Reactive hardenable polymer mixture and process for the preparation of hardened products therefrom

An acidic polymer selected from the group consisting of:

• (a) at least one compound of Formula I:
• ##STR20## wherein:
• R.sup.1 is a radical derived from at least one polymeric product containing hydroxy groups arranged along the backbone which product is selected from the group consisting of a polymerization and a condensation product and a combination thereof in the form of polyesters having a hydroxy number between 40 and 220, a polymer having a hydroxy number between 40 and 220 selected from the group consisting of a polymerization product of polyvinyl alcohol, at least partially saponified copolymers of vinylacetate with at least one unsaturated monomer, a homopolymer of hydroxyalkyl acrylate, meth-acrylate or maleinate and a copolymer of at least one of said hydroxyalkyl monomers with at least one olefinically unsaturated monomer;
• phenol resins having a hydroxy number between 150 and 300 and combinations thereof;
• R.sup.2 is derived from a radical selected from the group consisting of those of formula IIa and formula VI ##STR21## in which z is an integer from 1 to 4 inclusive:
• ##STR22## in which u is an integer from 1 to 8, inclusive or the corresponding free acids;
• wherein the bridging radical
• R.sup.4 is (a) a bi- to pentavalent radical selected from the group consisting of an aliphatic hydrocarbon group having 1 to 28 carbon atoms, (b) radical (a) being at least once interrupted by oxygen-bridges or by --HC.dbd.CH--group, and (c) a radical (a) being substituted by an ester group having 1 to 6 carbon atoms, (d) a radical (a) being substituted by a COOH--group, (e) an aromatic group having 6 to 43 carbon atoms of at least one of formulae ##STR23## the aromatic radicals being unsubstituted or substituted by at least one radical R.sup.6 selected from the group consisting of alkyl, alkoxy each having 1 to 6 carbon atoms and halogen, furthermore R.sup.4 is (f) a piperazine group, wherein in formulae XX and XXI the divalent radical
• X is a group of one of formulae ##STR24## wherein n is an integer from 1 to 8;
• R.sup.5 is a radical of an at least dibasic cyclic carboxylic acid having at least one COOH--group in an ortho-position to the ester bond and R.sup.5 may also be as defined for R.sup.2 ;
• (b) at least one compound corresponding to formula (I) as defined under (a) but with the proviso that the anhydride groups are replaced at least partially by a free acid or ester group or by both.

A reactive hardenable polymer mixture which comprises:

• (A) at least one aliphatic epoxy compound having 2 to 6 oxirane groups;
• and
• (B) at least one polycarboxylic acid compound in the form of a component selected from the group consisting of:
• at least one compound of Formula I:
• ##STR25## wherein:
• R.sup.1 is a polymer residue;
• R.sup.2 is derived from a radical selected from the group consisting of those of formula IIa and formula VI ##STR26## in which z is an integer from 1 to 4 inclusive:
• ##STR27## in which u is an integer from 1 to 8, inclusive or the corresponding free acids;
• wherein the bridging radical
• R.sup.4 is (a) a bi- to pentavalent radical selected from the group consisting of an aliphatic hydrocarbon group having 1 to 28 carbon atoms, (b) radical (a) being at least once interrupted by oxygen-bridges or by --HC.dbd.CH--group, and (c) a radical (a) being substituted by an ester group having 1 to 6 carbon atoms, (d) a radical (a) being substituted by a COOH--group, (e) an aromatic group having 6 to 43 carbon atoms of at least one of formulae ##STR28## the aromatic radicals being unsubstituted or substituted by at least one radical R.sup.6 selected from the group consisting of alkyl, alkoxy each having 1 to 6 carbon atoms and halogen, furthermore R.sup.4 is (f) a piperazine group, wherein in formulae XX and XXI the divalent radical X is a group of one of formulae ##STR29## wherein n is an integer from 1 to 8;
• R.sup.5 is a radical of an at least dibasic cyclic carboxylic acid having at least one COOH--group in an ortho-position to the ester bond and R.sup.5 may also be as defined for R.sup.2.

A reactive hardenable polymer mixture which comprises:

• (A) at least one aliphatic epoxy compound having 2 to 6 oxirane groups;
• and
• (B) at least one polycarboxylic acid compound in the form of a component selected from the group consisting of:
• (a) at least one compound of Formula I:
• ##STR30## wherein:
• R.sup.1 is a radical derived from at least one polymeric product containing hydroxy groups arranged along the backbone which product is selected from the group consisting of a polymerization and a condensation product and a combination thereof in the form of polyesters having a hydroxy number between 40 and 220, a polymer having a hydroxy number between 40 and 220 selected from the group consisting of a polymerization product of polyvinyl alcohol, at least partially saponified copolymers of vinylacetate with at least one unsaturated monomer, a homopolymer of hydroxyalkyl acrylate, meth-acrylate or maleinate and a copolymer of at least one of said hydroxyalkyl monomers with at least one olefinically unsaturated monomer;
• phenol resins having a hydroxy number between 150 and 300 and combinations thereof;
• R.sup.2 is derived from a radical selected from the group consisting of those of formula IIa and formula VI ##STR31## in which z is an integer from 1 to 2 inclusive:
• ##STR32## in which u is an integer from 1 to 8, inclusive, or the corresponding free acids;
• wherein the bridging radical
• R.sup.4 is (a) a bi- to trivalent radical selected from the group consisting of an aliphatic hydrocarbon group having 2 to 8 carbon atoms, (b) radical (a) being at least once interruped by oxygen-bridges or by --HC.dbd.CH--group;
• R.sup.5 is a radical of an at least dibasic cyclic carboxylic acid having at least one COOH--group in an ortho-position to the ester bond and R.sup.5 may also be as defined for R.sup.2 ;
• (b) at least one compound of formulae (IIa) or (VI) together with at least one of the OH-group containing compounds from which the above defined group R.sup.1 is derived;
• (c) at least one compound corresponding to formula (I) as defined under (a) but with the proviso that the anhydride groups are replaced at least partially by a free acid or ester group or by both;
• (d) at least one compound as defined under (b) wherein the anhydride groups of the polycarboxylic acid compounds are replaced at least partially by a free acid or at least partially by an ester group or by both;
• and
• (e) any combination of (a) to (d).

An acidic polymer selected from the group consisting of:

• (a) at least one compound of Formula I:
• ##STR33## wherein:
• R.sup.1 is a radical derived from at least one polymeric product containing hydroxy groups arranged along the backbone which product is selected from the group consisting of a polymerization and a condensation product and a combination thereof in the form of polyesters having a hydroxy number between 40 and 220, a polymer having a hydroxy number between 40 and 220 selected from the group consisting of a polymerization product of polyvinyl alcohol, at least partially saponified copolymers of vinylacetate with at least one unsaturated monomer, a homopolymer of hydroxyalkyl acrylate, meth-acrylate or maleinate and a copolymer of at least one of said hydroxyalkyl monomers with at least one olefinically unsaturated monomer;
• phenol resins having a hydroxy number between 150 and 300 and combinations thereof;
• R.sup.2 is derived from a radical selected from the group consisting of those of formula IIa and formula VI ##STR34## in which z is an integer from 1 to 2 inclusive:
• ##STR35## in which u is an integer from 1 to 8, inclusive, or the corresponding free acids:
• wherein the bridging radical R.sup.4 is (a) a bi- to trivalent radical selected from the group consisting of an aliphatic tydrocarbon group having 2 to 8 carbon atoms, (b) radical (a) being at least once interrupted by oxygen-bridges or by --HC.dbd.CH--group;
• R.sup.5 is a radical of an at least dibasic cyclic carboxylic acid having at least one COOH--group in an ortho-position to the ester bond and R.sup.5 may also be as defined for R.sup.2 ;
• (b) at least one compound corresponding to formula (I) as defined under (a) but with the proviso that the anhydride groups are replaced at least partially by a freee acid or ester group or by both.