Multifunctional curing agents and their use in improving strength of composites containing carbon fibers embedded in a polymeric matrix

• US 9,617,398 B2
• Filed: 12/16/2013
• Issued: 04/11/2017
• Est. Priority Date: 12/16/2013
• Status: Active Grant

• Current Assignee: UT-Battelle LLC
• Original Assignee: UT-Battelle LLC
• Inventors: Vautard, Frederic, Ozcan, Soydan
• Primary Examiner(s): PAK, HANNAH J
• Application Number:
  US14/107,416
• Publication Number:
  US 20160102180A1
• Time in Patent Office: 1,212 Days
• CPC Class Codes: C08J 2367/06 Unsaturated polyesters
• CPC Class Codes: C08J 5/06 using pretreated fibrous materials
• CPC Class Codes: D06M 14/36 on to carbon fibres
• CPC Class Codes: D06M 15/263 of unsaturated carboxylic acids; Salts or esters thereof
• CPC Class Codes: D06M 15/273 of unsaturated carboxylic esters having epoxy groups
• CPC Class Codes: D06M 15/55 Epoxy resins
• CPC Class Codes: D06M 2101/40 Fibres of carbon
• CPC Class Codes: D06M 2200/40 Reduced friction resistance, lubricant properties; Sizing compositions
• CPC Class Codes: D06M 2400/01 Creating covalent bondings between the treating agent and the fibre

Abstract

A functionalized carbon fiber having covalently bound on its surface a sizing agent containing epoxy groups, at least some of which are engaged in covalent bonds with crosslinking molecules, wherein each of said crosslinking molecules possesses at least two epoxy-reactive groups and at least one free functional group reactive with functional groups of a polymer matrix in which the carbon fiber is to be incorporated, wherein at least a portion of said crosslinking molecules are engaged, via at least two of their epoxy-reactive groups, in crosslinking bonds between at least two epoxy groups of the sizing agent. Composites comprised of these functionalized carbon fibers embedded in a polymeric matrix are also described. Methods for producing the functionalized carbon fibers and composites thereof are also described.

Claims

1. A composition comprising a carbon fiber having covalently bound on its surface a sizing agent containing epoxy groups, with said epoxy groups partially or completely engaged in covalent bonds with crosslinking molecules, wherein each of said crosslinking molecules possesses at least two epoxy-reactive groups and at least one free functional group reactive with functional groups of a polymer matrix in which the carbon fiber is to be incorporated, wherein at least a portion of said crosslinking molecules are engaged, via at least two of their epoxy-reactive groups, in crosslinking bonds between at least two epoxy groups of the sizing agent.

2. The composition of claim 1, wherein said free functional group is an alkenyl group.

3. The composition of claim 1, wherein said free functional group is an isocyanate group.

4. The composition of claim 1, wherein a portion of said crosslinking molecules are engaged, via less than all of their epoxy-reactive groups, in an equivalent number of covalent bonds with said epoxy groups, wherein said crosslinking molecule possesses at least one free epoxy-reactive group in addition to the free functional group.

5. The composition of claim 4, wherein said at least one free epoxy-reactive group is an isocyanate group.

6. The composition of claim 1, wherein said sizing agent is partially cured by having at least a portion of epoxide groups in said sizing agent available as uncrosslinked epoxide groups.

7. The composition of claim 6, wherein the partially cured sizing agent is flexible.

8. The composition of claim 1, wherein said sizing agent is completely cured by having no epoxide groups in said sizing agent available as uncrosslinked epoxide groups.

9. The composition of claim 1, wherein said sizing agent comprises a difunctional or higher functional epoxy resin.

10. A solid composite comprising carbon fibers embedded in a polymeric matrix, wherein said carbon fibers have covalently bound on their surfaces a sizing agent containing epoxy groups, with said epoxy groups partially or completely engaged in covalent bonds with crosslinking molecules, wherein each of said crosslinking molecules possesses at least two epoxy-reactive groups and at least one functional group crosslinked with functional groups of said polymer matrix, wherein at least a portion of said crosslinking molecules are engaged, via at least two of their epoxy-reactive groups, in crosslinking bonds between at least two epoxy groups of the sizing agent.

11. The solid composite of claim 10, wherein said polymeric matrix is a cured vinyl ester resin.

12. The solid composite of claim 10, wherein said polymeric matrix is a cured unsaturated polyester resin.

13. The solid composite of claim 10, wherein said polymeric matrix is a vinyl addition polymer.

14. The solid composite of claim 10, wherein said sizing agent is comprised of a difunctional or higher functional epoxy resin.

15. The solid composite of claim 10, wherein a portion of said crosslinking molecules are engaged, via less than all of their epoxy-reactive groups, in an equivalent number of covalent bonds with said epoxy groups, wherein said crosslinking molecule is crosslinked with said polymeric matrix by at least one of its remaining epoxy-reactive groups in addition to being crosslinked to said polymeric matrix by said at least one functional group.

16. The solid composite of claim 15, wherein said at least one remaining epoxy-reactive group is an isocyanate group, which is in crosslinked form with an isocyanate-reactive group of said polymeric matrix.