Aliphatic polyester resin powder suitable for selective laser sintering and its preparation method

Patent metadata

Field	Value
Publication number	US-10787546-B2
Application number	US-201815953062-A
Country	US
Kind code	B2
Filing date	Apr 13, 2018
Priority date	Oct 13, 2015
Publication date	Sep 29, 2020
Grant date	Sep 29, 2020

Abstract

The crystalline aliphatic polyester resin powder obtained has good antioxidant property, good powder flowability, moderate size, smooth surface, suitable bulk density, and suitable dispersibility and particle size distribution. The aliphatic polyester resin powder is particularly suitable for selective laser sintering method.

First claim

The invention claimed is:

1. A method for preparing an aliphatic polyester resin powder, comprising:
a) heat dissolving a crystalline aliphatic polyester resin in an organic solvent to obtain an aliphatic polyester resin solution, wherein the crystalline aliphatic polyester is selected from polyesters formed by polymerizing C 4 -C 12 aliphatic dicarboxylic acids and C 2 -C 10 aliphatic diols, polyesters formed by polymerizing alpha-hydroxy C 2 -C 6 carboxylic acids, polycaprolactone, and mixtures thereof;
b) cooling the aliphatic polyester resin solution to precipitate a solid, thereby obtaining a solid-liquid mixture;
c) optionally adding an adjuvant to the solid-liquid mixture; and
d) conducting solid-liquid separation and drying to obtain an aliphatic polyester resin powder;
wherein the organic solvent is a ketone or a cyclic ether, and
has a solubility in the range of 10.0-25.0 MPa 0.5 and a boiling point not higher than 160° C. under atmospheric pressure.

2. The method according to claim 1 , wherein the crystalline aliphatic polyester is selected from polyesters formed by polymerizing C 4 -C 12 aliphatic dicarboxylic acids and C 2 -C 10 aliphatic diols.

3. The method according to claim 1 , wherein the crystalline aliphatic polyester is selected from crystalline polylactic acid, polyglycolide, poly(DL-lactide-co-glycolide), polyethylene succinate, polybutylene succinate, polybutylene adipate, polybutylene succinate/adipate copolymer, polycaprolactone, and mixtures thereof.

4. The method according to claim 1 , wherein the aliphatic polyester is a crystalline polylactic acid, or a mixture of L-polylactic acid resin and D-polylactic acid resin.

5. The method according to claim 1 , wherein the organic solvent is selected from C 3 -C 10 ketone solvents, C 3 -C 10 cyclic ether solvents, C 3 -C 5 ketone solvents, and C 3 -C 5 cyclic ether solvents, acetone, butanone, 2-pentanone, 3-pentanone, cyclopentanone, methylisopropyl ketone, tetrahydrofuran, dioxane, dioxolane, and mixtures thereof.

6. The method according to claim 1 , wherein the organic solvent is in an amount of 600 to 1200 parts by weight, based on 100 parts by weight of the aliphatic polyester resin.

7. The method according to claim 1 , which is characterized in that, in step a), the aliphatic polyester resin is maintained at a temperature of 60-200° C. for 30-90 minutes.

8. The method according to claim 1 , wherein, in step b), the crystalline aliphatic polyester resin solution is cooled down to a target temperature at an average cooling rate of 0.1° C./min to 1° C./min.

9. The method according to claim 1 , wherein, in step b), the crystalline aliphatic polyester resin solution is cooled to a target temperature via one or more intermediate temperatures in the range of 40-100° C. and held at said one or more intermediate temperatures for 30-90 minutes.

10. The method according to claim 1 , further comprising adding a nucleating agent in the aliphatic polyester resin solution in step a), wherein the nucleating agent is selected from silica, calcium oxide, calcium carbonate, barium sulfate, hydrotalcite, talc, carbon black, kaolin, mica, and mixtures thereof.

11. The method according to claim 10 , wherein the nucleating agent is in an amount of 0.01-2 parts by weight, based on 100 parts by weight of the crystalline aliphatic polyester resin.

12. The method according to claim 1 , wherein the adjuvant in step c) is selected from antioxidants, powder release agents, antistatic agents, antibacterial agents, and glass fiber reinforcements.

13. The method according to claim 12 , wherein the adjuvant is antioxidant 1010 , antioxidant 168, or a mixture thereof, and the adjuvant is in an amount of 0.1-0.5 parts by weight, based on 100 parts by weight of the crystalline aliphatic polyester resin.

14. The method according to claim 12 , wherein the adjuvant is a powder release agent selected from an alkali or alkaline earth metal based on alkane monocarboxylic or dimer acids, a nano-oxide, a nano-metal salt, sodium stearate, potassium stearate, zinc stearate, calcium stearate, lead stearate, silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, calcium carbonate, barium sulfate, and mixtures thereof; and the powder release agent is in an amount of 0.01-10 parts by weight, based on 100 parts by weight of the crystalline aliphatic polyester resin.

15. A crystalline aliphatic polyester resin powder prepared by the method according to claim 1 , having a particle shape of spherical and/or spheroidal, a particle size of 25-150 μm, and a particle size distribution in which D10=24-64 μm, D50=48-95 μm, and D90=71-128 μm.

16. A selective laser sintering method, comprising sintering the crystalline aliphatic polyester resin powder prepared by the method according to claim 1 .

17. A method of manufacturing a three-dimensional object, comprising selective laser sintering the crystalline aliphatic polyester resin powder prepared by the method according to claim 1 .

18. The method according to claim 1 , wherein the ketone or the cyclic ether has a solubility in the range of 14.5-23.0 MPa 0.5 and a boiling point not higher than 150° C. under atmospheric pressure.

19. The method according to claim 1 , wherein the ketone or the cyclic ether has a solubility in the range of 18.5-20.5 MPa 0.5 and a boiling point not higher than 100° C. under atmospheric pressure.

20. The method according to claim 4 , wherein a weight ratio between L-polylactic acid resin and D-polylactic acid resin in the mixture is about 1:1.

21. The method according to claim 5 , wherein the organic solvent is selected from acetone, butanone, 2-pentanone, 3-pentanone, cyclopentanone, methylisopropyl ketone, tetrahydrofuran, dioxane, dioxolane, and mixtures thereof.

22. The method according to claim 6 , wherein the organic solvent is in the amount of 800 to 1000 parts by weight.

23. The method of claim 7 , wherein the aliphatic polyester resin is maintained at a temperature of 70-190° C.

24. The method of claim 7 , wherein the aliphatic polyester resin is maintained at a temperature of 80-160° C.

25. The method according to claim 8 , wherein, in step b), the crystalline aliphatic polyester resin solution is held for 30-90 minutes at the target temperature of 10-30° C.

26. The method according to claim 9 , wherein said one or more intermediate temperatures are in the range of 50-90° C.

27. The method according to claim 11 , wherein the amount of the nucleating agent is 0.1-0.5 parts by weight.

28. The method of claim 12 , wherein the amount of the adjuvant is 0.2-0.4 parts by weight.

29. The method of claim 14 , wherein the amount of the powder release agent is 0.1-5 parts by weight.

30. The method of claim 14 , wherein the amount of the powder release agent is 0.5-1 parts by weight.

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp

Inventors

• Liu Jianye
• Chu Liqiu
• Lyu Yun
• Zhang Shijun
• Zhang Liying
• Zou Hao
• Dong Mu
• Gao Dali
• Chou Baige
• Bai Yiqing
• Shao Jingbo
• Xu Meng
• Xu Yihui
• Chen Ruoshi

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08G63/88

  Post-polymerisation treatment · CPC title

• C08J3/212

  and solid additives · CPC title

• B29C67/00

  Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 · CPC title

• C08L67/04

  Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C08L67/06 takes precedence) · CPC title