Fiber-reinforced composites made with thermoplastic resin compositions and reactive coupling fibers

Patent metadata

Field	Value
Publication number	US-10407553-B2
Application number	US-201715639065-A
Country	US
Kind code	B2
Filing date	Jun 30, 2017
Priority date	Nov 22, 2013
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

Methods of making fiber-resin compositions are described. The methods may include the providing of a thermoplastic resin to an extruder, where the thermoplastic resin may include at least one reactive moiety capable of forming a covalent bond with a coupling agent on a plurality of reactive fibers. The methods may further include combining the thermoplastic resin with the plurality of reactive fibers also supplied to the extruder. The reactive fibers are sized with the coupling agent that reacts with the thermoplastic resin to form the fiber-resin composition, which may be extruded from the extruder. Methods of making fiber-reinforced composite articles from the fiber-resin composition are also described.

First claim

What is claimed is:

1. A fiber-resin composition for making a fiber-reinforced article, the fiber-resin composition comprising:
fibers, wherein at least some of the fibers are glass fibers that include a coupling agent bonded to the glass fibers; and
a thermoplastic resin comprising a polyamide polymer, wherein the polyamide polymer includes a plurality of amide moieties that form covalent bonds with the coupling agent bonded to the glass fibers,
wherein the thermoplastic resin is in a molten state in the fiber-resin composition, and
wherein the coupling agent comprises:
(i) a silicon-containing moiety covalently bonded to the glass fibers,
(ii) a reactive isocyanate moiety capable of forming the covalent bond with the at least one reactive moiety of the thermoplastic resin when a blocking group is released from the reactive isocyanate moiety, and
(iii) a linking moiety selected from the group consisting of an unsubstituted alkyl group, an unsubstituted aryl group, and an unsubstituted alkyl-aryl group, wherein the linking moiety covalently bonds the silicon-containing moiety and the reactive isocyanate moiety together in the coupling agent.

2. The fiber-resin composition of claim 1 , wherein the glass fibers have a length of less than 0.5 inches in the fiber-resin composition.

3. The fiber-resin composition of claim 1 , wherein the glass fibers have a length ranging from 0.5 inches to 2 inches in the fiber-resin composition.

4. The fiber-resin composition of claim 1 , wherein the glass fibers comprise at least one type of glass selected from the group consisting of E-glass, A-glass, C-glass, S-glass, ECR-glass, and T-glass.

5. The fiber-resin composition of claim 1 , wherein the silicon-containing moiety has a formula of:

wherein R 1 , R 2 , and R 3 may be the same or different, and each may represent an alkyl group, an aryl group, an alkoxy group, a halogen, a hydroxyl group, or a cyclic structure.

6. The fiber-resin composition of claim 1 , wherein the reactive isocyanate moiety has a formula of:

wherein BLK represents the blocking group that is reversibly bonded to a carbon atom on the reactive isocyanate moiety.

7. The fiber-resin composition of claim 1 , wherein the blocking group is selected from the group consisting of oximes, lactams, and organosilicon compounds.

8. The fiber-resin composition of claim 7 , wherein the oximes are selected from the group consisting of methyl ethyl ketoxime, acetone oxime, and cyclohexanone oxime.

9. The fiber-resin composition of claim 7 , wherein the lactams comprise ε-caprolactam.

10. The fiber-resin composition of claim 1 , wherein the polyamide polymer is selected from the group consisting of polyamide-6; polyamide-6,6; polyamide-6,12; polyamide-4,6; polyamide-6,10; polyamide-12; polyamide 6T; and polyamide 6I.

11. A fiber-reinforced article comprising:
fibers; and
a thermoplastic polyamide polymer, wherein the thermoplastic polyamide polymer includes a plurality of amide moieties that are covalently bonded to the fibers by a coupling agent that is covalently bonded to both the fibers and the thermoplastic polymer,
wherein the fiber-reinforced article is formed from a fiber-resin composition that includes a molten amalgam of the fibers and the thermoplastic polymer,
wherein at least a portion of the fibers in the fiber-resin composition are reactive glass fibers bonded to the coupling agent, and
wherein the coupling agent comprises:
(i) a silicon-containing moiety covalently bonded to the glass fibers,
(ii) an unblocked isocyanate moiety that has decoupled from a blocking group at the melting temperature of the thermoplastic polymer, wherein the unblocked isocyanate moiety forms the covalent bond with the thermoplastic polymer, and
(iii) a linking moiety selected from the group consisting of an unsubstituted alkyl group, an unsubstituted aryl group, and an unsubstituted alkyl-aryl group, wherein the linking moiety covalently bonds the silicon-containing moiety and the isocyanate moiety together in the coupling agent.

12. The fiber-reinforced article of claim 11 , wherein the fibers have a length of less than 0.5 inches in the fiber-reinforced article.

13. The fiber-reinforced article of claim 11 , wherein the fibers have a length ranging from 0.5 inches to 2 inches in the fiber-reinforced article.

14. The fiber-reinforced article of claim 11 , wherein the polyamide polymer is selected from the group consisting of polyamide-6; polyamide-6,6; polyamide-6,12; polyamide-4,6; polyamide-6,10; polyamide-12; polyamide 6T; and polyamide 6I.

15. The fiber-reinforced article of claim 11 , wherein the article is selected from the group consisting of a turbine blade, a vehicle part, an appliance part, and a container.

16. A system for making a fiber-reinforced article, the system comprising:
a supply of fibers, wherein the fibers comprise glass reactive fibers that are covalently bonded to a coupling agent;
a supply of thermoplastic resin, wherein the thermoplastic resin comprises a polyamide polymer, and wherein the polyamide polymer includes a plurality of amide moieties capable of covalently bonding to isocyanate moieties on the coupling agents, wherein the coupling agent further comprises:
a silicon-containing moiety covalently bonded to the glass fibers, and
a linking moiety selected from the group consisting of an unsubstituted alkyl group, an unsubstituted aryl group, and an unsubstituted alkyl-aryl group, wherein the linking moiety covalently bonds the silicon-containing moiety and the isocyanate moiety together in the coupling agent;
an extruder that combines the fibers and the thermoplastic resin into a molten amalgam; and
a molding machine that accepts the molten amalgam from the extruder and molds into the fiber-reinforced article.

17. The system of claim 16 , wherein the supply of fibers are short glass fibers having a length of less than 0.5 inches in the fiber-reinforced article.

18. The system of claim 16 , wherein the supply of fibers are long glass fibers having a length ranging from 0.5 inches to 2 inches in the fiber-reinforced article.

19. The system of claim 16 , wherein the coupling agent comprises a blocking group coupled to the isocyanate moiety in the supply of sized fibers, wherein the blocking group is decoupled from the isocyanate moiety in the molten amalgam of the fiber and the thermoplastic resin.

20. The system of claim 19 , wherein the blocking group is selected from the group consisting of oximes, lactams, and organosilicon compounds.

21. The system of claim 19 , wherein the blocking group comprises ε-caprolactam.

22. The system of claim 16 , wherein the polyamide polymer is selected from the group consisting of polyamide-6; polyamide-6,6; polyamide-6,12; polyamide-4,6; polyamide-6,10; polyamide-12; polyamide 6T; and polyamide 6I.

23. The system of claim 16 , wherein the molding machine is selected from the group consisting of an injection molding machine and a compression molding machine.

Assignees

• Johns Manville

Inventors

• Block Michael J
• Zhang Mingfu
• Yohannes Asheber
• Gleich Klaus Friedrich
• Asrar Jawed

Classifications

• C08J2377/06

  Polyamides derived from polyamines and polycarboxylic acids (C08J2377/10 takes precedence) · CPC title

• C08J5/06

  using pretreated fibrous materials · CPC title

• C08J5/08 Primary

  glass fibres · CPC title

• C08G69/48

  Polymers modified by chemical after-treatment · CPC title

• B29C48/022

  characterised by the choice of material · CPC title