# US 2021/0277225 A1 · Method of making a three-dimensional object using a poly(ether ether ketone) polymeric component

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- Number: US 2021/0277225 A1
- Document ID: US20210277225A1
- Status: Published application
- Kind: A1
- Application number: 16/607,149
- Filed: 2018-03-30
- Published: 2021-09-09
- Earliest claimed: 2017-04-25
- Applicants: Solvay Specialty Polymers USA, LLC
- Inventors: Stéphane JEOL; Nancy J. SINGLETARY; Hai VAN; James Brown HICKS
- Web page: https://patentgrep.com/patent/US20210277225A1

## CPC

- C08L 61/16: of ketones with phenols
- B29C 64/118: using filamentary material being melted, e.g. fused deposition modelling [FDM]
- B29C 64/314: Preparation
- B33Y 10/00: Processes of additive manufacturing
- B33Y 40/10: Pre-treatment
- B33Y 70/00: Materials specially adapted for additive manufacturing
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- C08G 65/4012: {Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones}
- C08L 71/00: Compositions of polyethers obtained by reactions forming an ether link in the main chain (of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06); Compositions of derivatives of such polymers
- B29K 2071/00: Use of polyethers {, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof}, as moulding material
- C08G 2650/40: containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2205/03: containing three or more polymers in a blend
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## 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.

## Claims

### Claim 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 PEEK polymer(s) comprises at least 95 mol. % of recurring units (RPEEK) 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.

### Claim 2 (depends on 1)

The method of claim 1, wherein the part material a se 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.

### Claim 3 (depends on 1)

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 hydroxyapatite, α-tricalcium phosphate (α-TCP), β-TCP and barium sulfate (BaSO4).

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 1)

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

### Claim 6 (depends on 1)

The method of claim 1, wherein the PEEK polymer(s) comprises at least 95 mol. % of the recurring units are recurring units (RPEEK) of formula (J-A″):
the mol. % being based on the total number of moles in the polymer.

### Claim 7 (depends on 1)

The method of claim 1, wherein the part material comprising 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.

### Claim 8 (depends on 7)

The method of claim 7, wherein the part material comprising 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.

### Claim 9

A filament material 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 PEEK polymer(s) comprises at least 95 mol. % of recurring units (RPEEK) 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.

### Claim 10 (depends on 9)

The filament material of claim 9, 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.

### Claim 11 (depends on 9)

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.

### Claim 12 (depends on 9)

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

### Claim 13

(canceled)

### Claim 14

(canceled)

### Claim 15

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 PEEK polymer(s) comprises at least 95 mol. % of recurring units (RPEEK) 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.

### Claim 16 (depends on 15)

The method of claim 15, wherein the filament has a cylindrical geometry and a diameter comprised between 0.5 and 5 mm±0.15 mm.

### Claim 17 (depends on 5)

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.

### Claim 18 (depends on 17)

The method of claim 17, wherein the filament has a diameter comprised between 1 and 3.5 mm±0.15 mm.

### Claim 19 (depends on 9)

The filament material of claim 9, wherein the PEEK polymer(s) comprises at least 95 mol. % of the recurring units are recurring units (RPEEK) of formula (J-A″):
the mol. % being based on the total number of moles in the polymer.