Semicrystalline pulverulent polyarylethersulfones and method to make them
A semicrystalline polyarylethersulfone (PAES) useful for additive manufacturing may be made by a method comprising: dissolving an amorphous polyarylethersulfone in a polar aprotic halogenated hydrocarbon solvent at a temperature adequate to effectively form a solution, and subsequently and spontaneously bring about reprecipitation of a semicrystalline polyarylethersulfone from the solution. The semicrystalline polyarylethersulfone may have a crystallinity of at least 30% by weight. The semicrystalline PAES, upon being heated, melting and uniting together in layers during additive manufacturing cools without substantially recrystallizing, allows for deformation-free articles to be formed having low residual stress.
1. A method of forming a semicrystalline polyarylethersulfone comprising:
(i) dissolving an initial polyarylethersulfone that is amorphous or has a crystallinity of less than about 30% by weight in a polar aprotic halogenated hydrocarbon solvent at a temperature to form a solution with dissolved polyarylethersulfone, and
(ii) precipitating spontaneously the dissolved polyarylethersulfone from the solution to form the semicrystalline polyarylethersulfone, wherein, when the initial polyarylethersulfone is amorphous the semicrystalline polyarylethersulfone has a crystallinity of at least about 10% to about 100% and when the initial polyarylethersulfone has a crystallinity of less than 30%, the crystallinity of the semicrystalline polyarylethersulfone is at least about 20% greater than the crystallinity of the initial polyarylethersulfone.
2. The method of claim 1 , wherein the temperature is about the same throughout the method.
3. The method of either claim 2 , wherein the temperature is held within +5° C.
4. The method of claim 1 , wherein the temperature is from about 20° C. to about 60° C.
5. The method of claim 1 , wherein the solvent is comprised of a halogenated hydrocarbon having from 1 to 3 carbons.
6. The method of claim 5 , wherein the solvent is comprised of dichloromethane.
7. The method of claim 1 , wherein the dissolving and precipitating is performed at ambient conditions.
8. The method of claim 1 , wherein the initial polyarylethersulfone has a crystallinity of at most 15% by weight.
9. The method of claim 1 , wherein the initial polyarylethersulfone is amorphous.
10. The method of claim 1 , wherein the initial polyarylethersulfone is comprised of one represented by:
wherein n is an integer value such that the polarylethersulfone has a weight average molecular weight of about 30 to 200 kDa, m is from 0 to 10, R 1 is an aryl group having from 5 to 10 carbons, R 2 in each occurrence is independently C 1 -C 20 alkyl, C 5 -C 18 aryl or fused ring of 5-10 carbon atoms.
11. The method of claim 10 , wherein —R 1 —S(═O) 2 —R 1 — is represented by:
12. The method of claim 1 , wherein the semicrystalline polyarylethersulfone has a crystallinity of greater than 30% to 60% by weight.
13. The method of claim 10 , wherein the initial polyarylethersulfone is comprised of one or more of a polyethersulfone, poly (1,4-phenylene-ether-ether-sulfone, polyphenylenesulfone, and poly (bisphenol-A-sulfone).
14. A method of forming a semicrystalline polyarylethersulfone comprising:
(i) dissolving an initial polyarylethersulfone that is amorphous or has a crystallinity of less than about 30% by weight in a polar aprotic halogenated hydrocarbon solvent at a temperature to form a solution with dissolved polyarylethersulfone, and
(ii) precipitating by cooling the dissolved polyarylethersulfone from the solution to form the semicrystalline polyarylethersulfone, wherein, when the initial polyarylethersulfone is amorphous the semicrystalline polyarylethersulfone has a crystallinity of at least about 10% to about 100% and when the initial polyarylethersulfone has a crystallinity of less than 30%, the crystallinity of the semicrystalline polyarylethersulfone is at least about 20% greater than the crystallinity of the initial polyarylethersulfone.
15. The method of claim 14 , wherein the temperature is from about 20° C. to about 60° C.
16. The method of claim 15 , wherein the cooling does not exceed cooling arising from allowing the solution to cool under ambient conditions.
17. The method of claim 14 , wherein the initial polyarylethersulfone is amorphous.
18. The method of claim 16 , wherein the initial polyarylethersulfone is comprised of one represented by:
wherein n is an integer value such that the polarylethersulfone has a weight average molecular weight of about 30 to 200 kDa, m is from 0 to 10, R 1 is an aryl group having from 5 to 10 carbons, R 2 in each occurrence is independently C 1 -C 20 alkyl, C 5 - C 18 aryl or fused ring of 5-10 carbon atoms.
19. The method of claim 18 , wherein —R 1 —S (=O) 2 -R 1 — is represented by:
20. The method of claim 18 , wherein the initial polyarylethersulfone is comprised of one or more of polyethersulfone, poly (1,4-phenylene-ether-ether-sulfone, polyphenylenesulfone, and poly (bisphenol-A-sulfone).