DE3508399A1 - IMPLEMENTATION PRODUCT OF OLEFINICALLY UNSATURATED COMPOUNDS WITH HYDROGEN-ACTIVE COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND BASED 2-COMPONENT PAINTS - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 85 / F O36J Dr.I & St

Reaction product of olefinically unsaturated compounds with hydrogen-active compounds, process for its production and 2-component paints based on it

It is known to combine unsaturated compounds, such as cinnamic acid esters, with Η-active compounds, e.g. malonic acid esters or acetoacetic ester, by Michael addition to form substituted compounds, e.g. substituted malonic acid esters, implement (Krauch-Kunz "Name reactions of organic chemistry" 5th edition 1976, page 42).

It is also known to use an acrylate resin containing OH groups or an acrylate resin modified with ε-caprolactone to be used in a mixture with polyisocyanates as two-component paints (DE-PS 3 005 9 ^ 5, 3 027 776 and 3 148 022). Another publication describes the reaction of acrylate copolymers containing epoxy groups with a partially blocked isocyanate and the use of the reaction product as a paint binder (DE-OS 3 I30 545).

Some of the well-known products have proven themselves well. However, attempts have been made to find more environmentally friendly products by starting with systems without free isocyanate.

Thus, in another publication, an oxazolidine-containing acrylate resin is described, the water or humidity uses as a hardener (EP-OS 34 720). This system has the disadvantage that the hardened surface a deeper penetration of water into the lower layers of the coating counteracts and thus a complete Hardening prevented by the entire layer thickness.

It is also a two-component system that reacts without isocyanate known. This consists of an epoxy

group-containing acrylic resin which is curable with another acrylic resin containing tertiary amino groups. In the case of the product produced by this process, the insufficient degree of crosslinking leads to an insufficient one chemical resistance, so that the coatings produced with this system are only used for a limited area of application are suitable.

U.S. Patent No. 4,408,018 describes acrylic polymers into which acetoacetate moieties have been introduced and which are crosslinked via the Michael addition in the presence of strong bases with Λ, / 3-olefinically unsaturated esters can. The acetoacetate group is introduced via the acetoacetic esters of hydroxymethyl acrylates or

15 methacrylate and subsequent copolymerization with

further copolymerizable monomers or by reaction of polymers containing OH groups with the precursor of the acetoacetic ester component, the diketen. As an organic component that crosslinks with the polymers contained in acetoacetate groups are polyacrylates with more than two acrylate groups, reaction products of polyisocyanates with Acrylic esters containing hydroxyl groups and reaction products of epoxy resins with acrylic acid. These However, compounds have the disadvantage that the strong bases acting as catalysts such as alkali metal hydroxides or alcoholates lead to severe yellowing and clouding of the paint.

The invention is now based on the object of providing the paint binders available on the market to expand a system that does not require free isocyanates for curing, i.e. is environmentally friendly. Here will be Catalysts are used that do not shorten the pot life and also do not cause yellowing of the paint films and which 35

result in coatings when using small amounts of catalyst, meet the high requirements in terms of hardening properties and chemical resistance.

The present invention therefore relates to a reaction product of A) compounds with at least two rVc ^ F ^ -X groups (I) with B) compounds that

a) at least two active Η atoms or

b) at least two groups with active H atoms of the type -AH- (II) or

c) at least one active H atom and at least one Type (II) group

contain or form the corresponding number of this group (II), in which in formula (I)

X -CO-, either directly or via the remainder of a polyvalent Alcohol or an amine to another

12 λ RR C = CR group is bound,

R ^{1 is} hydrogen or a hydrocarbon radical with 1 to 10, such as alkyl, phenyl, benzyl, naphthyl, preferably with up to 4 carbon atoms,

R ^{2 is} hydrogen, a hydrocarbon radical with 1 to 10, preferably 1 to 4 carbon atoms, such as alkyl, phenyl,

4 Benzyl, naphthyl, an ester group with the radical R of a monohydric alcohol with up to 12 carbon atoms, -CN, -

25 -NO ₀ , a CO-NHR ¹ - or a CO-R ¹ group,

3 2

R has the same meaning as R and hereby equals or

is different

in formula (II) -AH- one of the groupings -CH-, -NH- and -SH with the proviso that reaction products of

A) Polyacrylates with at least two free acrylic acid groups, reaction products of polyisocyanates with OH groups Acrylic acid esters or reaction products of epoxy resins with acrylic acid with B) diketene or acetoacetic acid esters are excluded from hydroxyethyl acrylate or methacrylate. Component A is in the reaction product a Michael acceptor, component B) a Michael donor.

The product according to the invention has the advantage that it is made from components that are not toxic and which can therefore be used without special precautionary measures.

Although in the implementation of compounds A) with two groups (I) each with compounds B) with two active H atoms or two groups (II), even if they contain only one hydrogen atom, due to the mutual bifunctionality it is to be expected that only chain elongation occurs here, surprisingly the cured crosslinked reaction products according to the invention. The effective groups of compounds A) and B) can also be contained in a single molecule, so that systems are present that are intermolecular Crosslinking are curable and self-crosslinking.

If a higher reactivity and thus stronger crosslinking of the product is sought, one can with advantage proceed so that in at least one of the compounds A) and B) three or more groups of type (I) or active H atoms and / or groups of type (II) are present.

According to one embodiment of the invention, the rest

ι? λ
RRC = CR-X (I) of a mono- or polyunsaturated at most dibasic carboxylic acid, e.g. mono- and / or dicarboxylic acid, with 2 to 10, preferably 3 to 6, carbon atoms, such as cinnamic acid, crotonic acid, citraconic acid or their anhydride, Mesaconic acid, fumaric acid, dehydrolevulinic acid, sorbic acid, but preferably acrylic acid, methacrylic acid and / or maleic acid or their anhydride, and also from unsaturated ketones such as divinyl ketone, dibenzalacetone; also of unsaturated nitriles, such as maleic acid mononitrile monoesters of polyhydric alcohols,

- M-

of cyanoacrylic acid esters of the formula HC = C (CN) -COOR, of nitrites of the formula ROOC-R- ⁵ C = CH-NO ₂ , of alkylidene malonic acid esters of the formula ROOC-C (COOR J = CR ¹ R ² , alkylidene acetoacetic esters of the formula ROOC- C (CO-CH) = CR R or the corresponding nitriles, where in the above formulas R is the radical of a polyhydric alcohol, R ¹ and R ^{2 are} hydrogen or alkyl, or the like They can be bonded to the radical of a polyhydric alcohol, a compound with NH groups such as a polyamine, polyamide or polyminoamide of a polyhydric phenol, preferably an oligomer and / or polymer. For example, the compound A) can be derived from saturated and / or unsaturated polyethers or polyesters containing OH groups, for example those based on maleic acid, phthalic acid and diols; Acrylic resins containing OH groups; aliphatic or preferably aromatic epoxy resins, optionally containing OH groups, for example those based on diphenylolpropane and / or methane, hydantoin and / or amine resins. The residue (I) bonded in the form of an ester may have arisen, for example, from the addition of acrylic or methacrylic acid to the epoxy group. Polyhydric alcohols suitable as starting substances for A) are, for example, alkanediols and triols, such as ethanediol, the various propane, butane, hexane, octanediols or their homologues, the corresponding oligomeric ethers, and also glycerol, trimethylolethane or propane, hexanetriol , Pentaerythritol, dipentaerythritol, sorbitol, polyvinyl alcohol or the like.

Starting compounds containing NH groups for the compounds A are, for example, alkylenediamines and their oligomers, such as ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, tetramines and higher Homologues of these amines, also amino alcohols, such as Dläthanol-

amine or the like. Aminocarboxylic acid esters, for example, are also used as amines polyhydric alcohols in question. Compounds with NH groups are, for example, acrylic or Methacrylic acid polyamides, also polyurethanes, e.g. polyisocyanates, which are capped in the form of polyurethane groups such as those produced by the reaction of hydroxyethyl acrylate on polyisocyanates, amine resins such as methylolmalamines, preferably hexaraethylolmelamine, urea resins, the remainder (I) with the grouping -CO- on the amine groups of these compounds is bound as an amide. If these amine compounds via OH groups or alkylol groups have available, it is also possible that the radical (I) directly via an ester group (formula III see formula sheet) or indirectly is bound to these resins via an ether group (formula IV see formula sheet). For the ether binding of the rest (I) you can therefore from a hydroxyalkyl ester or a hydroxyalkylamide of an unsaturated acid, such as acrylic acid, go out. The same applies to a corresponding bond to polyhydroxy compounds.

The group -AH- (II) is derived in the compound B) aa) for the meaning -OH- from a compound with the group -CO-CHR-CO-, NC-CHR ¹ -CO-, NC-CH ^ - CN, = PO-CHR ¹ -CO-, = P0-CHR ¹ -CN, = PO-CHR ¹ -PO, -CO-CHR-NO ₀ ,

25 in which R is preferably hydrogen,

bb) for the meaning -NH-, which also includes NHj, from a

primary and / or secondary amine and cc) for the meaning -SH of a thioalcoholic acid ester, -amid and / or a mercaptan.

30 ß-dioxo compounds are preferred.

Suitable compounds B) of type aa) are, for example, ketones, such as acetylacetone, benzoylacetone, acetyldibenzoylmethane, also esters of optionally alkyl-substituted acetoacetic acid such as o- and / or γ-methylacetoacetic acid, or acetone dicarboxylic acid, bonded like an ester

Malonic acid units of malonic acid and their monoalkyl derivatives, straight-chain or branched, with 1 to 6 carbon atoms in the alkyl radical, e.g. methyl, ethyl and η-butyl or phenyl, or cyanoacetic acid with monohydric to hexahydric alcohols with 1 to 10 carbon atoms. The alkyl substituted esters, e.g. α-Methyl- or ο, γ-Dimethylacetessigester, have only one active Η atom and are therefore preferably used in the form of di- or polyesters of polyhydric alcohols to to have a sufficient number of reactive groups available. Suitable alcohols for the esterification of the above Acids are, for example, methanol, ethanol, butanol, octanol and / or, which is preferred, polyhydric alcohols or polyhydroxy compounds like those mentioned as starting substances for A). Other compounds B) are e.g. acetoacetic ester, Ethanediol bisacetoacetic ester, glycerol tris-malonic acid ester, trimethylolpropane-acetoacetic ester, partial esters of these Acids with polyhydric alcohols, also the corresponding esters of acrylic resins containing OH groups, Polyesters, polyethers, polyester amides and imides, polyhydroxylamines, and nitriles of these acids, provided these exist, e.g. malonic acid mono- or dinitrile, alkoxycarbonyl-methanephosphonic acid ester and the corresponding Bis-methanephosphonic acid ester (formula VII see formula sheet). The acids mentioned above can also in the form of amides to amines, preferably polyamines, for example to those in connection with compound A) mentioned, which also comprise oligomers and / or polymers including amine resins, aliphatic amines are preferred.

Also suitable as compounds aa) are reactive nitro compounds, e.g. nitroacetic acid derivatives, such as tris (nitroacetic acid) glycerol esters or trimethylolpropane nitroacetic acid ester.

- Q -

Primary and / or, for example, are suitable as connections bb) secondary polyamines, especially aliphatic di-, tri- and higher amines, e.g. their homologues, oligomers and / or polymers including amine resins as described above, urea and its derivatives, also cyclic, for example aromatic, polyamines such as phenylenediamine or the like or mixtures of aliphatic and aromatic amines, aliphatic amines preferably also being used in this case.

Suitable compounds B) with a group -SH of type cc) are e.g. thioglycolic acid, ß-mercaptopropionic acid- or thiosalicylic acid esters of polyhydric alcohols and thio alcohol ethers and esters, mercaptans, for example Ethyl, propyl mercaptan and their homologues or their ethers, e.g. thioglycerols, substitution products cyclic amines with thioalkanols or the like.

Compounds B) which form groups of type (II) include, for example, diketene and its mono-a-alkyl substitution products, also to mention tetrahydrodioxin, which with suitable components to form acetoacetic ester or amld groups can respond.

The reaction component B) can at least one polyvalent compound of the group mono- or polyhydric alcohols, Polymers containing OH groups, e.g. those mentioned above, polyamines and polymercaptans bound and is multivalued based on the CH puncture. So it can, for example, by esterification of a polyepoxide with a group -AH- (II) forming Carboxylic acid, e.g. cyanoacetic acid (equation V, see formula sheet). This is how you get a component B) with two active Η atoms per epoxy group.

Here, aromatic or aliphatic polyepoxides can be used, e.g. those mentioned above.

If you start from polyamines, compounds B) can be both of type aa) in the form of amides and also those of type bb). Palis the grouping -AH- has the meaning -CH-, one can e.g. from 1 mole of an alkylenediamine go out, which is reacted with 2 moles of acetoacetic ester to form the compound VI (see formula sheet), which also has four hydrogen atoms activated by amld groups. As compounds B) in which group (II) -NH- means that the polyamines as such are sufficient.

In this way, for example, 1 mole of trimethylolpropane trisacrylate React with 3 moles of ethylendlamine, the free amine groups of the product still with other active Acrylate double bonds can react with crosslinking.

The invention also comprises a process for the preparation of reaction products of A) compounds with at least

ι 2 ^
two RRC = CR -X groups (I) with B) compounds that

a) at least two active Η atoms or

b) at least two groups with active hydrogen atoms 20 of the type -AH- (II) or

c) at least one active Η atom and at least one group of type (II)

contain, or form the corresponding number of this group (II), in which in formula (I)

χ -CO-, which either directly or via the remainder of a polyhydric alcohol or an amine to another

12?
RRC = CR group is bound,

R is hydrogen or a hydrocarbon radical with 1 to 10 carbon atoms,

R is hydrogen, a hydrocarbon radical with 1 to 10 carbon atoms, an ester group with the radical R of a monohydric alcohol with up to 12 carbon atoms, -CN, -NO ₀ ,

11 a CO-NHR or a CO-R group,

ο ο

35 R ^{J has the} same meaning as R in formula (II)

. ₁₀ .

-AH- one of the groupings -CH-, -NH- and -SH, characterized in that the compounds A) and B) are reacted to form an oligomeric and / or polymeric reaction product, in the case that -AH- a represents the groups -OH- or -SH, the reaction in the presence of at least one catalyst takes place from the group diazoabicyclo-octane (DABCO), halides of quaternary ammonium compounds, alone or in a mixture with silicic acid alkyl esters, amidines, organic phosphonium salts with 1 to 20 carbon atoms in the alkyl radical and / or aryl radical, tertiary phosphines of the general formula P (CHp-Y) ο > ^{ln which} Y is identical or different is the radical -OH, -CH CN or -N (Z), where Z is a Is an alkyl radical having 1 to 5 carbon atoms, tertiary phosphines of the general formula

P (r \ r ⁵ , R), in which the radicals R ² *, R ⁵ and R ^{6 are} an alkyl radical with 1 to 12 carbon atoms or a phenyl radical, unsubstituted or substituted with at least one alkyl, alkoxy or dialkylamino group each denotes 1 to 4 carbon atoms in the alkyl radical, R, R and R are identical or different, but at least one of the radicals represents a phenyl radical and aminophosphoranes of the general formula (R ⁷ , R ⁸ , R ⁹ ) P = NC (R ¹⁰ , R ¹¹ , R ¹² ), in which R ⁷ , R ⁸ , R ^{9 are} identical or different and are an alkyl radical with 1 to 12 carbon atoms or a phenyl radical, unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each having 1 to 4 carbon atoms in the alkyl radical and R,

1 1 12
R, R are identical or different and are an alkyl radical

with 1-5 carbon atoms or a phenyl radical.

The invention further comprises a process for the preparation of the reaction products mentioned in claim 1, wherein im If -AH- represents one of the groups -OH- or -SH, the reaction in the presence of at least one quaternary ammonium compound or an alkali metal alcoholate as a catalyst

35 takes place.

These procedures go very smoothly. Since oligomeric and / or polymeric compounds A) and B) are preferably used as a starting point, oligomeric and / or polymeric reaction products are also obtained. The reaction is generally carried out at -10 to l80, preferably 0 to 100, especially 20 to 8O ⁰ C. For example, is obtained at room temperature after 2 to 2 ¹ I hours or at 6O ⁰ C after 10 to 40 minutes, products with good hardness .

The reaction of compounds B) in which the grouping (II) is —NH— or —NH ”can be carried out without a catalyst. In contrast, one or more catalysts are generally used, provided the -AH- group represents an -OH group (preferred form) or an -SH group. Catalysts suitable for the Michael addition are, for example, those from the group diaza-bicyclo-octane (DABCO), halides of quaternary ammonium compounds, such as alkyl, aryl and / or benzylammonium bromides, chlorides, and in particular fluorides, the halides optionally in Combination with silicic acid alkyl esters can be used to improve the activity of the catalyst. Examples are, for example, alkylbenzyldimethylammonium halides (alkyl = C ₆ -C ₂₂ ), benzyltrimethylammonium halides, tetrabutylammonium halides, in particular the fluorides and polymerized tryphenylvinylphosphonium fluoride. Also suitable as 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, tributylhexadecylphosphonium bromide, amides such as tetramethylguanidine, diaza-bicyclo-undecene, dlaza-bicyclo-noneceno, and others.

Further suitable catalysts for the process for the production of Michael adducts are the phosphanes (formerly

- ye. -

-β '

referred to as phosphines e.g. a) tertiary phosphines

P (CH ₉ -Y) - such as tris-2-cyanoethylphosphine, trisdiethylaminomethylphosphine, preferably trishydroxymethylphosphine and trisdimethylaminomethylphosphine, b) tertiary phosphines P (R, R, R) such as triphenylphosphine, tris-p-tolylphosphine, trisylis-o-anis -pdimethylaminophenylphosphine, phenyl-di-p-anisylphosphine, phenyl-di-o-anisylphosphine, diphenyl-p-anlsylphosphine, diphenyl-o-anisylphosphine, diphenyl-p-dimethylaminophenylphosphine, butyl-diphenylphosphine, methyl-di-phosphine, methyl-di- -p-anisylphosphine, (diethylaminomethyl) -diphenylphosphine, preferably tris-p-anisylphosphine, methyl-diphenylphosphine and methyl-di-p-anisylphosphine, and c) iminophosphoranes (R ⁷ , R ⁸ , R ⁹ ) P = NC (R ¹⁰ , R ¹¹ , R ¹² ) such as α, α-dimethylbenzylimino-tris (dimethylamino) - phosphorane, α, α-dimethylbenzyliminomethyl-diphenylphosphorane, t-butylimino-tri-phenyl-phosphorane, preferably α, α-dimethylbenzylimino-tri- butylphosphorane.

For the preparation of certain reaction products, catalysts for the Michael addition can also be used, for example, from the alkali metal alcoholate group, such as lithium butylate, sodium, potassium methylate, quaternary ammonium compounds such as alkyl, aryl and / or benzylammonium hydroxides, carbonates. (Alkyl = _C, gC ₂₂₎ in detail, for example, alkyl benzyldimethylammoniumhydroxid be mentioned are benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide. The catalysts or catalyst mixtures mentioned can be used in the presence of tertiary aliphatic amines which are not per se inactive at room temperature, such as, for example, triethylamine, N-methyldiethanolamine, N-methyl-di-isopropanolamine or N-butyldlethanolamine. These auxiliaries can be 0.1 - 5, preferably

35 wise 0.1-1 wt. ?, be present.

The amount of the catalyst is generally from 0.01 to 5, preferably 0.02 to 2 wt. Ji, based on the total solids content of the starting product. You can depending on the reactivity of the compounds A) and B) and the intended Procedure can be varied. The catalyst can also be added in portions, i.e. in several stages.

According to one embodiment of the invention, the compounds A) in a mixture with a minor proportion of those compounds A) which only have one group of the formula I contain, or the compounds B) in a mixture with a minor proportion of compounds B), which only one containing active H atom or only one group of the formula (II), implemented. But one only gets from this possibility then make use of it if you want to reduce the cross-linking density and the associated properties of the Product would like to vary accordingly. This is especially the case when at least one of the components A) and

B) due to a relatively high proportion of reactive groups, e.g. when using a monomolecular hexaacrylic acid ester, causes a particularly strong crosslinking, so that, if necessary, with an undesirable tightening of the reaction product and therefore the risk of possible embrittlement is to be expected. In this embodiment the proportion of compounds with only one group (I) or (II) a maximum of 20, preferably a maximum of 10, in particular up to to 5 wt .- / S, based on the respective analogous compound A) or B). With such an addition you can use the Control the hardness and elasticity of the reaction product to a certain extent. The ones to be used for this variant Compounds A) with only one reactive group (I) are, for example, the esters or amines of the unsaturated ones listed for A) Carboxylic acids which, however, are only esterified with monohydric alcohols or monoamines or reacted with amide formation have been.

Suitable compounds B) for this embodiment are, for example, those with the groups mentioned above under aa) in which R _{elne has a} meaning other than hydrogen, for example the alkyl substitution products of acetoacetic acid and malonic acid which have only been esterified with a monohydric alcohol or reacted with a monoamine are. Compounds B) of type bb) are amines with only one active H atom on the amino group, such as secondary monoamines, eg diethamine, and those of type cc) are alkanol mercaptans which contain only one mercaptan group, eg ethyl mercaptan.

The inventive method can be in one or perform several stages. As a rule, however, the one-step procedure is preferred for economic reasons, by, for example, using equivalent proportions of the components each having two active groups or H atoms works (equation XII see formula sheet see underlined Η-atoms). The choice of process stages, the pot life and properties of the product therefore depend on the process conditions, i.e. on the type and amount of starting materials, the dosage of the catalyst and the temperature control. So the elasticity of the networked Product within a tolerance range, e.g. by the chain length of the oil used for A) or B)

25 control gomers and / or polymers.

Although the process according to the invention is generally discontinuous is operated, it is also within the scope of the invention, the mixing of the components and the course of the reaction to be carried out continuously, for example by means of an automatic painting device.

In the case of the multistage process, one can or add several of the components in portions. For example, 1 mol of butanediol bis-acrylate can be used in the first stage

3508393

- 45 · -

be implemented by means of 2 moles of malonic acid diamide (equation XI s. Formula sheet) to form a product that has two Contains groups (II) each with an active (underlined) H atom. This product can be used in at least one other Stage with further molecules of a compound A) are reacted with chain extension and crosslinking. On analog For example, one mole of trimethylolpropane tris-acrylate can be used or react methacrylate in the first stage with three moles of acetylacetone.

The crosslinking in the second and, if appropriate, subsequent stages can take place, for example, by adding a catalyst. One can proceed in such a way that one works in the first stage only with a relatively small amount of catalyst, for example less than 2 %, or with a relatively little active catalyst. If the second or subsequent stage is carried out relatively shortly after the preparation of the intermediate product, it is not necessary to remove the catalyst used in the first stage. You can now use either a higher dose of the same catalyst and / or a different catalyst in the second stage. There is also the possibility of producing a preliminary product in the first stage that is stable over a longer period of time: and can even be sent to the processor. In this case, the catalyst will advantageously be removed, for example by neutralization or distillation, or a catalyst will be used which is either bound from the outset to a polymer, such as polymerized triphenylvinylphosphonium fluoride, or which is bound to a polymer during the reaction. Before the final application, the crosslinking reaction is started by adding a sufficient amount of catalyst again.

The inventive method can be carried out in the presence or absence of organic solvents, which may also exert an influence on the activity of the catalysts. Suitable solvents are e.g. aromatic and aliphatic hydrocarbons such as toluene, the various xylenes, mixtures of aliphatic and / or aromatic hydrocarbons, mineral oil fractions, esters, ethers, alcohols or the like.

All reaction components can be used individually or in a mixture, provided they are compatible with one another, are used.

Although the process according to the invention usually takes place under normal pressure, it may be desirable in individual cases be able to work under increased pressure to increase the curing speed.

The mutual quantitative ratio of the reaction components

A) and B) depends on the number of unsaturated groups (I) of the compound A) and the sum of the active Η atoms in Compound B) including those in groups (II) (hereinafter referred to as "active double bonds: active Η atoms "). In the case of the multistage process, it can be used to produce the preliminary products can be varied within a wide range. However, for the production of the crosslinked end product the said ratio of active double bonds: active Η atoms is generally about 2.4: 0.8 to 0.8: 2.4, preferably about 2: 1 to 1: 2, in particular about (0.8 to 1.2): 1 to 1: (0.8 to 1.2). For one mole of xthanediol bisacrylate Therefore, because of the two active Η atoms in the acetoacetic ester, e.g. only about 0.8 to 1.2 mol of acetoacetic ester are used. If, on the other hand, only one Η atom of the acetoacetic ester is to be converted, then you can also use 2x (0.8 to 1.2) mol

-TT-

Use acetoacetic ester (formula XII see formula sheet). As can be seen from this formula, the reaction product still contains a reactive group (see underlined H atom), so that it can network either with other molecules or with itself. The relationship active double bonds: active Η-atoms is then 1: 1. On the other hand, it is also possible to use a mixture of the Components A on the one hand and / or B on the other hand, each with different functionality to use to control the degree of crosslinking of the end products.

The reaction mixture according to the invention is a 2-component system, the pot life shows, depending on the selection of compounds A) and B) as well as the type and amount of Between 5 minutes and about 12 hours. This is a high processing security guaranteed. Due to this beneficial property related to the product with its rapid and flawless curing at room temperature or elevated temperature and its chemical Resistance it is ideally suited as a binder for coatings.

The 2-component systems can be used as coatings apply a variety of substrates, e.g. on organic or inorganic materials such as wood, wood fibers, e.g. as wood sealing, textiles of natural or synthetic origin, plastics, glass, ceramics, Building materials, such as concrete, fiberboard, artificial stone, but especially on metal. The covers can also be used for Objects and devices are used in the household and trade, e.g. refrigerators, washing machines, electrical devices, Windows, doors, furniture or the like. However, use for motor vehicles is preferred. That can apply by brushing, spraying, dipping or electrostatically

be performed. Of course, the 2-component systems still contain the usual additives such as dyes, pigments, fillers, plasticizers, Stabilizers, leveling agents, neutralizing substances such as tertiary amines and catalysts that are used in the usual Quantities can be used. These substances can be added to the individual components and / or the total mixture will.

Examples of dyes or pigments that can be of an inorganic or organic nature are: Titanium dioxide, graphite, soot, zinc chromate, strontium chromate, barium chromate, lead chromate, lead cyanamide, lead silica chromate, Calcium molybdate, manganese phosphate, zinc oxide, cadmium sulfide, chromium oxide, zinc sulfide, nickel titanium yellow, chromium titanium yellow, Iron oxide red, iron oxide black, ultramarine blue, phthalocyanine complexes, Napthol red or the like.

Suitable fillers are e.g. talc, mica, kaolin, chalk, quartz powder, asbestos flour, slate flour, barium sulfate, various silicas, silicates or the like.

The usual solvents are used for the fillers, for example aliphatic and aromatic hydrocarbons, Ethers, esters, glycol ethers and their esters, ketones, chlorinated hydrocarbons, terpene derivatives such as toluene, Xylene, ethyl and butyl acetate, ethylene glycol monoethyl or butyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Cyclohexanone, 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 coatings, preferably automotive paints and especially automotive refinish paints suitable. Here is the xylene resistance and

at the same time a good resistance to premium gasoline, of particular interest. The use of the reaction products according to the invention is therefore particularly advantageous. Since, according to a preferred embodiment of the invention, the 2-component system can cure itself in a relatively short time at room temperature without releasing environmentally harmful substances, its use as a car refinish paint is of considerable practical importance.
10

In the regulations and examples below, % mean in each case by weight? and T each part by weight. The vacuum is understood to mean that of the water jet pump.

15 examples

I) Production of component A (Michael acceptor) A 1) 400 parts of a solvent-free acrylate resin ^ Macrynal SM 510 from Hoechst AG) (OH number 150) were mixed with 400 parts of acrylic acid, 200 parts of toluene, 3 parts of hydroquinone monomethyl ether and 3 parts of p -Toluenesulfonic acid added. While air was passed through, the mixture was heated on the water separator _{until the evolution of H p O had ceased.} After cooling to room temperature and washing with water, the excess acrylic acid was removed. The organic phase was freed from the solvent by distillation under vacuum and diluted to a solids content of 60%. C = C equivalent weight 864.

A 2) 510 parts of the acrylate resin mentioned under A 1 were mixed with 500 parts of methyl acrylate, 3 parts of hydroquinone monomethyl ether and 6 parts of dibutyltin oxide. Within 30 h 26 T methanol were distilled off at 80 to 9O ⁰ C internal temperature over a Vigreux column. The excess methyl acrylate was distilled off in vacuo. The residue was diluted to 60 % pest body content with xylene. C = C equivalent weight 1083

A 3) 1000 T of a glycidyl group-containing acrylic resin prepared from styrene, glycidyl methacrylate and dimethyl maleate (Epoxidäquivalentgewlcht 510) were dissolved in 660 parts of xylene at 70 ⁰ C. At 7O ⁰ C 127 T T Tetraäthylammoniumbromld acrylic acid and 1 were added. While passing air ⁰ C. Stirring was continued until the acid number 1 at 8O. The light yellow solution was diluted with 17 P xylene. Pest body content 62.5 %, C = C equivalent weight 1022.

A 4) 570 parts of the resin solution from Example A 3) were admixed with 0.1 part of dibutyltin dilaurate and 50 parts of n-butyl isocyanate. It was stirred at 6O ⁰ C for 4 hours stirring (NCO value 0.2%). Pest body content 65 %; C = C equivalent weight 1112.

A 5) 296 parts of trimethylolpropane trisacrylate were placed in a 1-1 flask equipped with a stirrer, reflux condenser and a gas inlet, and 200 parts of isopropanol and 1.5 parts of triethylamine were added. 17 T of hydrogen sulfide were absorbed at room temperature. The mixture was stirred ^{at 30 °} C. for a further hour. The heavier product phase formed was then separated off as an almost colorless liquid. Pest body content 88 %; C = C equivalent weight 172.

A 6) In a three-necked flask equipped with a stirrer, thermometer and distillation column with descending condenser, 657 parts of a melamine resin of the hexamethoxymethylmelamine type (molecular weight 399), 1053 parts of 2-hydroxyethyl acrylate, 3.3 parts of hydroquinone monomethyl ether and 1.65 parts of sulfuric acid were added submitted. The mixture was ^{heated to 75 °} C. in vacuo and heated to 95 ^° C. within 4 h. After cooling to room temperature, it was neutralized with 10 parts of a 10% methanolic potassium hydroxide solution and filtered. 141 parts of a low-viscosity, clear resin solution were obtained. C ^ C equivalent weight 175
35

-fr-

A 7) 220 T Isophorondilsocyanat were added to 1 t of dibutyltin dilaurate and heated to 50 ⁰ C. At the same temperature, 2 parts of hydroquinone monomethyl ether, dissolved in 232 parts of hydroxyethyl acrylate, were added dropwise over the course of one hour. The mixture was stirred until the N = C = O content was less than 0.5. After addition of 7 T a glycidyl ester of a saturated, in α-position _q C ..- fatty acid (epoxy equivalent 260) 0.5 T branched and chromium III octoate was 5 hours then stirred at 8O ⁰ C and subsequently with 115 parts of xylene offset. Pest body content 80 %; C = C equivalent weight 289.

II) Production of component B (Michael donor)

B 1) In a 2-1 glass flask equipped with a distillation bridge, stirrer and contact thermometer, 312 parts of neopentyl glycol and 706 parts of methyl acetoacetate were heated to 130 to 160 ° C. _{under N p as a protective gas.} After completion of the methanol Abdestlllation (after about 7 h) C was cooled to 12O ^0th The excess methyl acetoacetate was distilled off in vacuo. 819 parts of a clear, pale liquid remained as a residue. CH equivalent weight 70.

B 2) In a 4-1 apparatus analogous to B 1), 670 parts of trimethylolpropane and 1972 parts of methyl acetoacetate were heated from 130 to 180 ° C. over the course of 5 h. After the distillation had ended, there were 465 parts of methanol in the receiver. After cooling to 15O ⁰ C, the low-boiling fraction was distilled off in vacuo. 1950 parts of a colorless liquid remained as a residue. CH equivalent weight 64.

B 3) In the same apparatus as according to B 1) 335 of trimethylolpropane and 2400 T of diethyl malonate under Np as a protective gas to 150 were heated to 170 ⁰ C. After finished

—22--

The excess diethyl malonate was removed by distillation of the ethanol distilled off in vacuo at 150 to 160 ° C., 1201 parts of a colorless liquid remained as a residue. C-H equivalent weight 79

B 4) 92 parts of glycerol and 426 parts of 2,2,6-trimethyl-4-oxo-4H-1,3-dioxin were placed in an apparatus as in B 1). With stirring, 160 parts of acetone were distilled off at 180 ° C. over the course of 5 hours. Then, the residue at 12O ⁰ C in a vacuum of low-boiling fractions were removed. 348 parts of a yellow, low-viscosity liquid remained. CH equivalent weight 58.

B 5) While stirring, 300 T of ethyl acetoacetate, 3 T 4 T potassium hydroxide solution and hydroquinone monomethyl ether were placed in a 1-1-Drelhalskolben which was equipped with a stirrer, reflux condenser and contact thermometer, and heated to 130 ⁰ C. 198 parts of butanediol diacrylate were metered in over the course of one hour. After a further 2 hours, the proportion of double bonds was less than 0.2 %. The potassium hydroxide solution was then neutralized with methanolic hydrochloric acid. The low-boiling components were removed ^{at 100 °} C. by applying a high vacuum. 464 parts of a light yellow viscous liquid remained. CH equivalent weight 232.

B 6) 250 T a Polyäthylenglykoldiamins (amine number 243) dissolved in 166 T diethylene glycol dimethyl ether was added dropwise at -2O ⁰ C to a solution of 190 T 134 T diketene in diethylene glycol dimethyl ether. After 1 1/2 hours of stirring at -28 C ⁰ 1O ⁰ C to + was heated and stirred until the amine number of less than. 1 After 10 parts of ethanol had been added, the mixture was heated ^{to 90 ° C. for 40 min.} The solvent was then distilled off in vacuo. The residue was taken up in 100 parts of dimethoxyethane. A light yellow clear solution was obtained. Solids content 8l %; CH equivalent weight 122.

- 33 -

B 7) 134 parts of trimethylolpropane and 327 parts of methyl cyanoacetate were treated with 4 parts of titanium acetylacetonate from 100 to 180.degree heated with distilling off methanol. After 4 h, the mixture was cooled to 140 ° C. and the low-boiling portion in vacuo distilled off. 341 parts of a yellow liquid remained. C-H equivalent weight 57.

B 8) 750 parts of the acrylate resin mentioned under A 1) (OH number 150) and 260 parts of ethyl acetoacetate were heated ^{to 150 ° C. in a distillation apparatus.} The mixture was heated ^{to 170 ° C. within 2 h.} After the ethanol had been distilled off, the low-boiling portion was removed after applying a vacuum. After cooling to 100 ^° C., 306 parts of xylene were added. A clear, light yellow liquid was obtained.

15 solids content 75 %; CH equivalent weight 310.

B 9) 510 parts of a polyester (OH number 110) prepared on the basis of trimethylolpropane, terephthalic acid, adipic acid and neopentyl glycol were heated to 140.degree. C. together with 130 parts of ethyl acetoacetate. ^{The mixture was heated to 170 °} C. over the course of 3 h with continuous distillation of volatile constituents. After cooling to 140 ° C., the low-boiling portion was distilled off in vacuo. It was then diluted with 198 parts of xylene. A light yellow clear solution was obtained. Solids content 75 %, CH equivalent weight 402.

B 10) 300 T, referred to under A 1 OH-group-containing acrylate resin was dissolved in 200 parts of xylene at 7O ⁰ C. After cooling to room temperature, 0.025 T dimethylaminopyridine was added. 60 parts of diketene were added dropwise over the course of 6 hours. After a further 12 hours, the free diketene content was 0.2 %. Solids content 65 %; CH equivalent weight 392.

B 11) 440 parts of coconut oil fatty acid ethyl ester (saponification number 255) were heated to 180 ° C. in a distillation apparatus together with 268 parts of trimethylolpropane and 1 part of butyl titanate. Within 7 h, the temperature with continued distillation of methanol was slowly raised to 25O ⁰ C. After a total of 59 parts of methanol had been distilled off, the mixture was ^{cooled to 100 °} C. and 585 parts of ethyl acetoacetate were added. After heating to 14O ⁰ C C was heated with continuous distillation of 3 hours to 175 ^0th A total of another 175 T of distillate was obtained. After cooling to 15O ⁰ C, the low-boiling fraction was removed in vacuo. 992 parts of a viscous light yellow liquid were obtained. CH equivalent weight 124.

B 12) 200 T acetylacetone and 0.5 T trimethylbenzylammonium hydroxide were heated to 4O ⁰ C. 170 parts of trimethylolpropane trisacrylate were added dropwise over the course of 2 hours. The mixture was then subsequently stirred until the double bond content was below 0.5 % . A light yellow viscous liquid was obtained. CH-

20 equivalent weight 162.

III) Production of a self- crosslinking implementation product according to the invention

C) (Example 17) 924 T of a 70-JJigen solution of an acrylate resin (OH number 130) (carrier substance) in xylene produced by radical polymerization of styrene, hydroxyethyl methacrylate and methyl methacrylate were incubated at 4O ⁰ C with 258 t of a 70-Jiigen solution of toluene diisocyanate half-blocked with hydroxyethyl acrylate (N = C = O content 9.8 %, C = C equivalent weight 290) (component A) in xylene in the presence of 5 T dibutyltin dilaurate to an isocyanate content of less than 0.3 % . Then 2 parts of dimethylaminopyridine were added and 25 parts of diketene (component B) were added dropwise at room temperature with stirring.

After stirring for 24 hours at room temperature, no more free diketene could be detected. Pest body content 71 %; C = C equivalent weight 2022; CH equivalent weight 2020. Instead of diketene, the equivalent amount of acetoacetic ester can be converted, whereby a product with the same key figures is obtained.

IV) Preparation of the coatings - Examples 1 to 51

Examples 1 to 51 according to the invention are summarized in Tables 1 and 2. There are also four comparative tests V 1 to 4 carried out with commercially available products.

The amounts by weight of components A and B given in Tables 1 and 2 below were mixed. as A copolymer prepared from 31 parts of glycidyl methacrylate, 15 parts of dimethyl maleate and 54 parts of styrene was used as the comparison substance. Diethylenetriamine served as the hardener for this system. In the case of the pigmented coatings, the one desired The amount of titanium dioxide corresponding to the degree of pigmentation is mixed in and the mixture is rubbed on a bead mill. The coating material obtained was used as such or, if necessary, after admixing the specified Catalyst applied by means of a doctor blade in a wet film thickness of 100 μπι on glass plates and cured at room temperature or at 80 ° C (30 min).

The abbreviations used in the tables below mean:

ABAH: alkylbenzyldimethylammonium hydroxide (alkyl = Cg-C ₂₂ )

BTAH: benzyltrimethylammonium hydroxide

DETA: diethylenetriamine

35 HH: hot curing "for 30 minutes at 8O ⁰ C

-25--

TBAF
TBAH
TMPSG TMPTA TPTP
MDPP
PDOAP DPOAP TPAP
MDPAP DPPDAPP THMP
TCEP

TDAMP TDAIP TBIP
TPP
DBU

DBN
TMG
DABCO

Room temperature

Tetrabutylammonium fluoride

Tetrabutylammonium hydroxide

Trimethylolpropane trithioglycolic acid ester

Trimethylol propane trisacrylate

Tris-p-tolylphosphine

Methane diphenylphosphine

Phenyl-di-o-anisylphosphine

Diphenyl-o-anisylphosphine

Tris-p-anisylphosphine

Methyl di-p-anisylphosphine

Diphenyl-p-dimethylaminophenylphosphine

Trishydroxymethylphosphine

Tris-2-cyanoethylphosphine

Tris-diethylaminomethylphosphine

Tris-dimethylamino-ljl-dimethylberizyliminophosphorane

Trlbutyl-1,1-dimethyl-benzyliminophosphorane

Triphenylphosphine

1,8-diazabicyclo- [5> 4.0] -undec-7-ene

1,5-diazabicyclo- [4,3,0] -non-5-en

Ν, Ν, Ν ', N'-tetramethylguanidine

1, iJ-diazabicyclo- [2.2.2] octane

Clear coat film (100 μ wet film)

Tabel

Example component A component B play

Type amount type amount

Catalyst Pot life Type Quantity Hartwig's pendulum hardness according to König temperature (s)

after 1 day 10 days

Resistance to xylene (after 10 days)

1 TMPTA 49 B 2 32 2 A 6 88 B 2 32 3 A 6 88 B 2 32 4th TMPTA 99 B 6 122 5 A 3 102 B 2 6.5 6th A 3 102 B 2 6.5 7th TMPTA 99 B 8 310 θ A 6 88 B 8 310 9 A 6 44 B 8 310 10 TMPTA 74 B 12 40.5 U A 5 12th B 8 22nd 12th A 3 30.7 TMPSG 3.6 13th A 3 30.7 DETA 0.7 14th - - Type C - 54 15th A3 102 B2 6.5 16 A3 102 B2 6.5 17th A3 102 B2 6.5 18th A3 102 B2 6.5 19th A3 102 B2 6.5

TBAH 0.4 , 7 0.6 RT BTAH 0.6 , 4 0.3 RT ABAH 0.6 , 4 1 RT BTAH 1.0 , 4 0.25 RT BTAH 0.6 , 2 0.3 RT TBAF 0.6 5 RT TBAF 4.0 b RT TBAF 4.0 8th RT TBAF 3.5 11th RT BTAH 0.6 0.3 RT TBAH 0.3 0.5 HH TBAF 0.2 0.6 HH - 0.3 HH TBAF 0.3 0.4 RT TPP 0 28 RT TPTP 0 12th HH HDPAP 0 10 HH TPAP 0 16 HH DBN 0 1.5 RT

80

157

104

122

143

98

70

80

160

193

169

191

151

125

143

136 139 125 169

170 195 140 165 190 202 104 123 200 206 194 200 160 199

199

217 216 210 203

h h

> 24 h> 24 h> 24 h * 24 h> 24 h> 24 h

30 min> 24 h

2 h

1 h 30 min

2 h

> 24 h

> 24 h> 24 h> 24 h> 24 h

Table 1 (continued)

Clear coat film (100 μ WaBfH m)

at Component A lot Component B lot catalyst 0.2 Pot life Hardening Pendulum hardness according to after 1 day King Resistance to game 102 6.5 0.4 lh) temperature (S) 196 (after 10 days) Type 102 Type 6.5 0.4 124 10 days Xylene 20th A3 102 B2 6.5 Type amount 0.4 1.5 HH 136 203 > 24 h 21 A3 102 B2 6.5 IMG 0.4 11th HH 133 189 > 24 h 22nd A3 102 B2 6.5 MDPP 0.4 15th HH 142 192 > 24 h 23 A3 102 B2 6.5 RDQAP 0.4 17th HH 141 196 > 24 h 24 A3 102 B2 6.5 DPQAP 0.4 4.5 HH 122 202 > 24 h 25th A3 102 B2 6.5 DPPDAPP 0.4 1.5 RT 130 200 > 24 h 26th A3 102 B2 6.5 THMP 0.4 6th HH 140 201 > 24 h 27 A3 102 B2 6.5 TCEP 0.7 16 HH 140 199 > 24 h 28 A3 102 B2 8.0 TDAMP 0.7 2.5 HH 98 202 > 24 h 29 A3 102 B2 8.0 TDAIP 0.4 9 RT 95 198 > 24 h 30th A3 102 B3 8.0 TBIP 0.7 12th HH 101 176 14 h 31 A3 102 B3 8.0 TBIP 0.4 25th HH 120 172 18 h 32 A3 102 B3 8.0 DPPDAPP 0.4 8th HH 104 182 12 h 33 A3 102 B3 8.0 TDAIP 0.4 1 RT 145 193 > 24 h 34 A3 102 B3 8.0 MDPP 0.4 24 RT 130 191 > 24 h 35 A3 102 B3 8.0 MDPP 0.8 5.5 HH 125 202 > 24 h 36 A3 102 B3 8.0 DABCO 4.8 HH 92 207 > 24 h. 37 A3 B3 TMG 5.5 HH 181 > 24 h 38 A3 B3 DBU 24 HH 179 10 h TBAF

(Comparison) 45.8 DETA 2.1.

(") 45.8 DETA 2.1

Tg = day

H H

RT HH

65 132

117 142

Io min
15 minutes

2O min 5O min

O GO CO CD CO

Table 2

Pigmented Coatings (100 μ NaSflim)

For component A component B catalyst TiO pot life hardening pendulum hardness according to Koenig Resistance to play (h ) temperature (s) (after 10 daysi

Type Quantity Type Quantity Type Quantity after 1 Tg 10 Tg xylene

39 TMPTA ") 49 5 B 2 32 , 5 BTAH 0.5 65, 2 2 5 * RT 40 A 6 88 5 B 2 32 BTAH 0.9 96 5 15th RT 41 A 6 88 0 B 2 32 TBAF 1.3 96 5 35 RT 42 TMPTA 49 7th B 2 32 (TBAF 0.3) 65, 2 30th RT 7th , 6 (BTAH 0.3) 43 A 5 86 8th B 2 32 , 7 BTAH 0.8 86 5 15th RT 44 (A 6 44) 8th B 2 32 ,1 TBAF 1 81 2 35 RT (TMPTA 25) ,1 45 TMPTA 25th B 11 31 BTAH 0.8 45 20th RT 46 TMPTA 74 B 12 40 BTAH 1.2 91, 6th 45 RT 47 A 3 255, B 2 32 BTAH 1.4 154 5 RT 48 A 3 255, B 2 32 TBAF 1.4 154 30th RT 49 A 3 128, B 8 39 TBAF 0.8 87 40 RT 50 A'3 30, TMPSG 3 TBAF 0.4 18 2 35 HH 51 A 3 "30, DETA O ^- 15, 9 25th HH (Comparison) 45, DETA 2 _ 38, 3 16 h RT ( 45, DETA 2 - - 38, 3 16 h HH

131 98 172 > 24 H t 151 141 171 > 24 H 145 190 > 24 H ° \ 127 174 > 24 H I. 118 162 > 24 H 145 175 6th H 81 125 30th min 60 104 > 24 H 126 168 3 H CJ
f TI 97 174 > 24 H \ J I
O
co 77 162 8th H 25 mtfl> 180 182 1 H 5O mt £ $ 140 157 30th min 55 117 12th min 138 147 2O min

V4

Tg = day

V) Discussion of the results

As can be seen from Table 1, the products of Examples 1 to 38 show high chemical resistance and high Hardness, i.e. they are completely cross-linked, although some hardening only took place at room temperature. on the other hand if they still have favorable pot lives, compare in particular Examples 6 to 9, 16-18, 22, 23, 27, 30. The last-mentioned examples show that a suitable selection of the catalysts allows a pot life in the range of 5 up to approx. 20 h can be achieved. Examples 11 to and 16, 19-21, 24, 28, 33 to 37 show that in Forced drying (hot curing 30 min / 80 ° C) high hardness values can be obtained after just 1 day.

In comparison to Table 1, Table 2 shows that the pot lives of the pigmented systems are somewhat shorter than that but they are still sufficient for safe processing. As can be seen from Examples 39 to 49, the films cure completely at room temperature. The chemical resistance of the products according to Table 2 is on average higher than that of the unpigmented systems in Table 1.

Examples 12, 13, 50 and 51 show that the amine and mercapto compounds as component B are also complete Curing and good chemical resistance of the products result, in the case of Examples 13 and 51 even without Catalyst is working. The physical values of the comparative tests V 1 to V 4 indicate a low resistance to xylene recognize and also a less pronounced degree of hardening. The products according to the invention are therefore superior to the comparison samples.

Formula sheet

• · »—H ₂ C

...- H ₂ (III)

CH

CH ₂ —...

j

- 'c C-

CH ₂ - O - CO - CH = CH ₂ 2 - O - CO - CH = CH ₂

Vq _ _N ^ - « ₂ -O- (CH ₂ ) _n -O-CO-CH = CH ₂ XH ₂ -O- (CH ₂ J _n -O-CO-CH = CH ₂

(IV)

...- CH -CH ₂ + NC - CH ₂ - COOH

■> - ... -. CHOH - CH ₂ - O - CO - CH ₂ - CN

(V)

CH ₃ -CO-CH ₂ -CO-NH- (CH ₂ ) _n -NH-CO-CH ₂ -CO-CH, (VI)

η 2 - 10

(Alkyl O) ₂ PO - CH ₂ - COOR (VII)

Q Q

(CH ₃ O) ₂ P-CH ₂ -CO-O- (CH ₂ ) ₂ -0-CO-CH ₃ -P (OCH,) _a ( _V HI)

Ϊ fl

NC-CH ₂ -PO-CH ₂ -C (CH ₃ ) ₂ -CH ₂ -0-P-CH ₂ -CN (ΐχ)

OR ⁶ OR ⁶

(R ⁶ O) ₂ -P-CH- (CH ₂ ) ₂ -CO-O- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -0-C0- (CH ₂ ) ₂ -CH-P- ( Ol £) ₂ O = P (OES) ₂ O = P (ORS) ₂

R ⁶ = C _1-5 alkYl (X)

H ₂ C = CH-CO-O- (CH ₂ ) ₄ -0-CO-CH = CH ₂

+ 2 CH ₂ (CONH ₂ ) 2 >

(H ₂ NOC) j CH-CH ₂ -CH ₂ -COO- (CH ₂ ) ₄ -00C- (CH ₂ ) ₂ -CH (CONH ₂ ) ₂ . (XI)

2 H ₂ C = CH-COO- (CH ₂ ) _a -OOC-CH = CH ₂ +2 CH, -CO-CH ₂ -COOR

CO - CH ₃ H ₂ C = CH-COO- (CHj) ₂ -OOC-CH ₂ -CH ₂ - ^ C - COOR

ROOC-CH-CH ₂ -CH ₂ -COO- (CH ₂ ) ₂ -0OC-CH ₂ -CH ₂ (XII)

CO-CH,

Claims (12)

PATENT CLAIMS: 'HOE 8 S / r 036J Iy reaction product of A) compounds with at least two R ¹ R ² C = CR ^ -X groups (I) with B) compounds that a) at least two active Η atoms or b) at least two groups with active Η atoms of the type -AH- (II) or c) at least one active H atom and at least one Type (II) group contain or form the corresponding number of this group (II), in which in formula (I) 10 X -CO-, either directly or through the remainder of a polyhydric alcohol or an amine to a white 12 ^
tere RR C = CR group is bound, R ^{1 is} hydrogen or a hydrocarbon radical with 1 to 10, such as alkyl, phenyl, benzyl, naphthyl, preferably with 1 to 4 carbon atoms, R ^{2 is} hydrogen, a hydrocarbon radical with 1 to 10, preferably 1 to 4 carbon atoms, such as alkyl, phenyl, benzyl, naphthyl, an ester group with the Ii
Radical R of a monohydric alcohol with up to 12 C atoms, -CN, -NO, a CO-NHR ¹ - or a 1 group ^l
3 CO-R R has the same meaning as R and is hereby the same or is different, in formula (II) -AH- one of the groupings -CH-, -NH- and -SH, with the proviso that reaction products of A) polyacrylates with at least two free acrylic acid groups, reaction products of polyisocyanates with OH groups Acrylic acid esters or reaction products of epoxy resins with acrylic acid with B) diketene or acetoacetic acid esters of hydroxyethyl acrylate or -meth- 35 acrylate are excluded. 2. Process for the preparation of reaction products of A) Compounds with at least two R R C = CR -X groups (I) with B) compounds that
a) at least two active Η atoms or b) at least two groups with active Η atoms of the Type -AH- (II) or
c) at least one active Η atom and at least one Type (II) group contain or form the corresponding number of this group (II), in which in formula (I) X -CO-, which either directly or via the remainder of a polyhydric alcohol or an amine to a white 12 λ tere R R C = CR group is bonded, rI hydrogen or a hydrocarbon radical with 1 up to 10, such as alkyl, phenyl, benzyl, naphthyl, preferably with 1 to 4 carbon atoms, R ^{2 is} hydrogen, a hydrocarbon radical with 1 to 10, preferably 1 to 4 carbon atoms, such as alkyl, phenyl, benzyl, naphthyl, an ester group with the radical R of a monohydric alcohol with up to 12 C atoms, -CN, -NO, a CO-NHR - or a 1 2 25 CO-R group 3 2 R has the same meaning as R and is hereby the same or is different,
in formula (II)
-AH- one of the groups -CH-, -NH- and -SH, characterized in that the compounds A) and B) are reacted to form an oligomeric and / or polymeric reaction product, in the case that -AH- a represents the groups -6h- or -SH, the reaction in the presence of at least one catalyst takes place from the group diazabicyclo-octane (DABCO), Halo- --33-- Genides of quaternary ammonium compounds, alone or in a mixture with silicic acid alkyl esters, amidines, organic phosphonium salts with 1 to 20 carbon atoms in the alkyl radical and / or aryl radical, tertiary phosphines of the general formula P (CH _p -Y) _, in which Y is identical or different and Z is an alkyl radical with 1 to 5 carbon atoms, denotes the radical -OH, -CH_CN or -N (Z) ₀ , where tertiary phosphines of the general formula P (R, R ^P , R), in which the radicals R ⁿ , R- * and R an alkyl radical with 1 to 12 carbon atoms or a phenyl radical, unsubstituted or substituted with at least one alkyl, alkoxy or Dialkylamino group each with 1 to 4 carbon atoms in the Aiii cg
kyl radical, RR and R are identical or different, but at least one of the radicals represents a phenyl radical and aminophosphoranes of the general formula (R ⁷ , R ⁸ , R ⁹ ) P = NC (R ¹⁰ , R ⁿ , R ¹² ), in the R ⁷ , 8 Q
R, R ^{7 are} identical or different and denote an alkyl radical with 1 to 12 carbon atoms or a phenyl radical, substituted or unsubstituted by at least one alkyl, alkoxy or dialkylamino group, each with 1 to 4 carbon atoms in the alkyl radical, and R ¹⁰ , R ¹¹ , R ^{12 are} identical or different and represent an alkyl radical with 1-5 carbon atoms or a phenyl radical. 3. Process for the preparation of reaction products according to claim 1, characterized in that A) compounds 12 λ with at least two RR C = CR -X groups (I) with B) connections, the a) at least two active Η atoms or b) at least two groups with active Η atoms of the Type -AH- (II) or
c) at least one active Η atom and at least one Type (II) group contain, or form the corresponding number of this group (II), in which the formula explanation given in claim 1 applies, to be reacted with the formation of an oligomeric and / or polymeric reaction product, where Im In the event that -AH- represents one of the groups -OH- or -SH, the reaction in the presence of at least one quaternary ammonium compound or an alkali metal alcoholate takes place as a catalyst. 4. The method according to claim 2, characterized in that fluorides or phosphines are used as catalysts will. 5. The method according to claim 2 or 4, characterized in that the catalysts trishydroxymethylphosphane, Trisdimethylaminomethylphosphine, tris-p-anisylphosphine, methyl-diphenylphosphine, methyl-d-p-anisylphosphine, α, α-Dimethylbenzylimino-tri-butylphosphorane. 6. Embodiment make one or more of claims 1 to 5, characterized in that in compound A) the radical R ¹ RC = CR-X (I) is derived from acrylic acid and compound B) ester-like bonded Ma- Contains 20 ionic acid. 7. Embodiment according to one or more of the claims 1 to 6, characterized in that the radical R ¹ R ² C = CR ^ -X (I), where XR ^{3 is} hydrogen or alkyl with 1 to 8 carbon atoms, of a mono- or polyunsaturated, at most dibasic carboxylic acid with 2 to 10, preferably 3 to 6, carbon atoms, preferably Acrylic acid, methacrylic acid and / or maleic acid is derived. 8. Embodiment according to one or more of claims 1 to 7 »characterized in that in the compounds A) the groups (I) on the remainder of a polyol or polyamine, preferably an oligomer and / or poly 35 mers are bound. 9. Embodiment according to one or more of claims 1 to 8, characterized in that the compound A) from a polyester containing OH groups, acrylic resin containing OH groups, epoxy resin and / or 5 is derived from amine resin. 10. Embodiment according to one or more of claims 1 to 9, characterized in that the grouping -AH- (II) of compound B) aa) for the meaning -CH- of a compound with the grouping -CO-CHR ¹ -CO-, NC-CHR ¹ -CO-, NC-CH ₂ -CN, = P0-CHR ¹ -C0-, = CHR ¹ -CN, = P0-CHR ¹ -P0 =, -C0-CHR ¹ -N0 ₂ , bb) for the meaning -NH- of a primary and / or secondary polyamine and cc) for the meaning -SH derived from a thioalcoholic acid ester, amide and / or a mercaptan. 11. Embodiment according to one or more of claims 1 to 10, characterized in that the connection B) of an at least divalent compound from the group consisting of polyols, polyamines and / or polymercaptans derives. 12. Embodiment according to one or more of claims 1 to 11, characterized in that it is on one Substrate, in particular a metal, is preferably located in a thin layer. 13. Embodiment according to one or more of claims 2 to 12, characterized in that the reaction is carried out at a temperature of -10 to 180, preferably 0 to 100 ⁰ C, optionally in the presence of a catalyst. 14. 2-component lacquer consisting of A) compounds with 12 ^ at least RR C = CR -X groups (I) and B) compounds, the a) at least two active Η atoms or * b) at least two groups with active Η atoms des Type -AH- (II) or c) at least one active Η atom and at least one group of type (II) contain or form the corresponding number of this group (II), in which the formula explanation given in claim 1 applies, on its own or in combination with common additives.