Method of making a three-dimensional object using a poly(ether ether ketone) polymeric component

Patent metadata

Field	Value
Publication number	US-11453774-B2
Application number	US-201816607149-A
Country	US
Kind code	B2
Filing date	Mar 30, 2018
Priority date	Apr 25, 2017
Publication date	Sep 27, 2022
Grant date	Sep 27, 2022

Abstract

The present disclosure relates to method of making three-dimensional (3D) objects using an additive manufacturing system wherein the part material comprises a polymeric component comprising at least one poly(ether ether ketone) polymer (PEEK) having a weight average molecular weight (Mw) ranging from 75,000 to 100,000 g/mol (as determined by GPC), for example in the form of filaments or spherical particles, for use in additive manufacturing systems to print 3D objects.

First claim

The invention claimed is:

1. A method of making a three-dimensional (3D) object, comprising extruding a part material to print layers of the 3D object, wherein the part material comprises a polymeric component selected from the group consisting of:
i) at least one poly(ether ether ketone) polymer (PEEK) having a weight average molecular weight (Mw) ranging from 75,000 to 100,000 g/mol (as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C., with polystyrene standards), and
ii) at least two PEEK polymers having different Mw, the blend thereof having a weight average molecular weight (Mw) ranging from 75,000 to 100,000 g/mol (as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C., with polystyrene standards),
wherein the term PEEK polymer denotes any polymer comprising at least 95 mol. % of recurring units (R PEEK ) of formula (J-A), based on the total

number of moles in the polymer:

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

2. The method of claim 1 , wherein the part material further comprises up to 30 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 enhancer and stabilizers.

3. The method of claim 1 , wherein the part material a further comprises up to 30 wt. %, based on the total weight of the part material, of at least one additive selected from the group consisting of hydroxyapatite, α-tricalcium phosphate (α-TCP), β-TCP and barium sulfate (BaSO 4 ).

4. The method of claim 1 , wherein the polymeric component of the part material comprises at least 80 wt. % of PEEK polymer(s), based on the total weight of polymeric component of the part material.

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

6. The method of claim 1 , wherein the PEEK polymer(s) comprises at least 95 mol. % of the recurring units are recurring units (R PEEK ) of formula (J″-A):

the mol. % being based on the total number of moles in the polymer.

7. The method of claim 1 , wherein the part material comprises a polymeric component comprising:
ii1) a PEEK polymer having a Mw ranging from 50,000 to 85,000 g/mol, and
ii2) a PEEK polymer having a Mw ranging from 85,000 to 120,000 g/mol,
as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C., with polystyrene standards.

8. The method of claim 7 , wherein the part material comprises a polymeric component comprising:
ii1) from 10 to 60 wt. % of a PEEK polymer having a Mw ranging from 50,000 to 85,000 g/mol, and
ii2) from 40 to 90 wt. % of a PEEK polymer having a Mw ranging from 85,000 to 120,000 g/mol,
as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C., with polystyrene standards.

9. A filament material for its use in 3D printing having a cylindrical geometry and a diameter comprised between 0.5 and 5 mm±0.15 mm, said filament material comprising a polymeric component selected from the group consisting of:
i) at least one poly(ether ether ketone) polymer (PEEK) having a weight average molecular weight (Mw) ranging from 75,000 to 100,000 g/mol (as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C., with polystyrene standards), and
ii) at least two PEEK polymers having different Mw, the blend thereof having a weight average molecular weight (Mw) ranging from 75,000 to 100,000 g/mol (as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C., with polystyrene standards),
wherein the term PEEK polymer denotes any polymer comprising at least 95 mol. % of recurring units (R PEEK ) of formula (J-A), based on the total number

of moles in the polymer:

where
R′, at each location, is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sultanate, alkyl sultanate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
J′, for each R′, is independently zero or an integer ranging from 1 to 4;
wherein the polymeric component comprises at least 80 wt. % of the PEEK polymer(s), based on the total weight of polymeric component of the filament.

10. The filament material of claim 9 , further comprising from 0.1 to 30 wt. % of an additive selected from the group consisting of fillers, colorants, lubricants, plasticizers, flame retardants, nucleating agents, flow enhancers and stabilizers.

11. The filament material of claim 9 , having a diameter comprised between 1 and 3.5 mm±0.15 mm.

12. A method for the manufacture of a filament to be used in the manufacture of three-dimensional objects, comprising:
using a part material comprising a polymeric component selected from the group consisting of:
i) at least one poly(ether ether ketone) polymer (PEEK) having a weight average molecular weight (Mw) ranging from 75,000 to 100,000 g/mol (as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C., with polystyrene standards), and
ii) at least two PEEK polymers having different Mw, the blend thereof having a Mw ranging from 75,000 to 100,000 g/mol (as determined by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C., with polystyrene standards),
wherein the term PEEK polymer denotes any polymer comprising at least 95 mol. % of recurring units (R PEEK ) of formula (J-A), based on the total number of moles in the polymer:

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

13. The method of claim 12 , wherein the filament has a cylindrical geometry and a diameter comprised between 0.5 and 5 mm±0.15 mm.

14. The method of claim 5 , wherein the filament has a cylindrical geometry and a diameter comprised between 0.5 and 5 mm±0.15 mm.

15. The method of claim 14 , wherein the filament has a diameter comprised between 1 and 3.5 mm±0.15 mm.

16. The filament material of claim 9 , wherein the PEEK polymer(s) comprises at least 95 mol. % of the recurring units are recurring units (R PEEK ) of formula (J″-A):

Assignees

• Solvay Specialty Polymers Usa

Inventors

• Jeol Stéphane
• Singletary Nancy J
• Van Hai
• Hicks James Brown

Classifications

• B29K2071/00

  Use of polyethers {, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof}, as moulding material · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B29C64/314

  Preparation · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title