Thermosetting polyester composition containing normally solid carboxy-containing diene polymer

Abstract

A thermosettable composition suitable for preparing reinforced plastic articles is prepared by combining an unsaturated polyester, a normally solid carboxy-containing polymer of a conjugated diene, a vinyl monomer, a catalyst and a reinforcing agent or filler. Preferably the composition is prepared utilizing a mixer giving moderate shear such as a twin-rotor mixer. The resulting composition when cured exhibits high impact strength and good surface finish.

What is claimed is: 
     
       1. A .Iadd.cured thermoset article produced by subjecting to heat a thermosetting .Iaddend.composition comprising: a. an unsaturated polyester prepared by reacting an unsaturated dicarboxylic acid and a polyol;   b. .Iadd.a diene component consisting essentially of .Iaddend.a normally solid carboxy-containing polymer of a conjugated diene having a weight average molecular weight within the range of .[.30,000.]. .Iadd.50,000 .Iaddend.to .[.400,000.]. .Iadd.250,000 and wherein said carboxy-containing polymer has a polymerized conjugated diene content of from 55 to 100 weight percent.Iaddend.;   c. a vinyl monomer;   d. a catalyst; and   e. .[.at least one of.]. a .Iadd.fibrous .Iaddend.reinforcing agent .[.or a filler.]..   
     
     
       2. .[.A composition.]. .Iadd.An article .Iaddend.according to claim 1 wherein said polymer of a conjugated diene has .[.a weight average molecular weight within the range of 50,000 to 250,000 and.]. an inherent viscosity within the range of 0.6 to 2. 
     
     
       3. .[.A composition.]. .Iadd.An article .Iaddend.according to claim 1 wherein said polymer of a conjugated diene is a copolymer of butadiene and styrene. 
     
     
       4. .[.A composition.]. .Iadd.An article .Iaddend.according to claim 1 wherein said polyester is prepared by reacting fumaric acid and propylene glycol. 
     
     
       5. .[.A composition.]. .Iadd.An article .Iaddend.according to claim 1 wherein said vinyl monomer is styrene. 
     
     
       6. .[.A composition.]. .Iadd.An article .Iaddend.according to claim 1 wherein a ratio of (a) to (b) is within the range of 5:1 to 1:1 and wherein said vinyl monomer is present in an amount within the range of 30 to 200 parts by weight per 100 parts by weight of (a) plus (b). 
     
     
       7. .[.A composition.]. .Iadd.An article .Iaddend.according to claim 1 wherein said catalyst is a peroxide .Iadd.and said composition contains in addition a lubricant and a thickener. .Iaddend. 
     
     
       8. .[.A composition.]. .Iadd.An article .Iaddend.according to claim 1 .[.containing.]. .Iadd.wherein said fibrous reinforcing agent is composed of .Iaddend.glass fibers and .Iadd.wherein said composition contains in addition .Iaddend.calcium carbonate. 
     
     
       9. .[.A composition.]. .Iadd.An article .Iaddend.according to claim 1 wherein said unsaturated polyester is produced by reacting fumaric acid and propylene glycol, said normally solid carboxy-containing polymer is a copolymer of butadiene and styrene characterized by a vinyl addition of 5 to 76 percent and having 0.01 to 5 weight percent carboxyl content, said vinyl monomer is styrene, a ratio of (a) to (b) being within the range of 5:1 to 1:1, said vinyl monomer is present in an amount within the range of 30 to 200 parts by weight per 100 parts by weight of (a) plus (b), said catalyst is tertiary butyl perbenzoate present in an amount within the range of 1-5 parts by weight per 100 parts by weight of (a) plus (b).Iadd., said fibrous reinforcing agent is composed of glass fibers present in an amount within the range of 40 to 200 parts by weight per 100 parts by weight of (a) plus (b) .Iaddend.and wherein said composition contains calcium carbonate filler in an amount within the range of 200 to 800 parts by weight of filler per 100 parts .[.per.]. .Iadd.by .Iaddend.weight of (a) plus (b), .[.glass fiber reinforcing agent in an amount within the range of 40 to 200 parts by weight per 100 parts by weight of (a) plus (b),.]. 1 to 15 parts by weight of zinc stearate per 100 parts by weight of (a) plus (b) and 1 to 10 parts by weight of magnesium hydroxide per 100 parts by weight of (a) plus (b). .[.10. A cured article produced by subjecting the composition of claim 9 to heat..]. .[.11. A cured article produced by subjecting the composition of 
     
     
        claim 1 to heat..]. 12. A method of forming thermosetting compositions suitable for preparing reinforced plastic articles comprising milling together under conditions of moderate shear: a. an unsaturated polyester prepared by reacting an unsaturated dicarboxylic acid and a polyol;   b. a normally solid carboxy-containing polymer of a conjugated diene having a weight average molecular weight within the range of 30,000 to 400,000;   c. a vinyl monomer;   d. a catalyst; and   e. .[.at least one of.]. a .Iadd.fibrous .Iaddend.reinforcing agent .[.or a   
     
     
        filler.].. 13. A method according to claim 12 wherein said milling is done 
     
     
        with a twin-rotor mixer using sigma blades. 14. A method according to claim 13 wherein said unsaturated polyester is produced by reacting fumaric acid and propylene glycol, said normally solid carboxy-containing polymer is a copolymer of butadiene and styrene characterized by a vinyl unsaturation of 5 to 76 percent and having 0.01 to 5 weight percent carboxyl content, said vinyl monomer is styrene, a ratio of (a) to (b) is within the range of 5:1 to 1:1, said vinyl monomer is present in an amount within the range of 30 to 200 parts by weight per .[.110.]. .Iadd.100 .Iaddend.parts by weight of (a) plus (b), said catalyst is tertiary butyl perbenzoate.Iadd., said fibrous reinforcing agent is composed of glass fibers present in an amount within the range of 40 to 200 parts by weight per 100 parts by weight of (a) plus (b) .Iaddend.and wherein said composition contains calcium carbonate filler in an amount within the range of 200 to 800 parts by weight of filler per 100 parts .[.per.]. .Iadd.by .Iaddend.weight of (a) plus (b), .[.glass fiber reinforcing agent in an amount within the range of 40 to 200 parts by weight of (a) plus (b),.]. 1 to 15 parts by weight of a lubricant per 100 parts by weight of (a) plus (b) and 1 to 10 parts by weight of an oxide or hydroxide of a 
     
     
        group II metal. 15. A method according to claim 13 wherein said shear 
     
     
        produces a temperature rise of 2° to 30° C. 16. A method according to claim 12 wherein the resulting composition is subjected to curing conditions of 100° C. to 200° C. for a time within the range of 1 to 15 minutes. .Iadd. 17. A composition consisting essentially of: a. an unsaturated polyester prepared by reacting an unsaturated dicarboxylic acid and a polyol;   b. a normally solid carboxy-containing polymer of a conjugated diene having a weight average molecular weight within the range of 30,000 to 400,000 and wherein said carboxy-containing polymer has a polymerized conjugated diene content of from 55 to 100 weight percent;   c. a vinyl monomer;   d. a catalyst;   e. a fibrous reinforcing agent;   f. a lubricant selected from aluminum stearate, barium stearate, clacium stearate, magnesium stearate of zinc stearate;   g. a thickener selected from oxides and hydroxides of magnesium, calcium, strontium, barium and zinc; and   h. a filler. .Iaddend. .Iadd. 18. A composition according to claim 17 wherein said unsaturated polyester is prepared by reacting fumaric acid and propylene glycol, said normally solid carboxy-containing polymer is a copolymer of butadiene and styrene characterized by a vinyl unsaturation of 5 to 76 percent and having 0.01 to 5 weight percent carboxyl content, said vinyl monomer is styrene, a ratio of (a) to (b) is within the range of 5:1 to 1:1, said vinyl monomer is present in an amount within the range of 30 to 200 parts by weight per 100 parts by weight of (a) plus (b), said catalyst is tertiary butyl perbenzoate present in an amount within the range of 1-5 parts by weight per 100 parts by weight of (a) plus (b), said fibrous reinforcing agent is composed of glass fibers present in an amount within the range of 40 to 200 parts by weight per 100 parts by weight of (a) plus (b), said lubricant is zinc stearate present in an amount within the range of 1-15 parts by weight per 100 parts by weight of (a) plus (b), said thickener is magnesium hydroxide present in an amount within the range of 1-10 parts by weight per 100 parts by weight of (a) plus (b) and said filler is calcium carbonate present in an amount within the range of 200 to 800 parts by weight per 100 parts by weight of (a) plus (b). .Iaddend.