Novel cationic epoxy resin esters and process of producing same

• US 4,579,932 A
• Filed: 11/07/1983
• Issued: 04/01/1986
• Est. Priority Date: 11/05/1982
• Status: Expired due to Fees

• Current Assignee: Vianova Kunstharz AG A-8402 Werndorf Austria
• Original Assignee: Vianova Kunstharz AG (Eastman Chemical Company)
• Inventors: Paar, Willibald, Honig, Helmut
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US06/549,328
• Time in Patent Office: 876 Days
• Field of Search: 528/113, 528/114, 528/96
• US Class Current: 528/114
• CPC Class Codes: C09D 5/4426 Esterified polyepoxides

Abstract

Cationic epoxy resin esters suitable as binders for stoving coating compositions, particularly for application by electrodeposition, and as mill base resins for grinding pigments and extenders; and a process for producing same is described. The resin esters are produced through reaction of a resinous compound carrying at least two 1,2-epoxy groups with carboxylic acids and, optionally, with primary and/or secondary alkyl- and/or alkanolamines. The carboxylic acid employed, totally or partially, is the reaction product of a dicarboxylic acid anhydride and a tertiary amine which has the structure - ##STR1## wherein R and R_x are a hydrogen atom or an alkyl radical or an aryl radical which may be substituted, R₇ is an alkyl radical, an amino-alkyl radical having the primary amino groups, if present, blocked (as a ketimine) or the moiety remaining after the reaction with an active hydrogen atom of an acrylic or methacrylic monomer monofunctional with regard to the double bond, and wherein n is 2 or 3, the quantity of basic component being chosen in order that the epoxy-free final product has an amine value of at least 35, and preferably of from 40 to 140 mg KOH/g.

Claims

1. Cationic epoxy resin esters obtained by the reaction of a compound carrying at least two 1,2-epoxy groups with a carboxylic acid, said carboxylic acid being the reaction product of a dicarboxylic acid anhydride and a tertiary amine, said amine having the structure- ##STR12## wherein R and R_x are a hydrogen atom;

an alkyl radical or an aryl radical and n is 2 or 3, and R_y is an alkyl radical, an amino-alkyl radical having the primary amino groups, if present, being in the form of ketimine blocked amino groups, and said tertiary amine being obtained through ring formation with an aldehyde, water being split off, from at least one member of the group-

(a) an N-substituted ethanolamine or N-substituted propanolamine;

(b) primary β

-hydroxyethylamines or β

-hydroxypropylamines or γ

-hydroxyethylamines or γ

-hydroxypropylamines, or a substituted derivative of said amines, after blocking the primary amino group as a ketimine or through reaction with acrylate monomers, and

(c) reaction product of a primary alkyl amine with a monoepoxy compound;

the quantity of tertiary amine being such that the epoxy resin ester is at least substantially free of epoxy groups and has an amine value of at least 35 mg KOH/g.

2. The cationic epoxy resin esters of claim 1 wherein said reaction product of epoxy group containing compound and carboxylic acid further includes a primary or secondary alkyl or alkanol amine.

3. The cationic epoxy resin esters of claim 1 wherein said epoxy resin ester has an amine value of from about 40 to 140 mg KOH/g.

4. The cationic epoxy resin esters of claim 1 wherein the components of said ester are selected to provide an ester containing a minimum of 0.8 chain end double bonds in 1000 molecular weight units to provide a self-crosslinking binder.

5. A process for producing cationic epoxy resin esters comprising the steps of reacting a resinous compound carrying at least two 1,2-epoxy groups with a carboxylic acid characterized in that said carboxylic acid is a reaction product of a dicarboxylic acid anhydride and a tertiary amine having the structure- ##STR13## wherein R and R_x are a hydrogen atom;

an alkyl radical or an aryl radical, and n is 2 or 3, and R_y is an alkyl radical, an amino-alkyl radical having the primary amino groups, if present, being in the form of ketimine blocked amino groups, and said tertiary amine being obtained through ring formation with an aldehyde, water being split off, from at least one member of the group-

(a) an N-substituted ethanolamine of N-substituted propanolamine;

(b) primary β

-hydroxyethylamines or β

-hydroxypropylamines or γ

-hydroxyethylamines or γ

-hydroxypropylamines, or a substituted derivative of said amines, after blocking the primary amino group as a ketimine or through reaction with acrylate monomers, and

(c) reaction product of a primary alkyl amine with a monoepoxy compound;

the quantity of tertiary amine being such that the esters are at least substantially free of epoxy groups and have an amine value of at least 35 mg KOH/g.

6. Process according to claim 5 wherein said reaction is carried out at 60°

to 75°

C., the carboxylic acid being reacted with the epoxy compound to an acid value of below 3 mg KOH/g.

7. Process according to claim 5 including the step of treating said epoxy resin esters with water for several hours at 50°

to 80°

C. in the presence of 10 millimoles of said per 100 g of resin solids.

8. Process according to claim 5 wherein the reaction of the dicarboxylic acid anhydride with the tertiary amines is carried out at from 50°

to 100°

C.

9. The process of claim 5 further including the step of modifying the reaction product of epoxy containing compound and carboxylic acid with a primary or secondary alkyl or alkanolamine.

10. The process of claim 8 wherein said amine value is from about 40 to 140 mg KOH/g.