Polyolefin resin powder suitable for selective laser sintering and its preparation method

Patent metadata

Field	Value
Publication number	US-10920025-B2
Application number	US-201615768429-A
Country	US
Kind code	B2
Filing date	Apr 15, 2016
Priority date	Oct 13, 2015
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

Abstract

A method for preparing a polyolefin resin powder has the steps of
a) heat dissolving a polyolefin resin in an organic solvent having a solubility parameter less than or equal to the solubility parameter of the polyolefin resin to obtain a polyolefin resin solution; b) cooling the polyolefin resin solution to precipitate a solid, thereby obtaining a solid-liquid mixture; c) optionally adding an adjuvant to the solid-liquid mixture and mixing; and d) conducting solid-liquid separation and drying to obtain a polyolefin resin powder suitable for selective laser sintering.

The difference between the solubility parameters of the organic solvent and of the polyolefin resin is within 0-20% of the solubility parameter of the polyolefin resin.
The polyolefin resin powder obtained according to this method has good antioxidant property, good powder flowability, moderate size, smooth surface, suitable bulk density, and suitable dispersibility and particle size distribution.

First claim

The invention claimed is:

1. A method for preparing a polyolefin resin powder, comprising:
a) heating and dissolving a polyolefin resin in an organic solvent having a solubility parameter less than or equal to a solubility parameter of the polyolefin resin to obtain a polyolefin resin solution;
b) cooling the polyolefin resin solution to cause precipitation of 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 the separated solid to obtain a polyolefin resin powder,
wherein a difference between the solubility parameter of the organic solvent and the solubility parameter of the polyolefin resin is within 0-20% of the solubility parameter of the polyolefin resin,
wherein, in the polyolefin resin solution, an amount of the organic solvent is 600-1200 parts by weight, based on an amount of 100 parts by weight of the polyolefin resin,
wherein, in step b), the polyolefin resin solution is cooled to a target temperature via one or more intermediate temperatures and held for 30-90 minutes at each of said one or more intermediate temperatures,
wherein the one or more intermediate temperatures are in the range of 40-100° C., and
wherein the polyolefin resin powder obtained from step d) contains particles that are spherical or spheroidal particles having a particle size of 25-150 μm, and a particle size distribution D10=43-69 μm, D50=61-103 μm, and D90=85-138 μm.

2. The method according to claim 1 , wherein, in step a), the polyolefin resin is at least one selected from the group consisting of polypropylene resin, polyethylene resins, homopolypropylene resin, atactic polypropylene resin, and mixtures thereof.

3. The method according to claim 2 , wherein the homopolypropylene resin and the atactic polypropylene resin have a melt index of 20-100 g/10 min, measured at 210° C. and a load of 2.16 kg, and the polyethylene resin has a melt index of 20-100 g/10 min, measured at 190° C. and a load of 2.16 kg.

4. The method according to claim 1 , wherein the amount of the organic solvent is 800-1000 parts by weight, based on 100 parts by weight of the polyolefin resin.

5. The method according to claim 1 , wherein the organic solvent is selected from the group consisting of C 5 -C 12 alkanes, n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, n-octane, and n-nonane.

6. The method according to claim 1 , wherein, in step a), the polyolefin resin is heated to a temperature of 60-200° C. and held at said temperature for 30-90 minutes.

7. The method according to claim 1 , further comprising adding a nucleating agent to the polyolefin resin, wherein the nucleating agent is selected from the group consisting of silica, calcium oxide, calcium carbonate, barium sulfate, hydrotalcite, carbon black, kaolin, mica, and mixtures thereof.

8. The method according to claim 7 , wherein an amount of the nucleating agent is 0.01-2 parts by weight based on 100 parts by weight of the polyolefin resin.

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

10. The method according to claim 9 , wherein the antioxidant is antioxidant 1010, antioxidant 168, or a mixture thereof, wherein an amount of the antioxidant is 0.1-0.5 parts by weight based on 100 parts by weight of the polyolefin resin.

11. The method according to claim 9 , wherein the powder release agent is selected from the group consisting of an alkali metal based on alkane monocarboxylic or dimer acids, an 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 an amount of the powder release agent is 0.01-10 parts by weight based on 100 parts by weight of the polyolefin resin.

12. A polyolefin resin powder prepared by the method according to claim 1 , wherein the powder particles are spherical and/or spheroidal, and have a particle size of 25-150 μm, and a particle size distribution D10=43-69 μm, D50=61-103 μm, and D90=85-138 μm.

13. A selective laser sintering method, comprising sintering the polyolefin resin powder prepared according to the method of claim 1 using laser radiation.

14. A method of manufacturing a three-dimensional object, comprising sintering a polyolefin resin powder prepared according to the method of claim 1 .

15. The method according to claim 3 , wherein the homopolypropylene resin and the atactic polypropylene resin have a melt index of 30-80 g/10 min, measured at 210° C. and a load of 2.16 kg, and the polyethylene resin has a melt index of 30-80 g/10 min, measured at 190° C. and a load of 2.16 kg.

16. The method according to claim 6 , wherein, in step a), the polyolefin resin is heated to a temperature of 70-190° C. and held at said temperature for 30-90 minutes.

17. The method according to claim 16 , wherein, in step a), the polyolefin resin is heated to a temperature of 80-160° C. and held at said temperature for 30-90 minutes.

18. The method according to claim 8 , wherein the amount of the nucleating agent is 0.05-1 parts by weight, based on 100 parts by weight of the polyolefin resin.

19. The method according to claim 18 , wherein the amount of the nucleating agent is 0.1-0.5 parts by weight, based on 100 parts by weight of the polyolefin resin.

20. The method according to claim 10 , wherein the amount of the antioxidant is 0.2-0.4 parts by weight, based on 100 parts by weight of the polyolefin resin.

21. The method according to claim 11 , wherein the amount of the powder release agent is 0.1-5 parts by weight, based on 100 parts by weight of the polyolefin resin.

22. The method according to claim 21 , wherein the amount of the powder release agent is 0.5-1 parts by weight, based on 100 parts by weight of the polyolefin resin.

23. A method for preparing a polyolefin resin powder, comprising:
a) heating and dissolving a polyolefin resin in an organic solvent having a solubility parameter less than or equal to a solubility parameter of the polyolefin resin to obtain a polyolefin resin solution;
b) cooling the polyolefin resin solution to cause precipitation of 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 the separated solid to obtain a polyolefin resin powder,
wherein a difference between the solubility parameter of the organic solvent and the solubility parameter of the polyolefin resin is within 0-20% of the solubility parameter of the polyolefin resin,
wherein, in the polyolefin resin solution, an amount of the organic solvent is 600-1200 parts by weight, based on an amount of 100 parts by weight of the polyolefin resin, and
wherein, in step b), the polyolefin resin solution is cooled to a target temperature of 10° C.-30° C. at an average cooling rate of 0.1° C./min to 1° C./min, and is held for 30-90 minu

Assignees

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

Inventors

• Liu Jianye
• Zhang Shijun
• Chu Liqiu
• Zhang Liying
• Zou Hao
• Dong Mu
• Gao Dali
• Chou Baige
• Shao Jingbo
• Lyu Yun
• Yin Hua
• Yang Qingquan
• Li Jie
• Bai Yiqing
• Xu Yihui

Classifications

• B22F1/10

  Metallic powder containing lubricating or binding agents; Metallic powder containing organic material · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B29B13/04

  by cooling {(cooling moulded articles or half products B29C35/16)} · CPC title

• B29B13/007

  Treatment of sinter powders · CPC title

• B29B9/10

  by moulding the material, i.e. treating it in the molten state · CPC title