Reinforced unsaturated polyester resin compositions

• US 20030220035A1
• Filed: 05/17/2002
• Published: 11/27/2003
• Est. Priority Date: 05/17/2002
• Status: Abandoned Application

• Current Assignee: Flint Hills Resources LP (KOCH Industries Incorporated)
• Original Assignee: Flint Hills Resources LP (KOCH Industries Incorporated)
• Inventors: Fjare, Douglas E.
• Application Number:
  US10/151,746
• Publication Number:
  US 20030220035A1
• Time in Patent Office: Days
• US Class Current: 442/103
• CPC Class Codes: C08G 18/683 containing cyclic groups
• CPC Class Codes: C08K 7/02 Fibres or whiskers
• CPC Class Codes: C08L 75/14 Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: Y10T 428/24994 Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/249952 At least one thermosetting synthetic polymeric material layer
• CPC Class Codes: Y10T 442/2361 Coating or impregnation improves stiffness of the fabric other than specified as a size
• CPC Class Codes: Y10T 442/2926 Coated or impregnated inorganic fiber fabric
• CPC Class Codes: Y10T 442/2975 Coated or impregnated ceramic fiber fabric
• CPC Class Codes: Y10T 442/2984 Coated or impregnated carbon or carbonaceous fiber fabric

Abstract

Unsaturated polyester compositions modified with a polyisocyanate provide low cost thermosetting matrix resins with improve adhesion to carbon fibers. The modified polyester resins are useful in fabricating low cost carbon fiber-reinforced composites.

Claims

1. A composition comprising an unsaturated polyester, a polyisocyanate, and a copolymerizable liquid ethylenically unsaturated monomer, the molar ratio of the isocyanate groups to the hydroxyl groups in said composition lying in the range of from about 0.05 to about 0.65.

2. The composition of claim 1 wherein said unsaturated polyester has a reactive hydroxyl group content represented by a hydroxyl number of from about 30 to about 120 mg KOH/g of resin.

3. The composition of claim 1 wherein said monomer is a vinylaromatic monomer.

4. The composition of claim 1 wherein said monomer is styrene.

5. The composition of claim 1 wherein said polyisocyanate is selected from the group consisting of aromatic diisocyanates and aliphatic diisocyanates.

6. The composition of claim 1 wherein said polyisocyanate is selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, toluene diisocyanate, and oligomeric methylene diphenyl diisocyanate.

7. A composition comprising an unsaturated polyester having a reactive hydroxyl group content represented by a hydroxyl number of from about 30 to about 120 mg KOH/g of resin;

a polyisocyanate selected from the group consisting of aromatic diisocyanates and aliphatic diisocyanates; and

a copolymerizable liquid monomer, the molar ratio of the isocyanate groups to the hydroxyl groups in said composition lying in the range of from about 0.05 to about 0.65.

8. The composition of claim 7 wherein said unsaturated polyester is the product of the polyesterification of an aromatic dicarboxylic acid, an ethylenically unsaturated dicarboxylic acid, and at least one polyhydric alcohol.

9. The composition of claim 7 wherein said unsaturated polyester is the product of the polyesterification of an aromatic dicarboxylic acid selected from the group consisting of isophthalic acid, orthophthalic acid, terephthalic acid and esters and anhydrides thereof;

an unsaturated carboxylic acid selected from the group consisting of maleic acid, fumaric acid, citaconic acid, chloromaleic acid, allyl succinic acid, itaconic acid, mesaconic acid and alkyl esters and anhydrides thereof; and

at least one polyhydric alcohol selected from the group consisting of neopentyl glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, polyethylene glycol, mannitol, 1,2-propanediol, 1,6-hexanediol, and 1,3-butylene glycol.

10. The composition of claim 7 wherein said polyisocyanate is selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, toluene diisocyanate, and oligomeric methylene diphenyl diisocyanate.

11. The composition of claim 7 further comprising a polymerization catalyst.

12. A fiber-reinforced composite comprising from about 35 to about 60 volume percent carbon fibers, based upon the total volume of the composite, imbedded in the resin reaction product of a mixture comprising:

from about 30 to about 50 parts by weight of ethylenically unsaturated liquid monomer;

from about 70 to about 50 parts by weight of an unsaturated polyester having a reactive hydroxyl group content represented by a hydroxyl number of from about 30 to about 120 mg KOH/g of resin; and

an amount of an organic polyisocyanate sufficient to provide from about 0.05 to about 0.65 moles of isocyanate groups per mole of said reactive hydroxyl groups.

13. The fiber reinforced composite according to claim 12 further comprising a polymerization catalyst.

14. The fiber-reinforced composite according to claim 12 wherein said monomer is a vinylaromatic monomer.

15. The fiber-reinforced composite according to claim 12 wherein said polyester is the product of the polyesterification of an aromatic dicarboxylic acid, an ethylenically unsaturated dicarboxylic acid, and at least one polyhydric alcohol.

16. The fiber-reinforced composite according to claim 12 wherein said polyester is the product of the polyesterification of a dicarboxylic acid selected from the group consisting of isophthalic acid, orthophthalic acid, terephthalic acid and esters and anhydrides thereof;

maleic acid, or anhydride; and

at least one polyhydric alcohol selected from the group consisting of neopentyl glycol, ethylene glycol, diethylene glycol, and propylene glycol.

17. A method for making a carbon fiber-reinforced plastic comprising the step of impregnating continuous carbon fibers with a resin composition comprising an unsaturated polyester having a hydroxyl value of from about 30 to about 120, a copolymerizable liquid monomer and an amount of an organic polyisocyanate sufficient to provide from about 0.05 to about 0.65 moles of isocyanate groups per mole of said reactive hydroxyl groups, thereby providing impregnated carbon fiber prepreg containing from about 35 to about 60 volume percent carbon fiber.

18. The method of claim 17 further comprising the steps of molding and curing said prepreg.

19. The method of claim 17 wherein said polyester is the polyesterification product of an aromatic dicarboxylic acid selected from isophthalic acid, terephthalic acid and orthophthalic acid, or an ester or anhydride thereof;

maleic anhydride, and at least one polyhydric alcohol.

20. The method of claim 17 wherein said organic polyisocyanate is selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, toluene diisocyanate, and oligomeric methylene diphenyl diisocyanate.

21. In a composition comprising an unsaturated polyester having a reactive hydroxyl group content represented by a hydroxyl number of from about 30 to about 120 mg KOH/g of resin, a polyisocyanate, and a copolymerizable liquid monomer, the improvement wherein the molar ratio of the isocyanate groups to the hydroxyl groups is in the range of from about 0.05 to about 0.65.