Process for the production of fibers from poly(etheretherketone)-type polymers

• US 4,904,426 A
• Filed: 03/31/1988
• Issued: 02/27/1990
• Est. Priority Date: 03/31/1988
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Lundgard, Richard A., Beck, Henry N.
• Primary Examiner(s): Lorin, Hubert C.
• Application Number:
  US07/175,716
• Time in Patent Office: 698 Days
• Field of Search: 528/491, 528/480, 528/125, 528/126, 528/128, 264/41, 264/184, 264/203, 264/209.1, 264/211.14, 264/211.16, 264/211.19, 210/500.23, 210/500.28, 210/500.21, 210/500.27
• US Class Current: 264/41
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 67/0009 by phase separation, sol-gel transition, evaporation or solvent quenching
• CPC Class Codes: B01D 67/003 by selective elimination of components, e.g. by leaching
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 71/5222 Polyetherketone, polyetheretherketone, or polyaryletherketone
• CPC Class Codes: C08J 2371/00 Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
• CPC Class Codes: C08J 3/091 characterised by the chemical constitution of the organic liquid
• CPC Class Codes: D01D 5/247 Discontinuous hollow structure or microporous structure
• CPC Class Codes: D01F 6/665 from polyetherketones, e.g. PEEK

Abstract

A process for preparing microporous poly(etheretherketone)-type fibers comprising forming an extrusion mixture of at least one unsulphonated poly(etheretherketone)-type polymer and a solvent comprising at least one organic compound consisting predominantly of carbon and hydrogen, wherein the organic compound has a molecular weight of between about 160 and 450, contains at least one six membered aromatic ring structure, possesses a boiling point of between about 240 and 480 degrees Celsius, and is capable of dissolving at least about 10 weight percent of the poly(etheretherketone)-type polymer present at the extrusion temperature, extruding to form solid or hollow fibers, conveying the fibers through at least one quench zone, conveying the fibers through at least one leach zone, and drying the fibers, wherein the fibers so formed possess interconnecting or non-interconnecting pores.

Claims

1. A process for preparing microporous poly(etheretherketone)-type fibers, comprising

A. forming an extrusion mixture of

(1.) at least one unsulfonated poly(etheretherketone)-type polymer,

(2.) a solvent comprising at least one organic compound consisting predominantly of carbon and hydrogen and optionally oxygen, nitrogen, sulfur, halogen, and mixtures thereof, wherein the organic compound has a molecular weight of between about 160 and 450, contains at least one six membered aromatic ring structure, possesses a boiling point of between about 240 and 480 degrees Celsius, and is capable of dissolving at least about 10 weight percent of the poly(etheretherketone)-type polymer present at the extrusion temperature,

B. extruding the fluid to form solid or hollow fibers;

C. conveying the fibers through at least one quench zone wherein the fibers cool and solidify;

D. conveying the fibers through at least one leach zone wherein a substantial portion of the solvent is removed; and

E. drying the fibers;

wherein the fibers so formed possess interconnecting or non-interconnecting pores.

2. The process of claim 1 wherein the pores are non-interconnecting.

3. The process of claim 2 wherein the fibers are hollow.

4. The process of claim 2 wherein the fibers are solid.

5. The process of claim 2 wherein the concentration of poly(etheretherketone)-type polymer in the extrusion mixture is between about 10 to about 90 weight percent.

6. The process of claim 5 wherein the porosity ranges from about 10 to about 90 percent.

7. The process of claim 6 wherein the pore size ranges from about 1×

10^-3 to about 3.0 microns.

8. The process of claim 2 wherein the poly(etheretherketone)-type polymer contains predominantly ether, --R--0--R--, and ketone, --R--CO--R--, linkages, wherein R is a substituted or unsubstituted phenylene of the formula:

##STR4## wherein X is independently in each occurrence hydrogen, a C_1-4 alkyl, or a halogen; and

m is an integer between and 4 inclusive.

9. The process of claim 8 wherein the poly(etheretherketone)-type polymer is selected from the group consisting of poly(etherketone) (PEK), poly(aryletherketone) (PAEK), poly(etheretherketone) (PEEK), poly(etherketoneketone) (PEKK), poly(etheretheretherketone) (PEEEK), poly(etheretherketoneketone) (PEEKK), poly(etherketoneetherketoneketone) (PEKEKK), and mixtures thereof.

10. The process of claim 9 wherein the poly(etheretherketone)-type polymer is poly(oxy-p-phenyleneoxy-p-phenylenecarbonyl-p-phenylene) (PEEK) or poly(oxy-1,4-phenylenecarbonyl-1,4-phenylene) (PEK).

11. The process of claim 2 wherein the solvent is selected from the group consisting of diphenic acid, N,N-diphenylformamide, benzil, anthracene, 1-phenylnaphthalene, 4-bromobiphenyl, 4-bromodiphenyl ether, benzophenone, 1-benzyl-2-pyrrolidinone, o,o'"'"'-biphenol, phenanthrene, triphenylmethanol, triphenylmethane, triphenylene, 1,2,3-triphenylbenzene, diphenylsulfone, 2,5-diphenyloxazole, 2-biphenylcarboxylic acid, 4-bi-phenylcarboxylic acid, m-terphenyl, 4-benzoylbiphenyl, 2-benzoylnaphthalene, 3-phenoxybenzyl alcohol, fluoranthene, 2,5-diphenyl-1,3,4-oxadiazole, 9-fluorenone, 1,2-dibenzoyl benzene, dibenzoylmethane, p-terphenyl, 4-phenylphenol, 4,4'"'"'-dibromobiphenyl, diphenyl phthalate, 2,6-diphenylphenol, phenothiazine, 4,4'"'"'-dimethoxybenzophenone, 9,10-diphenylanthracene, pentachlorophenol, pyrene, 9,9'"'"'-bifluorene, a mixture of terphenyls, a mixture of partially hydrogenated terphenyls, a mixture of terphenyls and quaterphenyls, 1-phenyl-2-pyrrolidinone, 4,4'"'"'-isopropyldenediphenol, 4,4'"'"'-dihdroxybenzphenone, quaterphenyls, and mixtures thereof.

12. The process of claim 1 wherein the extrusion mixtures contains an additional component consisting of a non-solvent comprising at least one organic compound consisting predominantly of carbon and hydrogen and optionally oxygen, phosphorus, silicon, nitrogen, sulfur, halogen, and mixtures thereof, wherein the organic compound has a molecular weight of between about 120 and 455, possesses a boiling point of between about 240 and 480 degrees Celsius, and dissolves less than about 10 weight percent of the poly(etheretherketone)-type polymer present at the extrusion temperature, wherein the non-solvent is substantially removed in the leach zone along with the solvent.

13. The process of claim 12 wherein the pores are interconnecting.

14. The process of claim 13 wherein the fibers are hollow.

15. The process of claim 13 wherein the fibers are solid.

16. The process of claim 13 wherein the poly(etheretherketone)-type polymer contains predominantly ether, --R--0--R--, and ketone, --R--CO--R--, linkages, wherein R is a substituted or unsubstituted phenylene of the formula:

##STR5## wherein X is independently in each occurrence hydrogen, a C_1-4 alkyl, or a halogen; and

m is an integer between 0 and 4 inclusive.

17. The process of claim 16 wherein the poly(etheretherketone)-type polymer is selected from the group consisting of poly(etherketone) (PEK), poly(aryletherketone) (PAEK), poly(etheretherketone) (PEEK), poly(etherketoneketone) (PEKK), poly(etheretheretherketone) (PEEEK), poly(etheretherketoneketone) (PEEKK), poly(etherketoneetherketoneketone) (PEKEKK), and mixtures thereof.

18. The process of claim 17 wherein the poly(etheretherketone)-type polymer is poly(oxy-p-phenyleneoxy-p-phenylenecarbonyl-p-phenylene) (PEEK) or poly(oxy-1,4-phenylenecarbonyl-1,4-phenylene) (PEK).

19. The process of claim 12 wherein the non-solvent is selected from the group consisting of 1,3,5-triphenylbenzene, tetraphenylmethane, tetraphenylsilane, diphenylsulfoxide, 1,1-diphenylacetone, 1,3-diphenylacetone, 4-acetylbiphenyl, 4,4'"'"'-diphenylbenzophenone, 1-benzoyl-4-piperidone, diphenyl carbonate, bibenzyl, diphenylmethylphosphate, 1-bromonapthalene, 2-phenoxybiphenyl, triphenylphosphate, cyclohexylphenylketone, 1,4-dibenzoylbutane, 2,4,6-trichlorophenol, mineral oil, paraffin oil, petroleum oil, butyl stearate, 9-phenylanthracene, 2-phenylphenol, 1-ethoxynaphthalene, phenyl benzoate, 1-phenyldecane, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,3-diphenoxybenzene, 1,8-dichloroanthraquinone, 9,10-dichloro-anthracene, polyphosphoric acid, 1-chloronaphthalene, diphenyl ether, 1-cyclohexyl-2-pyrrolidinone, hydrogenated terphenyl, dioctyl phthalate, 5-chloro-2-benzoxazolone, dibenzothiophene, diphenyl sulfide, diphenyl chlorophosphate, fluorene, sulfolane, methyl myristate, methyl stearate, hexadecane, dimethyl phthalate, tetraethylene glycol dimethyl ether, diethylene glycol dibutyl ether, docosane, eicosane, dotriacontane, 2,7-dimethoxynaphthalene, 2,6-dimethoxynaphthalene, o-terphenyl, 1,1-diphenylethylene, epsilon-caprolactam, thianthrene, silicone oil, and mixtures thereof.

20. The process of claim 13 wherein the concentration of poly(etheretherketone)-type polymer in the extrusion mixture is between about 20 to about 70 weight percent.

21. The process of claim 20 wherein the fibers have a porosity of between about 20 to about 70 percent.

22. The process of claim 21 wherein the fibers have an average pore size of between about 1×

10^-3 and about 3.0 microns.

23. The process of claim 13 wherein the solvent/non-solvent ratio in the extrusion mixture is between about 0.05 to about 24.

24. The process of claim 14 wherein the fibers have a molecular weight cut-off based on a particle size for ultrafiltration in the range of about 10 to 500 Angstroms and a molecular weight cut-off based on a particle size for microfiltration in the range of about 0.05 to 7.0 microns.