from at least one acid selected from the groups consisting of acrylic acid, methacrylic acid, maleic acid and its anhydride and the compound B) contains malonic acid moieties attached by an ester linkage.

10. Reaction product as claimed in claim 1 wherein the radical R1R2C=CR3-X (I) in which X denotes -CO- and R3 denotes hydrogen or alkyl having 1 to 8 carbon atoms, is derived from a monounsaturated or polyunsaturated carboxylic acid having a basicity of not more than two and containing 2 to 10 carbon atoms.

11. Reaction product as claimed in claim 2 or 3 wherein the radical R1R2C=CR3-X (I) in which X denotes -CO- and R3 denotes hydrogen or alkyl having 1 to 8 carbon atoms, is derived from a monounsaturated or polyunsaturated carboxylic acid having a basicity of not more than two and containing 2 to 10 carbon atoms.

12. Reaction product as claimed in claim 5 or 7 wherein the radical R1R2C=CR3-X (I) in which X denotes -CO- and R3 denotes hydrogen or alkyl having 1 to 8 carbon atoms, is derived from a monounsaturated or polyunsaturated carboxylic acid having a basicity of not more than two and containing 2 to 10 carbon atoms.

13. Reaction product as claimed in claim 1 wherein the com-pound A) is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, an epoxide resin each containing OH-groups and amine resin.

14. Reaction product as claimed in claim 2 or 3 wherein the compound A) is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, an epoxide resin each containing OH-groups and amine resin.

15. Reaction product as claimed in claim 5 or 7 wherein the compound A) is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, an epoxide resin each containing OH-groups and amine resin.

16. Reaction product as claimed in claim 8 or 10 wherein the compound A) is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, an epoxide resin each containing OH-groups and amine resin.

17. Reaction product as claimed in claim 1 wherein the com-pound B) is derived from an at least bifunctional compound selec-ted from the group consisting of polyols and polymercaptans.

18. Reaction product as claimed in claim 3 wherein the com-pound B) is derived from an at least bifunctional compound selec-ted from the group consisting of polyols and polymercaptans.

19. Reaction product as claimed in claim 3, 5 or 7 wherein the compound B) is derived from an at least bifunctional compound selected from the group consisting of polyols and polyamines.

20. Reaction product as claimed in claim 10 or 13 wherein the compound B) is derived from an at least bifunctional compound selected from the group consisting of polyols and polymercaptans.

21. Reaction product as claimed in claim 1 wherein the pro-duct is present on a substrate.

22. Reaction product as claimed in claim 2 or 3 wherein the product is present on a substrate.

23. Reaction product as claimed in claim 5 or 7 wherein the product is present on a substrate.

24. Reaction product as claimed in claim 10, 13 or 17 where-in the product is present on a substrate.

25. Reaction product as claimed in claim 8 or 18 wherein the product is present on a substrate.

26. A process for the preparation of reaction products which comprises reacting compounds A) containing at least two R1R2C=CR3-X groups (I) in which formula (I) the radicals R1 to R3 and X have the meaning as defined in claim 1, with B) compounds of the type as defined in claim 1 under the formation of an oligomeric or polymeric reaction pro-duct, the reaction being carried out, in the event that -AH- represents one of the groups -?H- or -SH, in the presence of at least one catalyst as defined in claim 1.

27. The process as claimed in claim 26 wherein the catalyst(s) employed are fluorides or phosphanes.

28. A process as claimed in claim 26 wherein the reaction is carried out at a temperature from -10 to 180°C.

29. The process as claimed in claim 26 wherein the catalysts employed are trishydroxymethylphosphane, trisdimethylaminomethyl-phosphane, tris-p-anisylphosphane, methyldiphenylphosphane, methyl di-p-anisyl-phosphane or .alpha.,.alpha.-dimethylbenzylimonotributylphos-phorane.

30. The process as claimed in claim 28 wherein said reaction taken place in the presence of one or more catalyst selected from the group comprising trishydroxymethylphosphane, trisdimethyl-aminomethylphosphane, tris-p-anisyl-phosphane, methyldiphenyl-phosphane, methyl di-p-anisyl-phosphane or .alpha.,.alpha.-dimethylbenzyl-imonotributylphsphorane.

31. A process as claimed in claim 26 wherein a component A) is reacted in which the radical R1R2C=CR3-X (I), in which X de-notes -CO- and R3 denotes hydrogen or alkyl having 1 to 8 carbon atoms, is derived from a monounsaturated or polyunsaturated car-boxylic acid having a basicity of not more than two and containing 2 to 10 carbon atoms.

32. A process as claimed in claim 27 or 28 wherein a com-ponent A) is reacted in which the radical R1R2C=CR3-X (I), in which X denotes -CO- and R3 denotes hydrogen or alkyl having 1 to 8 carbon atoms, is derived from a monounsaturated or polyunsatur-ated carboxylic acid having a basicity of not more than two and containing 2 to 10 carbon atoms.

33. A process as claimed in claim 29 wherein a component A) is reacted in which the radical R1R2C=CR3-X (I), in which X de-notes -CO- and R3 denotes hydrogen or alkyl having 1 to 8 carbon atoms, is derived from a monounsaturated or polyunsaturated carboxylic acid having a basicity of not more than two and con-taining 2 to 10 carbon atoms.

34. A process as claimed in claim 31 wherein the carboxylic acid contains 3 to 6 carbon atoms.

35. A process as claimed in claim 31 wherein the carboxylic acid is acrylic acid, methacrylic acid and/or maleic acid.

36. A process as claimed in claim 31 wherein the catalyst employed are fluorides or phosphanes.

37. A process as claimed in claim 31 wherein said reaction is carried out at a temperature from -10 to 180°C.

38. A process as claimed in claim 36 or 37 wherein the car-boxylic acid contains 3 to 6 carbon atoms.

39. A process as claimed in claim 36 or 37 wherein the car-boxylic acid is acrylic acid, methacrylic acid and/or maleic acid.

40. A process as claimed in claim 26 wherein a compound A) is reacted in which groups (I) are attached to an oligomer and/or polymer.

41. A process as claimed in claim 27 or 28 wherein a com-pound A) is reacted in which groups (I) are attached to an oligomer and/or polymer.

42. A process as claimed in claim 29 wherein a compound A) is reacted in which groups (I) are attached to an oligomer and/or polymer.

43. A process as claimed in claim 31 or 36 wherein a com-pound A) is reacted in which groups (I) are attached to an oligomer and/or polymer.

44. A process as claimed in claim 26 wherein a compound A) is reacted which is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, epoxide resin each containing OH-groups and amine resin.

45. A process as claimed in claim 27 or 28 wherein a com-pound A) is reacted which is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, epoxide resin each containing OH-groups and amine resin.

46. A process as claimed in claim 29 wherein a compound A) is reacted which is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, epoxide resin each containing OH-groups and amine resin.

47. A process as claimed in claim 26 wherein a compound B) is reacted in which the grouping -AH- (II) is derived aa) when it denotes -?H-, from a compound containing the grouping -CO-CHR1-CO-, NC-CHR1-CO-, NC-CH2-CN, =PO-CHR1-CO-, =PO-CHR1-CN, =PO-CHR1-PO=, or -CO-CHR1-NO2, and bb) when it denotes -SH, from at least one component selected from the group consisting of thioalcohol, acid ester, amide and a mercaptan.

48. A process as claimed in claim 27, 28 or 29 wherein a compound B) is reacted in which the grouping -AH- (II) is derived aa) when it denotes -?H-, from a compound containing the grouping -CO-CHR1-CO-, NC-CHR1-CO-, NC-CH2-CN, =PO-CHR1-CO-, =PO-CHR1-CN, =PO-CHR1-PO=, or -CO-CHR1-NO2, and bb) when it denotes -SH, from at least one component selected from the group consisting of thioalcohol, acid ester, amide and a mercaptan.

49. A process as claimed in claim 31, 36 or 37 wherein a compound B) is reacted in which the grouping -AH- (II) is derived aa) when it denotes -?H-, from a compound containing the grouping -CO-CHR1-CO-, NC-CHR1-CO-, NC-CH2-CN, =PO-CHR1-CO-, =PO-CHR1-CN, =PO-CHR1-PO=, or -CO-CHR1-NO2, and bb) when it denotes -SH, from at least one component selec-ted from the group consisting of thioalcohol, acid ester, amide and a mercaptan.

50. A process as claimed in claim 40 or 44 wherein a com-pound B) is reacted in which the grouping -AH- (II) is derived aa) when it denotes -?H-, from a compound containing the grouping -CO-CHR1-CO-, NC-CHR1-CO-, NC-CH2-CN, =PO-CHR1-CO-, =PO-CHR1-CN, =PO-CHR1-PO=, or -CO-CHR1-NO2, and bb) when it denotes -SH, from at least one component selected from the group consisting of thioalcohol, acid ester, amide and a mercaptan.

51. A process as claimed in claim 26, 27 or 28 wherein a compound B) is reacted which is derived from an at least bifunc-tional compound selected from the group consisting of polyols and polymercaptans.

52. A process as claimed in claim 29, 31 or 36 wherein a compound B) is reacted which is derived from an at least bifunc-tional compound selected from the group consisting of polyols and polymercaptans.

53. A process as claimed in claim 37, 40 or 44 wherein a compound B) is reacted which is derived from an at least bifunc-tional compound selected from the group consisting of polyols and polymercaptans.

54. Two-component lacquer composed of A) compounds containing at least two R1R2C=CR3-X groups (I) in which formula (I) the radicals R1 to R3 and X have the meaning as defined in claim 1 and B) compounds as defined in claim 1, on its own or in combination with customary additives.