Remendable interfaces for polymer composites

Patent metadata

Field	Value
Publication number	US-9884944-B2
Application number	US-201113698399-A
Country	US
Kind code	B2
Filing date	May 18, 2011
Priority date	May 19, 2010
Publication date	Feb 6, 2018
Grant date	Feb 6, 2018

Abstract

Functionalized polymer matrix and/or reinforcement materials that are capable of a thermoreversible Diels-Alder reaction are useful for making composite materials. Also disclosed is a composite material which includes one or both of functionalized reinforcement materials and functionalized polymer matrix materials, as well as a method for repairing a composite material including the step of thermally treating the composite material at a temperature sufficient to react a functionality on one of the reinforcement material and the polymer matrix material with another functionality via a Diels-Alder reaction. A method of making a composite material including functionalizing one or both of a reinforcing material and a polymer matrix material with a first reactive group, providing a second reactive group capable of undergoing a Diels-Alder reaction with the first reactive group and reacting the first and second reactive groups to form a composite material, is also described.

First claim

The invention claimed is:

1. A composite material comprising:
a Diels-Alder reaction product of:
a polymer matrix material including at least a first reactive group that is capable of a thermoreversible Diels-Alder reaction; and
a reinforcing material including at least a second reactive group that is capable of a thermoreversible Diels-Alder reaction with the first reactive group of the polymer matrix material to produce a remendable composite material, wherein the second reactive group of the reinforcing material comprises a reactive group selected from the group consisting of a furan group, a fulvene group, and a maleimide group, and when said second reactive group comprises a maleimide group, said composite material is made by the steps of:
(i) silanating the reinforcing material with an amino group-containing silane,
(ii) functionalizing the silanated reinforcing material by reacting the amino group with a maleimide having two or more maleimide groups, and
(iii) reacting the reaction product of step (ii) with the polymer matrix material by a Diels-Alder reaction.

2. The composite material as claimed in claim 1 wherein the first reactive group of the polymer matrix material comprises a reactive group selected from the group consisting of a furan group, a fulvene group, and a maleimide group.

3. The composite material as claimed in claim 2 , wherein the first reactive group of the polymer matrix material comprises the furan group.

4. The composite material as claimed in claim 1 , wherein the second reactive group of the reinforcing material comprises the maleimide group and the first reactive group of the polymer matrix material comprises a furan group.

5. The composite material as claimed in claim 1 , wherein the composite material further comprises one or more capsules or particles housing a solution containing additional said second reactive group.

6. A composite material as claimed in claim 1 wherein the second reactive group of the reinforcing material comprises the maleimide group.

7. The composite material as claimed in claim 6 , wherein the second reactive group of the reinforcing material comprises the maleimide group and the reinforcing material is functionalized with a bismaleimide.

8. A method for repairing a composite material comprising a Diels-Alder reaction product of:
a polymer matrix material comprising a first reactive group that is capable of a thermoreversible Diels-Alder reaction, and
a reinforcing material comprising a second reactive group that is capable of a thermoreversible Diels-Alder reaction with the first reactive group of the polymer matrix material, wherein the second reactive group of the reinforcing material comprises a reactive group selected from the group consisting of a furan group, a fulvene group, and a maleimide group, and when said second reactive group comprises a maleimide group, said composite material is made by the steps of:
(i) silanating the reinforcing material with an amino group-containing silane,
(ii) functionalizing the silanated reinforcing material by reacting the amino group with a maleimide having two or more maleimide groups, and
(iii) reacting the reaction product of step (ii) with the polymer matrix material by a Diels-Alder reaction;
said method comprising the steps of:
thermally treating the composite material at a temperature sufficient to thermally reverse a Diels-Alder reaction between the first reactive group and the second reactive group, and
cooling said thermally treated composite material to a temperature at which the first reactive group reacts with the second reactive group via a Diels-Alder reaction.

9. The method as claimed in claim 8 , wherein the first reactive group of the polymer matrix material comprises a reactive group selected from the group consisting of a furan group, a fulvene group, and a maleimide group.

10. The method as claimed in claim 9 , wherein the first reactive group of the polymer matrix material comprises the furan group.

11. The method as claimed in claim 8 , wherein the second reactive group of the reinforcing material comprises the maleimide group and the first reactive group of the polymer matrix material comprises a furan group.

12. The method as claimed in claim 8 , wherein the composite material further comprises one or more capsules or particles housing a solution containing additional said second reactive group.

13. The method as claimed in claim 8 wherein the second reactive group of the reinforcing material comprises the maleimide group.

14. A method of making a composite material comprising the steps of combining a polymer matrix material functionalized with a first reactive group that is capable of a thermoreversible Diels-Alder reaction, and a reinforcing material that is functionalized with a second reactive group that is capable of a thermoreversible Diels-Alder reaction with said first reactive group, wherein the second reactive group of the reinforcing material comprises a reactive group selected from the group consisting of a furan group, a fulvene group, and a maleimide group; and
reacting the first reactive group with a second reactive group via a Diels-Alder reaction to form a composite material,
wherein when said second reactive group comprises a maleimide group, said composite material is made by the steps of:
(i) silanating the reinforcing material with an amino group-containing silane,
(ii) functionalizing the silanated reinforcing material by reacting the amino group with a maleimide having two of more maleimide groups, and
(iii) reacting the reaction product of step (ii) with the polymer matrix material by a Diels-Alder reaction.

15. The composite material as claimed in claim 4 , wherein the reinforcing material comprises functionalized glass fibers.

16. The composite material as claimed in claim 1 , wherein the polymer matrix material comprises polymer selected from the group consisting of: a polyamide, a polyester, a polycarbonate, a polyether, an epoxy polymer; a vinyl ester polymer; a polyimide, a phenol-formaldehyde polymer, an amine-formaldehyde polymer, a polysulfone; a poly(acrylonitrile-butadiene-styrene), a polyurethane; a polyolefin, a polystyrene, a polyacrylonitrile, a polyvinyl polymer, a polyacrylate, a poly(alkylacrylate), a polysilane and a polyphosphazene.

17. The composite material as claimed in claim 1 wherein the polymer matrix material comprises a furan-functionalized epoxy-amine thermoset.

18. The composite material as claimed in claim 1 , wherein the polymer matrix material comprises an elastomer.

19. The method as claimed in claim 11 , wherein the reinforcing material comprises functionalized glass fibers.

20. The method as claimed in claim 14 , for making a composite material using a maleimide having two or more maleimide groups, said method further comprising the steps of:
silanating the reinforcing material to provide a silanated reinforcing material, and
functionalizing the silanated reinforcing material with a maleimide having two or more maleimide groups via Michael addition to provide the reinforcing material having the second reactive group.

21. The composite material as claimed in claim 1 , wherein the second reactive group is the maleimide group and the second reactive group is introduced to the reinforcing material by functionalizing the reinforcing material with a polyfunctional maleimide selected from the group consisting of 1,1′-(methylene di-4,1-phenylene)bismaleimide, 1,3- or 1,4-dimaleimido benzene, 1,3- or

Assignees

• Palmese Giuseppe R
• Peterson Amy M
• Jensen Robert E
• Univ Drexel
• Us Army

Inventors

• Palmese Giuseppe R
• Peterson Amy M
• Jensen Robert E

Classifications

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08L71/02

  Polyalkylene oxides · CPC title

• C08G2261/126

  block · CPC title

• C08K9/04

  Ingredients treated with organic substances {(treated with macromolecular compounds C08K9/08)} · CPC title

• C08J5/04 Primary

  Reinforcing macromolecular compounds with loose or coherent fibrous material · CPC title