Thermoset volatile monomer molding compositions

• US 6,203,911 B1
• Filed: 06/17/1998
• Issued: 03/20/2001
• Est. Priority Date: 06/17/1998
• Status: Expired due to Term

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Weberg, Rolf Thomas, Simmons, Lawrence J., Gleason, Richard Reid
• Primary Examiner(s): TORRES VELAZQUEZ, NORCA LIZ
• Application Number:
  US09/099,888
• Time in Patent Office: 1,007 Days
• Field of Search: 526/328, 523/211, 523/400, 523/500, 428/413, 428/480, 428/482, 428/500
• US Class Current: 428/413
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 4/38 Mixtures of peroxy-compounds
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31794 Of cross-linked polyester
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 442/3415 Preformed metallic film or foil or sheet [film or foil or sheet had structural integrity prior to association with the woven fabric]
• CPC Class Codes: Y10T 442/3854 Woven fabric with a preformed polymeric film or sheet
• CPC Class Codes: Y10T 442/656 Preformed metallic film or foil or sheet [film or foil or sheet had structural integrity prior to association with the nonwoven fabric]
• CPC Class Codes: Y10T 442/674 Nonwoven fabric with a preformed polymeric film or sheet
• CPC Class Codes: Y10T 442/695 Including a wood containing layer

Abstract

A molding composition including reactive high-volatility monomeric groups, such as acrylics, at least one primary thermal initiator and at least one secondary thermal initiator is described. Molding processs using molding compositions including reactive high-volatility monomeric groups are also described.

Claims

1. A composition comprising:

(a) from about 10 to about 25% by weight of a liquid polymerizable material including at least one volatile monomer reactive material;

(b) at least one viscosity builder;

(c) at least one primary thermal initiator having a primary thermal initiator ten-hour half-life temperature; and

(d) at least one secondary thermal initiator having a secondary thermal initiator ten-hour half-life temperature at least about 5°

C. greater than the primary thermal initiator ten-hour half-life temperature;

wherein at least about 0.05% by weight is one or more crosslinking agents.

2. The composition of claim 1 wherein the secondary initiator ten-hour half-life temperature is in the range of from about 60°

to about 120°

C.

3. The composition of claim 1 wherein the composition is at least 95% cured when heated in a closed mold at a temperature of about 100°

to about 145°

C. for about 10 minutes or less.

4. The composition of claim 1 wherein the polymerizable material is selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, urethane acrylates, urethane methacrylates, epoxy acrylates, epoxy methacrylates, acrylate functionalized unsaturated polyesters, methacrylate functionalized unsaturated polyesters, vinyl monomers, urethanes, epoxies, unsaturated polyesters, siloxanes, silanes, and combinations thereof.

5. The composition of claim 4 wherein the polymerizable material is an ester of acrylic or methacrylic acid with an alcohol having 1-20 carbon atoms.

6. The composition of claim 1 wherein the volatile monomer is selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, acrylonitrile, methylacrylonitrile, vinyl acetate and combinations thereof.

7. The composition of claim 1 wherein the viscosity builder comprises from about 0.1 to about 25% by weight.

8. The composition of claim 1 wherein the viscosity builder is a polymeric setting agent having a weight average molecular weight greater than about 500,000.

9. The composition of claim 8 wherein the setting agent has a Tg equal to or greater than about 50°

C.

10. The composition of claim 8 wherein the setting agent has a weight average molecular weight greater than about 1,000,000.

11. The composition of claim 8 wherein the setting agent has a median particle size in the range of from about 2 to about 150 microns.

12. The composition of claim 11 wherein the setting agent has a median particle size in the range of from about 30 to about 150 microns.

13. The composition of claim 8 wherein the setting agent is selected from the group consisting of homopolymers and copolymers of acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, vinyl ethers, vinyl esters, acrylonitrile, methacrylonitrile, acrylamid, methacrylamid, styrene, substituted styrene, butadiene, and combinations thereof.

14. The composition of claim 1 wherein the primary thermal initiator comprises from about 0.01 to about 5% by weight.

15. The composition of claim 1 wherein the primary initiator ten-hour half-life temperature is in the range of from about 40f to about 80°

C.

16. The composition of claim 1 wherein the secondary thermal initiator comprises from about 0.001 to about 1% by weight.

17. The composition of claim 1 which further comprises from about 1% to about 20% by weight of a non-crosslinked resin polymer.

18. The composition of claim 17 wherein the non-crosslinked polymer resin has a weight average molecular weight of from about 30,000 to about 200,000.

19. The composition of claim 17 wherein the non-crosslinked resin polymer is selected from the group consisting of non-reactive materials and reactive materials.

20. The composition of claim 17 wherein the non-crosslinked polymer is selected from the group consisting of homopolymers of acrylate esters, copolymers of acrylate esters, homopolymers of methacrylate esters, copolymers of methacrylate esters, and combinations thereof.

21. The composition of claim 1 which further comprises from about 1% to about 80% by weight of a filler.

22. The composition of claim 21 wherein the filler is a mineral filler selected from the group consisting of alumina trihydrate, alumina monohydrate, Bayer hydrate, silica, glass spheres, magnesium hydroxide, calcium carbonate, barium sulfate, ceramic particles, and combinations thereof.

23. The composition of claim 21 wherein the filler is a decorative filler selected from the group consisting of polymer particles, mineral filled polymer particles, pigments, dyes, reflective flakes, metal particles, rocks, colored glass, colored sand, wood products, and combinations thereof.

24. The composition of claim 21 wherein the filler is a functional filler selected from the group consisting of flame retardants, antibacterial agents, and combinations thereof.

25. The composition of claim 1 which further comprises from about 0.05% to about 3% by weight of a fiber.

26. The composition of claim 25 wherein the fiber is selected from the group consisting of polyester, glass, polyaramid, and combinations thereof.

27. A molded article made from a molding composition comprising (a) from about 10 to about 25% by weight of a liquid polymerizable material including at least one volatile monomer reactive material, (b) at least one primary thermal initiator having a primary thermal initiator ten-hour half-life temperature, (c) at least one secondary thermal initiator having a secondary thermal initiator ten-hour half-life temperature of at least about 5°

C. greater than the primary thermal initiator ten-hour half-life temperature, wherein at least about 0.05% by weight is one or more crosslinking agents.

28. The molded article of claim 27 wherein the article comprises a functional core completely encapsulated by the molding composition.

29. The molded article of claim 27, wherein the article is made from at least a firs t charge unit and a second charge unit, the first charge unit having a molding composition that is different from a second charge unit molding composition.