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CN-122029235-A - High char yield thermoplastic polymer blends and corresponding articles and uses

CN122029235ACN 122029235 ACN122029235 ACN 122029235ACN-122029235-A

Abstract

Described herein are thermoplastic polymer blends (hereinafter "polymer blends") comprising a thermoplastic polymer and mesophase pitch, wherein the thermoplastic polymer comprises polyarylene sulfide ("PAS"), polyaryletherketone ("PAEK"), or polyphenyl ("PP"). As used herein, "thermoplastic polymer" does not include reference to asphalt (mesophase or otherwise). Surprisingly, the polymer blends have significantly increased char yield relative to those predicted. Furthermore, the polymer blends have a desirable viscosity, which makes them suitable for conventional thermoplastic polymer technology. Based at least in part on char yield and viscosity, the polymer blends are particularly desirable for use in the formation of carbon fibers, thermoplastic prepregs, carbon-carbon composites, and heat protection systems.

Inventors

  • M. JACKSON
  • N. Tritter
  • G. V. Deshpande
  • J.D. Cook

Assignees

  • 塞特工业公司

Dates

Publication Date
20260512
Application Date
20241008
Priority Date
20240126

Claims (20)

  1. 1. A polymer blend of a polymer and a blend of at least two polymers, it comprises: -30.0 wt to 90.0 wt% of a first thermoplastic polymer selected from the group consisting of polyarylene sulfide ("PAS"), polyaryletherketone ("PAEK") and polyphenyl ("PP") -10.0 Wt to 70.0 wt% mesophase pitch.
  2. 2. The polymer blend of claim 1, wherein the first thermoplastic polymer is PAS, preferably polyphenylene sulfide ("PPS").
  3. 3. The polymer blend of claim 1, wherein the first thermoplastic polymer is PAEK, preferably polyetherketoneketone ("PEKK").
  4. 4. The polymer blend of claim 1, wherein the first thermoplastic polymer is PP.
  5. 5. The polymer blend of any of claims 1-4, wherein the mesophase pitch has a softening temperature of at least 150 ℃ and not more than 350 ℃.
  6. 6. The polymer blend of any of claims 1-5, wherein the polymer blend comprises 20.0 wt to 50.0 wt% mesophase pitch, preferably 20.0 wt to 40.0 wt% mesophase pitch.
  7. 7. The polymer blend of any of claims 1-6, wherein the polymer blend comprises 50.0 wt to 80.0 wt% of the first thermoplastic polymer.
  8. 8. The polymer blend of any of claims 1-7, wherein the thermoplastic polymer consists essentially of the first thermoplastic polymer.
  9. 9. The polymer blend of any of claims 1 to 7, wherein the polymer blend further comprises a polysulfone ("PS"), preferably a polyphenylsulfone ("PPSU").
  10. 10. The polymer blend of claim 9, wherein the concentration of the first thermoplastic polymer is 7.0 wt to 50.0 wt%.
  11. 11. A thermoplastic prepreg comprising a carbon fiber substrate and the polymer blend of any one of claims 1 to 10.
  12. 12. The thermoplastic prepreg of claim 11 in which the carbon fiber substrate is a single layer substrate selected from the group consisting of tape, mat and fabric, preferably tape, or it is a 3D printed filament.
  13. 13. A green body comprising a laminate consolidated by the thermoplastic prepreg of any one of claims 11 or 12.
  14. 14. A method of making the green body of claim 13, the method comprising forming a laminate by consolidating the prepreg.
  15. 15. A method according to claim 14 comprising the steps of laying up two or more thermoplastic prepregs according to claim 11 such that each prepreg is in contact with one or two other prepregs and consolidating the laid thermoplastic prepregs by heating, optionally at a pressure above atmospheric pressure.
  16. 16. A method of making a carbon-carbon composite ("C/C composite") article, the method comprising pyrolyzing the green body of claim 13, wherein the pyrolyzing comprises heating the green body at a temperature of at least 1000 ℃.
  17. 17. Use of the polymer blend according to any one of claims 1 to 10 in a heat protection system.
  18. 18. A material film comprising the polymer blend of any one of claims 1 to 10.
  19. 19. A film according to claim 18, wherein the material film is in contact with an outer surface of a component selected from a battery compartment, rocket nozzle or spacecraft, preferably a battery compartment.
  20. 20. A filament or stabilized filament comprising the polymer blend of any one of claims 1 to 10.

Description

High char yield thermoplastic polymer blends and corresponding articles and uses Citation of related application The application claims priority from U.S. provisional application number 63/589583 filed on day 10 and 11 of 2023 and european patent application number 24154272.9 filed on day 1 and 26 of 2024, the entire contents of each of these applications are incorporated herein by reference for all purposes. Technical Field The present invention relates to polymer blends comprising a thermoplastic polymer and mesophase pitch. The invention further relates to articles and uses of such blends. Background High char yield polymers are advantageous in a number of applications including, but not limited to, forming meltspun carbon fibers and heat protection systems. In one conventional approach, thermosetting polymers are used, at least in part, due to their high char yield. However, the use of thermosetting polymers is accompanied by relatively long curing times and undesirable outgassing of volatiles (during curing). Although thermoplastic polymers have been investigated to address the following drawbacks of the thermoset polymer approach, carbon residue rates remain relatively low. Disclosure of Invention In a first aspect, the present invention relates to a polymer blend comprising 30.0 wt to 90.0 wt% of a first thermoplastic polymer selected from the group consisting of polyarylene sulfide ("PAS"), polyaryletherketone ("PAEK") and polyphenylene ("PP"), and 10.0 wt to 70.0 wt% of mesophase pitch. In some embodiments, the first thermoplastic polymer is PAS, preferably polyphenylene sulfide ("PPS"). In some embodiments, the first thermoplastic polymer is PAEK, preferably polyetherketoneketone ("PEKK"). In some embodiments, the first thermoplastic polymer is PP. The polymer blend advantageously comprises 20.0 wt to 50.0 wt% mesophase pitch, preferably 20.0 wt to 40.0 wt% mesophase pitch. The polymer blend comprises 50.0 wt to 80.0 wt% of the first thermoplastic polymer. In some embodiments, the thermoplastic polymer consists essentially of the first thermoplastic polymer. In an alternative embodiment, the polymer blend further comprises polysulfone ("PS"), preferably polyphenylsulfone ("PPSU"). The concentration of the first thermoplastic polymer is typically 7.0 wt to 50.0 wt%. In a second aspect, the present invention relates to a thermoplastic prepreg comprising a carbon fiber substrate and the polymer blend. In some embodiments, the carbon fiber substrate is a single layer substrate selected from the group consisting of a tape, a mat, and a fabric, preferably a tape. In some embodiments, the thermoplastic prepreg is a 3D printed filament. In another aspect, the invention relates to a green body comprising a laminate consolidated with thermoplastic prepreg, preferably wherein the carbon fiber substrate is a single layer substrate selected from the group consisting of tape, mat, and fabric. In yet another aspect, the present invention relates to a material film comprising the polymer blend. In some embodiments, the film of material is in contact with a surface of a component selected from the group consisting of a battery compartment, a rocket nozzle, or a spacecraft, preferably a battery compartment. In yet another aspect, the present invention relates to a filament or stabilized filament comprising the polymer blend according to any one of claims 1 to 10. Detailed Description Described herein is a thermoplastic polymer blend (hereinafter "polymer blend") comprising a thermoplastic polymer and mesophase pitch, wherein the thermoplastic polymer comprises a polymer selected from the group consisting of polyarylene sulfide ("PAS"), polyaryletherketone ("PAEK"), or polyphenyl ("PP"). As used herein, "thermoplastic polymer" does not include reference to asphalt (mesophase or otherwise). Surprisingly, the polymer blends have significantly increased char yield relative to those predicted. Furthermore, the polymer blends have a desirable viscosity, which makes them suitable for conventional thermoplastic polymer technology. Based at least in part on char yield and viscosity, the polymer blends are particularly desirable for use in the formation of carbon fibers, thermoplastic prepregs, carbon-carbon composites, and heat protection systems. As used herein with respect to ranges, a series of lower values are recited followed immediately by a series of higher values (where each value in the higher series is greater than the maximum value in the lower series), specifically considering each range formed by the combination of each of the lower values with each of the higher values. For example, in the following description, specifically contemplated and within the scope of the present disclosure, "in some embodiments, the concentration of species A is at least X or at least Y. In some embodiments, the concentration of species B does not exceed P, does not exceed D, or does not exceed Q, "is the concentration range of X to