Method of making a shaped article comprising printing layers of a polymer composition comprising at least one PEEK-PEmEK copolymer

Patent metadata

Field	Value
Publication number	US-11267938-B2
Application number	US-201816771697-A
Country	US
Kind code	B2
Filing date	Dec 20, 2018
Priority date	Dec 20, 2017
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

A method of making a shaped article comprising printing layers of a polymer composition comprising at least one PEEK-PEmEK copolymer having RPEEK and RPEmEK repeat units in a molar ratio RPEEK/RPEmEK ranging from 95/5 to 45/55, the polymer composition optionally including at least one reinforcing filler, at least one additive, or a combination thereof, and shaped articles obtained from the method. Also described are methods of making the PEEK-PEmEK copolymer and methods of making the polymer composition.

First claim

The invention claimed is:

1. A method of making a shaped article comprising printing layers of a polymer composition comprising at least one PEEK-PEmEK copolymer comprising at least 50 mol %, collectively, of repeat units (R PEEK ) and repeat units (R PEmEK ), relative to the total number of repeat units in the PEEK-PEmEK copolymer, wherein :
(a) repeat units (R PEEK ) are repeat units of formula :

and
(b) repeat units (R PEmEK ) are repeat units of formula (B) :

wherein :
each R 1 and R 2 , equal to or different from each other, is independently at each occurrence 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, each a and b is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEmEK copolymer includes the repeat units R PEEK and R PEmEK in a molar ratio R PEEK /R PEmEK ranging from 95/5 to 45/55.

2. The method of claim 1 , wherein the repeat units (R PEEK ) are repeat units of formula :

3. The method of claim 2 , wherein the repeat units (R PEmEK ) are repeat units of formula :

4. The method of claim 1 , wherein the PEEK-PEmEK copolymer exhibits a heat of fusion (ΔH) ranging from 1 J/g to 65 J/g, wherein the heat of fusion (ΔH) is determined as the area under the melting endotherm on the second heat scan in a differential scanning calorimeter (DSC) according to ASTM D3418-03 and E793-06, and using heating and cooling rates of 20° C/min.

5. The method of claim 4 , wherein the PEEK-PEmEK copolymer meets the following inequality :
Δ H≥− 0.0005(Tm) 2 +1.008(Tm)−226.33

wherein :
ΔH is the heat of fusion of PEEK-PEmEK copolymer in J/g, and Tm is the melting temperature of the PEEK-PEmEK copolymer in ° C. measured as the peak temperature of the melting endotherm on the second heat scan in a differential scanning calorimeter (DSC) according to ASTM D3418-03 and E794-06 and using heating and cooling rates of 20° C/min.

6. The method of claim 1 , wherein the polymer composition comprises at least one of a reinforcing filler, an additive, or a combination thereof.

7. The method of claim 1 , wherein the composition comprises at least 10 wt. % of PEEK-PEmEK copolymer, based on the total weight of the polymer composition.

8. The method of claim 1 , wherein the polymer composition comprises the at least one reinforcing filler selected from the group consisting of a glass fiber, a carbon fiber, and a combination thereof.

9. The method of claim 1 , by an extrusion-based additive manufacturing system, a powder-based additive manufacturing system or a continuous Fiber-Reinforced Thermosplastic (FRTP) printing method.

10. A shaped article obtained by the method of claim 1 .

11. A filament for making a shaped article by printing layers of the article, the filament being made of a polymer composition comprising at least one PEEK-PEmEK copolymer comprising at least 50 mol. %, collectively, of repeat units (R PEEK ) and repeat units (R PEmEK ), relative to the total number of repeat units in the PEEK-PEmEK copolymer, wherein:
(a) repeat units (R PEEK ) are repeat units of formula:

and
(b) repeat units (R PEmEK ) are repeat units of formula (B):

wherein:
each R 1 and R 2 , equal to or different from each other, is independently at each occurrence 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,
each a and b is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEmEK copolymer includes the repeat units R PEEK and R PEmEK in a molar ratio R PEEK /R PEmEK ranging from 95/5 to 45/55.

12. The filament of claim 11 , having a cylindrical geometry and a diameter ranging from 0.5 to 5 mm.

13. A powder for making a shaped article by printing layers of the article, the powder being made of a polymer composition comprising at least one PEEK-PEmEK copolymer comprising at least 50 mol. %, collectively, of repeat units (R PEEK ) and repeat units (R PEmEK ), relative to the total number of repeat units in the PEEK-PEmEK copolymer, wherein:
(a) repeat units (R PEEK ) are repeat units of formula:

and
(b) repeat units (R PEmEK ) are repeat units of formula (B):

wherein:
each R 1 and R 2 , equal to or different from each other, is independently at each occurrence 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,
each a and b is independently selected from the group consisting of integers ranging from 0 to 4, and
the PEEK-PEmEK copolymer includes the repeat units R PEEK and R PEmEK in a molar ratio R PEEK /R PEmEK ranging from 95/5 to 45/55.

14. The powder of claim 13 , having an average diameter (d 50 ) ranging from 1 to 200 μm, as measured by electron microscopy or laser scattering.

15. A process for the manufacture of a shaped article by printing layers of the article using the filaments of claim 11 in a 3D printer.

16. A process for the manufacture of a shaped article by printing layers of the article using the powder of claim 13 in a 3D printer.

17. The method of claim 3 , wherein the PEEK-PEmEK copolymer comprises at least 95 mol %, collectively, of the repeat units (R PEEK ) and the repeat units (R PEmEK ), relative to the total number of repeat units in the PEEK-PEmEK copolymer.

18. The method of claim 3 , wherein the PEEK-PEmEK copolymer comprises at least 99 mol %, collectively, of the repeat units (R PEEK ) and the repeat units (R PEmEK ), relative to the total number of repeat units in the PEEK-PEmEK copolymer.

19. The filament of claim 11 , wherein the PEEK-PEmEK copolymer comprises at least 95 mol %, collectively, of the repeat units (R PEEK ) and the repeat units (R PEmEK ), relative to the total number of repeat units in the PEEK-PEmEK copolymer.

20. The powder of claim 13 , wherein the PEEK-PEmEK copolymer comprises at least 95 mol %, collectively, of the repeat units (R PEEK ) and the repeat units (R PEmEK ), relative to the total number of repeat units in the PEEK-PEmEK copolymer.

Assignees

• Solvay Specialty Polymers Usa
• Solvay Specialty Polymers Usa Inc

Inventors

• Louis Chantal
• El-Hibri Mohammad Jamal

Classifications

• C09D161/00

  Coating compositions based on condensation polymers of aldehydes or ketones (with polyalcohols C09D159/00; with polynitriles C09D177/00); Coating compositions based on derivatives of such polymers · CPC title

• C08K3/26

  Carbonates; Bicarbonates · CPC title

• C08K7/06

  Elements · CPC title

• 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

• C08K7/14

  Glass · CPC title