Method for manufacturing a three-dimensional object

Patent metadata

Field	Value
Publication number	US-11654615-B2
Application number	US-201816771702-A
Country	US
Kind code	B2
Filing date	Dec 19, 2018
Priority date	Dec 27, 2017
Publication date	May 23, 2023
Grant date	May 23, 2023

Abstract

A method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising a step consisting in printing layers of the 3D object from the part material comprising a polymeric component comprising, based on the total weight of the polymeric component:from 5 to 95 wt. % of at least one polymer (P1) comprising at least 50 mol. % of recurring units (R1) consisting of an arylene group comprising at least one benzene ring, each recurring unit (R1) being bound to each other through C—C bonds, wherein the recurring units (R1) are such that, based on the total number of moles of recurring units (R1):less than 90 mol. % are rigid rod-forming arylene units (R1-a), and at least 10 mol. % are kink-forming arylene units (R1-b), andfrom 5 to 95 wt. % of at least one polymer (P2), having a glass transition temperature (Tg) between 140° C. and 265° C., and no melting peak, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

First claim

The invention claimed is:

1. A method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising a step consisting in printing layers of the 3D object from a part material comprising a polymeric component comprising, based on the total weight of the polymeric component:
from 5 to 95 wt. % of at least one polymer (P1) comprising at least 50 mol. % of recurring units (R1) consisting of an arylene group comprising at least one benzene ring, each recurring unit (R1) being bound to each other through C—C bonds, wherein the recurring units (R1) are such that, based on the total number of moles of recurring units (R1):
less than 90 mol. % are arylene units (R1-a),
at least 10 mol. % are arylene units (R1-b),
wherein (R1-a) is 1,4-phenylene and (R1-b) is 1,3-phenylene; and
wherein (R1-a) and (R1-b) are substituted or unsubstituted, and

from 5 to 95 wt. % of at least one polymer (P2), having a glass transition temperature (Tg) between 140° C. and 265° C., and no melting peak, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

2. The method of claim 1 , wherein the polymeric component of the part material comprises:
from 5 to 50 wt. % of at least polymer (P1), and
from 50 to 95 wt. % of at least polymer (P2).

3. The method of claim 1 , wherein the part material also comprises up to 60 wt. %, based on the total weight of the part material, of at least one additive selected from the group consisting of fillers, colorants, lubricants, plasticizers, flame retardants, nucleating agents, flow enhancers and stabilizers.

4. The method of claim 1 , wherein P 2 is selected from the group consisting of poly(aryl ether sulfone) (PAES) and poly(ether imide) (PEI).

5. The method of claim 1 , wherein P 2 is a poly(biphenyl ether sulfone) (co)polymer (PPSU).

6. The method of claim 1 , wherein P 2 is a poly(biphenyl ether sulfone) (co)polymer (PPSU) of Mw ranging from 30,000 to 80,000 g/mol.

7. The method of claim 1 , wherein the part material is in the form of a filament or pellets.

8. The method of claim 1 , wherein the step of printing layers comprises extruding the part material.

9. The method of claim 1 , wherein P 2 is a poly(biphenyl ether sulfone) (co)polymer (PPSU) comprising at least 50 mol. % of recurring units (R PPSU ) of formula (K), the mol. % being based on the total number of moles in the polymer:

where
R, at each location, is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium; and
h, for each R, is independently zero or an integer ranging from 1 to 4.

10. A part material for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising a polymeric component comprising, based on the total weight of the polymeric component:
from 5 to 95 wt. % of at least one polymer (P1) comprising at least 50 mol. % of recurring units (R1) consisting of an arylene group comprising at least one benzene ring, each recurring unit (R1) being bound to each other through C—C bonds, wherein the recurring units (R1) are such that, based on the total number of moles of recurring units (R1):
less than 90 mol. % are arylene units (R1-a),
at least 10 mol. % are arylene units (R1-b),
wherein (R1-a) is 1,4-phenylene and (R1-b) is 1,3-phenylene; and
wherein (R1-a) and (R1-b) are substituted or unsubstituted; and

from 5 to 95 wt. % of at least one polymer (P2), having a glass transition temperature (Tg) between 140° C. and 265° C., and no melting peak, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

11. The part material of claim 10 , wherein P 2 is selected from the group consisting of poly(aryl ether sulfone) (PAES) and poly(ether imide) (PEI).

12. A process for manufacturing three-dimensional objects, comprising using a part material comprising a polymeric component comprising, based on the total weight of the polymeric component:
from 5 to 95 wt. % of at least one polymer (P1) comprising at least 50 mol. % of recurring units (R1) consisting of an arylene group comprising at least one benzene ring, each recurring unit (R1) being bound to each other through C—C bonds, wherein the recurring units (R1) are such that, based on the total number of moles of recurring units (R1):
less than 90 mol. % are arylene units (R1-a), and
at least 10 mol. % are arylene units (R1-b),
wherein (R1-a) is 1,4-phenylene and (R1-b) is 1,3-phenylene; and
wherein (R1-a) and (R1-b) are substituted or unsubstituted, and

from 5 to 95 wt. % of at least one polymer (P2), having a glass transition temperature (Tg) between 140° C. and 265° C., and no melting peak, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

13. The process of claim 12 , wherein the part material is in the form of a filament or pellets.

14. The method of claim 1 , wherein P 1 comprises at least 90 mol % of R 1 .

15. The method of claim 1 , wherein P 1 comprises at least 95 mol % of R 1 .

16. The method of claim 1 , wherein P 1 comprises at least 99 mol % of R 1 .

17. The method of claim 1 , wherein P 1 is a homopolymer consisting of 100 mol % of R 1 .

18. The method of claim 1 , wherein the arylene group is substituted by a monovalent substituting group.

19. The method of claim 18 , wherein the monovalent substituting group is selected from the group consisting of: hydrocarbylketones [—C(═O)—R, where R is a hydrocarbyl group], and hydrocarbyloxyhydrocarbylketones [—C(═O)—R 1 —O—R 2 where R 1 is a divalent hydrocarbon group and R 2 is a hydrocarbon group].

20. The method of claim 1 , wherein P 2 is a poly(biphenyl ether sulfone) (PPSU) comprising at least 50 mol % of recurring units (R PPSU ) of formula (L″):

21. The method of claim 1 , wherein P 2 is a poly(biphenyl ether sulfone) (PPSU) comprising at least 95 mol % of recurring units (R PPSU ) of formula (L″):

22. The method of claim 1 , wherein P 2 is a poly(biphenyl ether sulfone) (PPSU) comprising at least 99 mol % of recurring units (R PPSU ) of formula (L″):

23. The part material of claim 10 , wherein P 1 comprises at least 90 mol % of R 1 .

24. The part material of claim 10 , wherein P 1 comprises at least 95 mol % of R 1 .

25. The part material of claim 10 , wherein P 1 comprises at least 99 mol % of R 1 .

26. The part material of claim 10 , wherein P 1 is a homopolymer consisting of 100 mol % of R 1 .

27. The part material of claim 10 , wherein the arylene group is substituted by a monovalent substituting group.

28. The part material of claim 27 , wherein the monovalent substituting group is selected from the group consisting of: hydrocarbylketones [—C(═O)—R, where R is a hydrocarbyl group], and

Assignees

• Solvay Specialty Polymers Usa

Inventors

• Jeol Stéphane
• Singletary Nancy J
• Hammonds Ryan
• Van Hai
• Thomas David B

Classifications

• C08L65/02

  Polyphenylenes · CPC title

• B33Y80/00

  Products made by additive manufacturing · CPC title

• B33Y70/10

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title

• C08G2261/312

  Non-condensed aromatic systems, e.g. benzene · CPC title

• B29C64/118 Primary

  using filamentary material being melted, e.g. fused deposition modelling [FDM] · CPC title