Sizing compositions for carbon fibers

Patent metadata

Field	Value
Publication number	US-10106680-B2
Application number	US-201515302148-A
Country	US
Kind code	B2
Filing date	Apr 6, 2015
Priority date	Apr 7, 2014
Publication date	Oct 23, 2018
Grant date	Oct 23, 2018

Abstract

The present invention provides aqueous, epoxy-based sizing compositions for carbon fibers. The size composition incorporates highly functionalized film forming epoxy novolac phenolic resins in combination with highly functionalized sulfonated polyesters having high Tg characteristics, sulfonate equivalent weights in the range from 2000 to 20,000 and number average molecular weights in the range from about 1000 to about 100,000. The present invention also provides corresponding sized carbon fibers and fiber-reinforced matrices.

First claim

What is claimed is:

1. A sizing composition, comprising:
a) at least one film forming, epoxy functional, novolac phenolic resin; and
b) at least one film forming, sulfonated polyester resin having a sulfonate equivalent weight in the range from 2000 to 20,000 and a number average molecular weight in the range from about 1000 to about 100,000; and
c) an aqueous liquid carrier.

2. The sizing composition of claim 1 , wherein the at least one film forming, sulfonated polyester resin has a Tg of at least 35° C.

3. The sizing composition of claim 2 , wherein the Tg is at least 50° C.

4. The sizing composition of claim 1 , wherein the at least one film forming, sulfonated polyester resin is linear.

5. The sizing composition of claim 1 , wherein the at least one film forming sulfonated polyester resin includes one or more polyester linkages, and wherein the at least one film forming, sulfonated polyester resin includes at least one additional polymerized linkage other than the one or more polyester linkages.

6. The sizing composition of claim 1 , wherein the at least one film forming, sulfonated polyester resin has a sulfonate equivalent weight in the range from 2000 to 6000.

7. The sizing composition of claim 1 , wherein the at least one film forming, sulfonated polyester resin incorporates a plurality of sulfonated backbone moieties according to the following structure, wherein M is a monovalent and/or divalent cation:

8. The sizing composition of claim 1 , wherein the at least one film forming, sulfonated polyester resin incorporates a plurality of sulfo-sulfonated backbone moieties.

9. The sizing composition of claim 1 , wherein the at least one film forming, epoxy functional, novolac phenolic resin includes epoxy functionality and at least one other functionality.

10. The sizing composition of claim 9 , wherein the at least one other functionality comprises alkyl functionality and /or ether functionality.

11. The sizing composition of claim 9 , wherein the at least one film forming, epoxy functional, novolac phenolic resin includes 0.2 to 10 phenolic repeating units on average.

12. The sizing composition of claim 9 , wherein the at least one film forming, epoxy functional, novolac phenolic resin includes 0.2 to 4 phenolic repeating units on average.

13. The sizing composition of claim 9 , wherein the at least one film forming, epoxy functional, novolac phenolic resin has an epoxy equivalent weight in the range from 150 to 250.

14. The sizing composition of claim 9 , wherein the at least one film forming, epoxy functional, novolac phenolic resin has an epoxy equivalent weight in the range from 165 to 190.

15. The sizing composition of claim 9 , wherein the at least one film forming, epoxy functional, novolac phenolic resin comprises a structure according to Formula 2, wherein z on average is 0.2 to 50:

16. The sizing composition of claim 1 , wherein the sizing composition includes 10 to 60 parts by weight of the at least one film forming, epoxy functional, novalac phenolic resin per 40 to 90 parts by weight of the at least one film forming, sulfonated polyester resin.

17. A fiber reinforced matrix, comprising:
a) a matrix; and
b) at least one coated carbon fiber incorporated into the matrix, said coated carbon fiber comprising:
(i) a carbon fiber; and
(ii) a coating provided on at least a portion of the carbon fiber, said coating being derived from ingredients comprising at least one film forming, epoxy functional, novolac phenolic resin; and at least one film forming, sulfonated polyester resin having a sulfonate equivalent weight in the range from 2000 to 20,000 and a number average molecular weight in the range from about 1000 to about 100,000.

18. A method of making a sizing composition, comprising the steps of:
a) providing at least one film forming, epoxy functional, novolac phenolic resin;
b) providing at least one film forming, sulfonated polyester resin having a sulfonate equivalent weight in the range from 2000 to 20,000 and a number average molecular weight in the range from about 1000 to about 100,000;
c) melting the at least one film forming, epoxy functional, novolac phenolic resin and the at least one film forming, sulfonated polyester resin;
d) blending the melted resins to provide a blended admixture comprising at least one melted, film forming, epoxy functional, novolac phenolic resin and at least one melted film forming, sulfonated polyester resin; and
e) combining the blended admixture with water in a manner effective to provide an aqueous dispersion, wherein at least a portion of said combining occurs while the blended admixture comprises at least one melted, film forming, epoxy functional, novolac phenolic resin and at least one melted film forming, sulfonated polyester resin.

19. The method of claim 18 , wherein step (e) comprises using 50 to 200 parts by weight of water per 100 parts by weight of the at least one film forming, sulfonated polyester resin.

20. The method of claim 18 , wherein step (c) comprises using 10 to 60 parts by weight of the film forming, epoxy functional, novolac phenolic resin per 40 to 90 parts by weight of the at least one film forming, sulfonated polyester resin.

Assignees

• Dow Global Technologies Llc

Inventors

• Kumar Bhawesh
• Sekharan Manesh Nadupparambil
• Kuo Tzu-Chi
• Young Timothy J
• Broderick Adam H

Classifications

• C08J5/042

  with carbon fibres · CPC title

• C08J2367/00

  Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers · CPC title

• C08J5/06

  using pretreated fibrous materials · CPC title

• C08L67/00 Primary

  Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain (of polyester-amides C08L77/12; of polyester-imides C08L79/08); Compositions of derivatives of such polymers · CPC title

• C08J2463/04

  Epoxynovolacs · CPC title