High strength composite

• US 5,552,208 A
• Filed: 10/29/1993
• Issued: 09/03/1996
• Est. Priority Date: 10/29/1993
• Status: Expired due to Term

• Current Assignee: Alliedsignal Inc.
• Original Assignee: Alliedsignal Inc.
• Inventors: Bhatnagar, Ashok, Wilson, Laura G., Lin, Leroy C.-T., Li, Hsin L.
• Primary Examiner(s): Withers, James
• Application Number:
  US08/148,732
• Time in Patent Office: 1,040 Days
• Field of Search: 428/229, 428/245, 428/286, 428/294, 428/902, 428/911, 428/113, 2/2.5
• US Class Current: 428/113
• CPC Class Codes: C08J 5/04 Reinforcing macromolecular compounds with loose or coherent fibrous material
• CPC Class Codes: C08J 5/24 Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• CPC Class Codes: F41H 5/0485 all the layers being only fibre- or fabric-reinforced layers
• CPC Class Codes: Y10S 428/902 High modulus filament or fiber
• CPC Class Codes: Y10S 428/911 Penetration resistant layer
• CPC Class Codes: Y10T 428/24124 Fibers
• CPC Class Codes: Y10T 428/249945 Carbon or carbonaceous fiber
• CPC Class Codes: Y10T 428/249946 Glass fiber
• CPC Class Codes: Y10T 428/249947 Polymeric fiber
• CPC Class Codes: Y10T 442/2623 Ballistic resistant

Abstract

An article made from at least one network of high strength fibers and a matrix composition that includes a vinyl ester and diallyl phthalate. Preferably, the article is made from at least one prepreg element which includes at least two adjacent layers of the high strength fiber network in the vinyl ester-containing matrix composition. The prepreg element is made by applying a mixture of vinyl ester, diallyl phthalate and a carbon-carbon saturated solvent to the high strength fiber network.

Claims

1. An article comprising at least one consolidated network of high strength fibers in a matrix composition, the high strength fibers having a tenacity of at least about 7 g/d, a tensile modulus of at least about 150 g/d and an energy-to-break of at least about 8 J/g, wherein prior to consolidation the matrix composition comprises at least one thermoset vinyl ester, diallyl phthalate, and at least one carbon-carbon saturated solvent, said solvent being substantially removed during consolidation, and said thermoset vinyl ester having a tenacity of about 10,000 to 50,000 psi (6.9×

10⁴ to 3.4×

10⁵ kPa), a tensile modulus of about 1×

10⁶ to 3×

10⁶ psi (6.9×

10⁶ to 2.1×

10⁷ kPa), a T_G of less than about 165°

C., and an elongation-to-break of about 2 to 1.4%.

2. An article according to claim 1, wherein the high strength fibers are selected from at least one of the group consisting of extended chain polyolefin fibers, aramid fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, liquid crystal copolyester, glass and carbon fibers.

3. An article according to claim 1, wherein the high strength fibers comprise extended chain polyethylene fibers.

4. An article according to claim 1, wherein the high strength fibers have a tenacity of at least about 22 g/d, a tensile modulus of at least about 900 g/d and an energy-to-break of at least about 27 J/g.

5. An article according to claim 1, wherein the vinyl ester comprises a reaction product of a polyfunctional epoxy resin and an unsaturated monocarboxylic acid.

6. An article according to claim 5, wherein the vinyl ester is selected from the group consisting of diglycidyl adipate, diglycidyl isophthalate, di-(2,3-epoxybutyl) adipate, di-(2,3-epoxybutyl) oxalate, di-(2,3-epoxyhexyl) succinate, di-(3,4-epoxybutyl) maleate, di-(2,3-epoxyoctyl) pimelate, di-(2,3-epoxybutyl) phthalate, di-(2,3-epoxyoctyl) tetrahydrophthalate, di-(4,5-epoxy-dodecyl) maleate, di-(2,3-epoxybutyl) terephthalate, di-(2,3-epoxypentyl) thiodipropronate, di-(5,6-epoxy-tetradecyl) diphenyldicarboxylate, di-(3,4-epoxyheptyl) sulphonyldibutyrate, tri-(2,3-epoxybutyl)-1,2,4-butanetricarboxylate, di-(5,6-epoxypentadecyl)maleate, di-(2,3-epoxybutyl) azelate, di-(3,4-epoxypentadecyl) citrate, di-(4,5-epoxyoctyl) cyclohexane-1,3-dicarboxylate, di-(4,5-epoxyoctadecyl) malonate and bisphenol-A-fumaric acid polyester.

7. An article according to claim 1, wherein after consolidation the matrix composition comprises about 5 to 15 weight % diallyl phthalate and the remainder vinyl ester, based on the total weight of the matrix composition.

8. An article according to claim 1, comprising at least two adjacent layers of the high strength fiber network in the matrix composition, wherein the fibers of each layer are unidirectionally aligned and the fiber direction of at least one fiber network layer is rotated at an angle of about 90°

relative to the fiber direction of the adjacent fiber network layer.

9. An article according to claim 8, wherein the vinyl ester comprises a reaction product of a polyfunctional epoxy resin and an unsaturated monocarboxylic acid.

10. An article according to claim 1, wherein the article is a ballistic resistant composite.

12. The article of claim 1 wherein the carbon-carbon saturated solvent is selected from the group consisting of methyl ethyl ketone, acetone, ethanol, methanol, isopropyl alcohol, cyclohexane and ethyl acetone.

13. The article of claim 12 wherein the carbon-carbon saturated solvent is methyl ethyl ketone.

11. The article of claim I wherein the carbon-carbon saturated solvent is selected from the group consisting of an alcohol that contains 1 to 5 carbon atoms, a ketone that contains 3 to 10 carbon atoms and an acetate that contains 1 to 5 carbon atoms.

14. A prepreg element comprising at least two consolidated adjacent layers of a network of high strength fibers in a matrix composition, the high strength fibers having a tenacity of at least about 7 g/d, a tensile modulus of at least about 150 g/d and an energy-to-break of at least about 8 J/g, wherein prior to consolidation of the coated high strength fiber networks the matrix composition comprises at least one thermoset vinyl ester, diallyl phthalate, and at least one carbon-carbon saturated solvent, said solvent being removed during consolidation, and said thermoset vinyl ester having a tenacity of about 10,000 to 50,000 psi (6.9×

10⁴ to 3.4 ×

10⁵ kPa), a tensile modulus of about 1×

10⁶ to 3×

10⁶ psi (6.9×

10⁶ to 2.1×

10⁷ kPa), a T_G of less than about 165°

C., and an elongation-to-break of about 2 to 14%.

15. A prepreg element according to claim 14, wherein the high strength fibers are selected from at least one of the group consisting of extended chain polyolefin fibers, aramid fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, liquid crystal copolyester, glass and carbon fibers.

16. A prepreg element according to claim 15, wherein the high strength fibers comprise extended chain polyethylene fibers.

17. A prepreg element according to claim 14, wherein the vinyl ester comprises a reaction product of a polyfunctional epoxy resin and an unsaturated monocarboxylic acid.

18. A prepreg element according to claim 17, wherein the vinyl ester is selected from the group consisting of diglycidyI adipate, diglycidyl isophthalate, di-(2,3-epoxybutyl) adipate, di-(2,3-epoxybutyl) oxalate, di-(2,3-epoxyhexyl) succinate, di-(3,4-epoxybutyl) maleate, di-(2,3-epoxyoctyl) pimelate, di-(2,3-epoxybutyl)phthalate, di-(2,3-epoxyoctyl) tetrahydrophthalate, di-(4,5-epoxy-dodecyl) maleate, di-(2,3-epoxybutyl) terephthalate, di-(2,3-epoxypentyl) thiodipropronate, di-(5,6-epoxy-tetradecyl) diphenyldicarboxylate, di-(3,4-epoxyheptyl) sulphonyldibutyrate, tri-(2,3-epoxybutyl)-1,2,4-butanetricarboxylate, di-(5,6-epoxypentadecyl)maleate, di-(2,3-epoxybutyl) azelate, di-(3,4-epoxypentadecyl) citrate, di-(4,5-epoxyoctyl) cyclohexane-1,3-dicarboxylate, di-(4,5-epoxyoctadecyl) malonate and bisphenol-A-fumaric acid polyester.

19. A prepreg element according to claim 14, wherein after consolidation the matrix composition comprises about 5 to 15 weight % diallyl phthalate and the remainder vinyl ester, based on the total weight of the matrix composition.

20. A prepreg element according to claim 14, wherein the fibers of each fiber network layer are unidirectionally aligned and the fiber direction of at least one fiber network layer is rotated at an angle of about 90°

relative to the fiber direction of the adjacent fiber network layer.

21. The prepreg element of claim 14 wherein the carbon-carbon saturated solvent is selected from the group consisting of an alcohol that contains 1 to 5 carbon atoms, a ketone that contains 3 to 10 carbon atoms and an acetate that contains 1 to 5 carbon atoms.

22. The article of claim 14 wherein the carbon-carbon saturated solvent is selected from the group consisting of methyl ethyl ketone, acetone, ethanol, methanol, isopropyl alcohol, cyclohexane and ethyl acetone.

23. The article of claim 22 wherein the carbon-carbon saturated solvent is methyl ethyl ketone.