Polycarboxylate ethers used as dispersing agents for epoxy resins

Patent metadata

Field	Value
Publication number	US-9617410-B2
Application number	US-201314441535-A
Country	US
Kind code	B2
Filing date	Oct 28, 2013
Priority date	Nov 9, 2012
Publication date	Apr 11, 2017
Grant date	Apr 11, 2017

Abstract

The invention relates to curable epoxy resin compositions containing at least one epoxy resin having on average more than one epoxide group per molecule, at least one inorganic filler and at least one polycarboxylate ether, wherein the inorganic filler is coated with the polycarboxylate ether. The invention also relates to multi-component systems for producing said epoxy resin compositions, cured epoxy resins, a powder component K3 for the multi-component system, uses and methods.

First claim

The invention claimed is:

1. A curable epoxy resin composition containing at least one epoxy resin having on average more than one epoxide group per molecule, at least one inorganic filler and at least one polycarboxylate ether, wherein the inorganic filler is coated with the polycarboxylate ether, wherein the polycarboxylate ether has side chains linked to a main chain via ester, amide and/or ether groups, wherein the main chain has at least one acrylic acid moiety or a salt thereof, and/or at least one methacrylic acid moiety or a salt thereof, and/or a maleic anhydride moiety or a salt thereof, and/or a maleic acid moiety or a salt thereof, and/or an itaconic acid moeity or a salt thereof, and/or a crotonic acid moiety or a salt thereof, and/or a fumaric acid moiety or a salt thereof.

2. The epoxy resin composition according to claim 1 , wherein the coated inorganic filler was obtained by impregnating with a solution or suspension containing the polycarboxylate ether and a solvent.

3. The epoxy resin composition according to claim 2 , wherein the solvent is a polar organic solvent.

4. The epoxy resin composition according to claim 1 , wherein the inorganic filler has a proportion of finely divided fillers of at least 5 wt. % based on the total weight of the inorganics filler.

5. The epoxy resin composition according to claim 1 , additionally containing at least one curing agent and/or at least one reactive diluent.

6. The epoxy resin composition according to claim 5 , wherein
the epoxy resin comprises at least one glycidyl ether, and/or
the curing agent contains at least one polyamine, which is selected from the group consisting of aliphatic, cycloaliphatic or arylaliphatic primary diamines, triamines, tetramines, polyamines with more than four amine groups per molecule, secondary amine group-containing polyamines, amine/polyepoxide adducts, poly(ethylene imines), polyamidoamines, Mannich bases and amino-terminated butadiene/acrylonitrile copolymers, and/or
the inorganic filler has at least one filler selected from silicon compounds of at least one of silica, silicates and precipitated and pyrogenic silicas, metal oxides of at least one of titanium dioxide, iron oxide, alumina, zinc oxide and magnesium oxide; metal carbonates of at least one calcium carbonate and dolomite; metal sulfates of at least one of calcium sulfate and barium sulfate; metal hydroxides of at least one of aluminum hydroxide, nitrides and carbides, clay minerals of at least one of kaolin, fly ash, cement, glass and ceramic materials.

7. A multi-component system for producing a curable epoxy resin composition according to claim 1 , comprising at least
one component K1 containing said at least one epoxy resin, and
optionally a curing agent component K2 containing said at least one curing agent,
wherein at least one curing agent is contained in said component K1 or K2,
wherein said at least one inorganic filler coated with the polycarboxylate ether is contained in said component K1, K2, and/or a further component K3.

8. The multi-component system according to claim 7 , comprising at least
one component K1 containing at least one epoxy resin,
one component K2 containing at least one curing agent, and
one solid component K3 containing
(a) 93 to 99.7 wt. % inorganic fillers,
(b) 0.01 to 2 wt. % polycarboxylate ether, and
(c) 0.02 to 5 wt. % solvent.

9. A cured epoxy resin obtainable by mixing the components and curing a multi-component system according to claim 7 .

10. A method comprising applying the multi-component system according to claim 7 to a substrate to bond, coat or seal the substrate, or to a mold to produce a molding therein.

11. A cured epoxy resin obtainable by curing an epoxy resin composition according to claim 1 .

12. A curable epoxy resin composition containing at least one epoxy resin having on average more than one epoxide group per molecule, at least one inorganic filler and at least one polycarboxylate ether, wherein the inorganic filler is coated with the polycarboxylate ether, wherein the polycarboxylate ether comprises:
a) at least one acid moiety A of formula (I):

wherein in formula (I):

each R 1 , R 2 and R 3 independently of one another represents H, —COOM, —CH 2 COOM or an alkyl group having 1 to 5 carbon atoms,
each R 4 independently of one another represents —COOM, —CH 2 COOM, —SO 2 —OM, —O—PO(OM) 2 and/or —PO(OM) 2 ,
or wherein R 3 together with R 4 forms a CO—O—CO-ring;
wherein M represents H, an alkali metal, an alkaline earth metal, ammonium, an ammonium cation, an organic ammonium compound, or mixtures thereof;

with the proviso that overall one or two of R 1 , R 2 , R 3 and R 4 is/are acid groups;
b) at least one structural moiety B of formula (II);

wherein in formula (II):
R 1 independently of one another represents H or CH 3 ;
R 2 independently of one another represents an ester group —CO—O— or an amide group —CO—NH—;
R 3 independently of one another represents a C 2 -C 6 alkylene group,
R 4 independently of one another represents H, a C 1 -C 12 alkyl or cycloalkyl radical, a C 7 -C 20 alkylaryl or aralkyl radical, or a substituted or unsubstituted aryl radical, or a monovalent organic radical having 1 to 30 carbon atoms, which optionally comprises heteroatoms, and
x independently of one another represents a value between 3 and 250,
wherein the main chain of the polycarboxylate ether is a linear copolymer which was obtained by polymerization using said at least one acid moiety or a salt or anhydride thereof,
wherein said structural moiety B is a component of this linear copolymer.

13. The epoxy resin composition according to claim 12 , wherein the polycarboxylate ether has at least one further structural moiety C, which is different from the structural moieties A and B, and which is selected from an ether, ester, amide or imide moiety, an acid moiety selected from carboxylic acid, sulfonic acid, phosphonic acid, phosphoric acid ester, carbonylamidomethylpropanesulfonic acid and salts thereof, or a polyoxyalkyleneoxycarbonyl, polyoxyalkyleneaminocarbonyl, polyoxyalkyleneoxyalkyl, polyoxyalkyleneoxy, hydroxyethyloxycarbonyl, acetoxy, phenyl or N-pyrrolidonyl group.

14. A method comprising dispersing an an inorganic filler in a curable epoxy resin composition with a polycarboxylate ether as a dispersing agent, wherein
the polycarboxylate ether has side chains linked to a main chain via ester, amide and/or ether groups wherein the main chain has at least one acrylic acid moiety or a salt thereof, and/or at least one methacrylic acid moiety or a salt thereof, and/or a maleic anhydride moiety or a salt thereof, and/or a maleic acid moiety or a salt thereof, and/or an itaconic acid moiety or a salt thereof, and/or a crotonic acid moiety or a salt thereof, and/or a fumaric acid moiety or a salt thereof.

15. A solid filler which is coated with a polycarboxylate ether, containing
(a) 93 to 99.97 wt. % inorganic fillers,
(b) 0.01 to 2 wt. % polycarboxylate, and
(c) 0.02 to 5 wt. % organic solvent, wherein
the polycarboxylate ether has side chains linked to a main chain via ester, amide and/or ether groups, wherein the main chain has at least one acrylic acid moiety or a salt thereof, and/or at least one methacrylic acid moiety or a salt thereof, and/or a maleic anhydride moiety or a salt thereof, and/or a maleic acid moiety or a

Assignees

• Sika Tech Ag

Inventors

• Beck Edda
• Schnabel Patrick

Classifications

• C08K2003/2268

  Ferrous oxide (FeO) · CPC title

• C08G59/502

  Polyalkylene polyamines · CPC title

• C08K3/34

  Silicon-containing compounds · CPC title

• C08L63/00 Primary

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08K2003/265

  Calcium, strontium or barium carbonate · CPC title