Claims
- 1. 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: ##STR13## 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 and, at least partially saponified copolymers of vinylacetate with at least one unsaturated monomer, a homopolymer of hydroxyalkylacrylate, methacrylate 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 ##STR14## in which z is an integer from 1 to 4 inclusive: ##STR15## 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 ##STR16## 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 ##STR17## 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 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).
- 2. A composition as claimed in claim 1 containing additionally at least one polycarboxylic anhydride, being not bound to the chain of the polymerisation or condensation resin and containing at least one group of one of the formulae ##STR18## and trimellitic anhydride, wherein Z is (CH.sub.2).sub.m, wherein m is an integer from 2 to 8, or z has the meaning of one of the formulae ##STR19##
- 3. 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.
- 4. A process for the preparation of hardened products from the composition claimed in claim 1 wherein the composition is cured at a temperature of from 0.degree. to 350.degree. C.
- 5. A process as claimed in claim 4, wherein curing is carried out at a temperature in the range from 20.degree. to 80.degree. C.
- 6. A composition as claimed in claim 1 wherein the ratio of the free carboxylic groups of the polycarboxylic acid compounds including the free carboxylic groups of the polycarboxylic acid compounds not bound to R.sup.1 in cases (b) to (e) to the epoxy equivalent in the epoxy compounds is between 1:5 and 5:1 and the ratio of the anhydride groups of the polycarboxylic acid units (B) of compound (a) or in cases in (b) to (c) of the polycarboxylic derivatives not bound to R.sup.1 to the off-groups of the epoxy compound is between 20:1 and 1:20.
- 7. A composition as claimed in claim 1 containing at least one liquid component (A) or (B).
- 8. A composition as claimed in claim 1 additionally containing up to 30% by weight of the total solids content of at least one heat-hardenable synthetic resin containing hydroxy groups.
- 9. A composition as claimed in claim 1 containing additionally up to 5% by weight, referred to the total solids content, of a catalyst.
- 10. A composition as claimed in claim 1 being in powdered form and having a softening point between 40.degree. and 200.degree. C. (according to Durrans) and a glass transition temperature between 22.degree. and 100.degree. C.
- 11. A composition as claimed in claim 1 wherein the COOH--groups of component (B) are present in the form of a metal salt or a quaternary ammonium salt and in an amount between 0.1 and 20%, referred to the COOH--group equivalents.
- 12. A process for the preparation of hardened products as claimed in claim 4 wherein the composition is cured between 20.degree. and 210.degree. C. in the presence of a solvent.
- 13. A process for the preparation of hardened products as claimed in claim 4 wherein a powdered composition is hardened between 80.degree. and 310.degree. C.
- 14. 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.
- 15. 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).
- 16. 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.
Priority Claims (2)
Number |
Date |
Country |
Kind |
2754399 |
Dec 1977 |
DEX |
|
2811914 |
Mar 1978 |
DEX |
|
Parent Case Info
This application is a continuation of U.S. application Ser. No. 06/150,706, filed May 19, 1980, now abandoned, which in turn is a continuation of U.S. application No. 05/961,556, filed Nov. 17, 1978, now abandoned.
US Referenced Citations (5)
Continuations (2)
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Number |
Date |
Country |
Parent |
150706 |
May 1980 |
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Parent |
961556 |
Nov 1978 |
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