Heat treated polymer powders

Patent metadata

Field	Value
Publication number	US-9587107-B2
Application number	US-201113879478-A
Country	US
Kind code	B2
Filing date	Sep 27, 2011
Priority date	Sep 27, 2010
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

The invention relates to heat treatment of polymorphic semicrystalline or crystallizable polymers to increase the content of the highest melting crystalline form. Such heat treatment results in a polymer powder that has a consistent, uniform melting range, improved flow and improved durability of the powder particle size for applications that require powder flow at elevated temperatures. In addition to improved powder properties, the articles produced from the powders also exhibit better physical properties in both appearance and in mechanical properties. Thus the invention also includes polymer powders and articles produced by the described processes.

First claim

What is claimed is:

1. A process for making a heat-treated polymer powder composition suitable for selective laser sintering, roto-molding or powder coating, said composition comprising at least two semicrystalline or crystallizable polyetherketoneketone polymorphs having at least two different melting points, said process comprising at least the steps of (a) determining heat treating conditions by selecting a temperature less than 20° C. below a melting point of a highest melting crystalline polymorph and at or above a melting point of another crystalline polymorph, and (b) heat-treating the polymer composition at said temperature less than 20° C. below the melting point of the highest melting crystalline polymorph and at or above the melting point of the other crystalline polymorph(s), for a time that increases the content of the highest melting crystalline polymorphs relative to the other crystalline polymorph(s) in the polymer composition, and wherein the polyether ketone ketone comprises repeating units represented by Formulas I and II:
-A-C(═O)-B-C(═O)—  I (Isomer T)

-A-C(═O)-D-C(═O)—  II (Isomer I)

where A is a p,p′-Ph-O-Ph- group, Ph is a phenylene radical, B is p-phenylene, and D is m-phenylene, wherein the T:I isomer ratio is in the range of from 60/40 to 80/20.

2. The process of claim 1 , further comprising grinding the heat-treated polymer composition into a powder wherein the crystallinity is not reduced.

3. The process of claim 1 , wherein the semicrystalline or crystallizable polymorphic polymers, prior to the heat treating and/or after heat treating, are in the form of particles having a weight average particle size of 15 to 150 microns.

4. The process of claim 1 , wherein the temperature of heat treatment is less than 15° C. below the melting point of the highest-melting crystalline polymorph.

5. The process of claim 1 , wherein the temperature of heat treatment is less than 10° C. below the melting point of the highest-melting crystalline polymorph.

6. The process of claim 1 , wherein the temperature of heat treatment is less than 5° C. below the melting point of the highest-melting crystalline polymorph.

7. The process of claim 1 , wherein the polymer composition further comprises one or more other components selected from the group consisting of non-polymorphic polymer(s), fillers, and fibers.

8. A heat-treated powder composition, made by the process of claim 1 .

9. A process comprising converting the heat-treated powder composition of claim 8 to an article or a coating on an article.

10. The process of claim 9 , wherein the process for converting the heat treated powder composition is selected from selective laser sintering, roto-molding, or powder coating.

11. The process of claim 1 wherein the heat treating temperature ranges from about 230° C. to about 300° C.

12. The process of claim 1 wherein the heat treating temperature ranges from about 270° C. to about 375° C.

13. The process of claim 1 wherein the resulting heat treated polymer composition contains 90% or more of Form I polyetherketoneketone based upon the total amount of Forms I and II in the polyetherketoneketone.

14. The process of claim 1 wherein the Form I polyetherketoneketone exhibits an X-ray diffraction pattern substantially the same as shown in FIG. 1 .

15. The process of claim 1 wherein the Form II polyetherketoneketone exhibits an X-ray diffraction pattern substantially the same as that shown in FIG. 2 .

16. A process for heat-treating a polymer powder composition comprising one or more polyetherketoneketone polymorphs having at least two crystalline forms having at least two different melting points, said process comprising at least the steps of (a) determining heat treating conditions by selected a temperature less than 20° C. below a melting point of a highest melting crystalline form and at or above a melting pint of another crystalline form, and (b) heat-treating the polymer composition at a temperature less than 20° C. below a melting point of a highest melting crystalline form and within or above a melting range of crystalline form(s), for a time that increases the content of the highest melting crystalline form relative to the other crystalline form(s) in the polymer composition, wherein the polyetherketoneketone polymers comprise repeating units represented by Formulas I and II:
-A-C(═O)-B-C(═O)—  I (Isomer T)

-A-C(═O)-D-C(═O)—  II (Isomer I)

where A is a p,p′-Ph-O-Ph- group, Ph is a phenylene radical, B is p-phenylene, and D is m-phenylene, wherein the T:I isomer ratio is in the range of from 60/40 to 80/20, such that the resulting powder composition is suitable for selective laser sintering, roto-molding or powder coating.

17. The process of claim 16 wherein the resulting heat treated polymer composition contains 40% or more of the highest melting crystalline form based on the total number of crystals in the polyetherketoneketone polymers.

18. The process of claim 16 wherein the resulting heat treated polymer composition contains 90% or more of the highest melting crystalline form based on the total number of crystals in the polyetherketoneketone polymers.

19. The process of claim 16 wherein the highest melting crystalline form of polyetherketoneketone exhibits an X-ray powder diffraction pattern having a characteristic peak at about 18.65° (scattering angle, 2 theta), corresponding to the main crystallographic plane of the principal unit cell.

20. The process of claim 16 further comprising the step of laser sintering the polymer composition.

21. A heat-treated polyetherketoneketone powder composition, made by the process of claim 16 .

22. A process comprising converting the heat-treated powder composition of claim 16 to an article or a coating on an article by selective laser sintering, rotomolding, or powder coating.

Assignees

• Bertelo Christopher A
• Garcia-Leiner Manuel A
• Decarmine Anthony
• Defelice Scott F
• Arkema Inc

Inventors

• Bertelo Christopher A
• Garcia-Leiner Manuel A
• Decarmine Anthony
• Defelice Scott F

Classifications

• C08L61/16 Primary

  of ketones with phenols · CPC title

• B29C39/08

  Introducing the material into the mould by centrifugal force · CPC title

• B29C64/153

  using layers of powder being selectively joined, e.g. by selective laser sintering or melting · CPC title

• C08G2650/40

  containing ketone groups, e.g. polyarylethylketones, PEEK or PEK · CPC title

• C08L71/00

  Compositions of polyethers obtained by reactions forming an ether link in the main chain (of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06); Compositions of derivatives of such polymers · CPC title