Heat-stabilized acrylate elastomer composition and process for its production
View Patent ↗Polyamide-filled acrylate copolymer compositions comprising a continuous acrylate copolymer phase and a discontinuous polyamide phase are produced by a melt mixing process. When crosslinked with diamine curatives the polyamide-filled acrylate copolymer compositions exhibit enhanced resistance to heat aging compared to carbon black-reinforced acrylate copolymer compositions.
1. A curable polyamide-filled acrylate copolymer composition comprising
A. a polymer blend composition comprising
1. 40 to 90 wt. % of one or more amorphous acrylate copolymers comprising
a) at least 50 wt. %, based on the total weight of the amorphous acrylate copolymer, of polymerized units of at least one monomer having the structure
Where R 1 is H or C 1 -C 10 alkyl and R 2 is -C 1 -C 12 alkyl, C 1 -C 20 alkoxyalkyl, -C 1 -C 12 cyanoalkyl, or -C 1 -C 12 fluoroalkyl, and
b) copolymerized units of a cure site monomer selected from the group consisting of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, unsaturated epoxides, and mixtures of two or more thereof; and
2. 10-60 wt. % of one or more polyamides having a melting peak temperature of at least 160° C.;
wherein i) the one or more polyamides are present as a discontinuous phase in the polymer blend composition, ii) the green strength of the polymer blend composition is less than about 2 MPa, as determined in accordance with ASTM D6746-10, and iii) the weight percentages of the one or more amorphous acrylate copolymers and the one or more polyamides are based on the combined weight of the one or more amorphous acrylate copolymers and one or more polyamides in the polymer blend composition; and
B. an amine curative.
2. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein the one or more amorphous acrylate copolymers of the polymer blend composition comprise polymerized units of at least one monomer selected from the group consisting of alkyl acrylates, alkyl methacrylates, alkoxyalkyl acrylates, alkoxyalkyl methacrylates, and mixtures of two or more thereof.
3. A composition of claim 2 wherein the monomer is an alkyl acrylate selected from the group consisting of methyl acrylate, ethyl acrylate, and butyl acrylate.
4. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein at least one of the one or more amorphous acrylate copolymers of the polymer blend composition comprises a cure site monomer selected from the group consisting of 1,4-butenedioic acids, anhydrides of unsaturated carboxylic acids, monoalkyl esters of 1,4-butenedioic acid, and mixtures of two or more thereof.
5. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein at least one of the one or more amorphous acrylate copolymers of the polymer blend composition additionally comprises copolymerized units of an olefin.
6. A composition of claim 5 wherein the olefin is ethylene.
7. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein at least one of the one or more amorphous acrylate copolymers of the polymer blend composition comprises a cure site monomer that is an unsaturated epoxide.
8. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein at least one of the one or more polyamides of the polymer blend composition is selected from the group consisting of i) polyamides formed by ring opening or condensation of aminocarboxylic acids and ii) polyamides having a melting peak temperature of less than 270° C. and an amine end group concentration of 60 meq/kg or less.
9. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein at least one of the one or more polyamides of the polymer blend composition has an inherent viscosity greater than 0.9 dL/g as determined in accordance with ASTM D2857-95, using 96% by weight sulfuric acid as a solvent at a test temperature of 25° C.
10. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein the polymer blend composition comprises 50 to 80 weight percent of one or more amorphous acrylate copolymers and 20 to 50 weight percent of one or more polyamides, based on the total weight of the one or more amorphous acrylate copolymers and one or more polyamides.
11. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein the polymer blend composition comprises 55 to 70 weight percent of one or more amorphous acrylate copolymers and 30 to 45 weight percent of one or more polyamides based on the total weight of the one or more amorphous acrylate copolymers and one or more polyamides.
12. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein the amine curative is selected from the group consisting of diamine carbamates, diamines and mixtures thereof.
13. A composition of claim 12 wherein the amine curative is selected from the group consisting of hexamethylenediamine, hexamethylenediamine carbamate, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.
14. A curable polyamide-filled acrylate copolymer composition of claim 1 additionally comprising at least one material selected from the group consisting of reinforcing fillers, antioxidants, accelerators, plasticizers, process aids, waxes, pigments, and colorants.
15. A composition of claim 14 wherein the material is an antioxidant selected from the group consisting of aryl amines, phenolics, imidazoles, phosphites, phosphorus esters, hindered phenolics and mixtures of two or more thereof.
16. A composition of claim 14 wherein the material is an accelerator selected from the group consisting of guanidines, arylguanidines, alkylguanidines, amidines, guanidine salts, arylguanidine salts, alkylguanidine salts, amidine salts, and mixtures of two or more thereof.
17. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein the polymer blend composition has a Mooney viscosity of less than 120 as determined according to ASTM D1646, ML 1+4, at 100° C.
18. A curable polyamide-filled acrylate copolymer composition of claim 1 having a cure response MH-ML of at least 2.5 dN-m as determined according to ASTM D5289-07a using an MDR 2000 from Alpha Technologies operating at 0.5° arc and test conditions of 177° C. for 24 minutes, where ML refers to the minimum torque value measured and MH refers to the maximum torque value attained after the measurement of ML.
19. A curable polyamide-filled acrylate copolymer composition of claim 1 wherein at least one of the one or more polyamides comprises nylon 6.