Fibers flash-spun from partially fluorinated polymers

• US 6,136,911 A
• Filed: 06/30/1998
• Issued: 10/24/2000
• Est. Priority Date: 01/11/1996
• Status: Expired due to Term

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Armstrong, John Edward, Shin, Hyunkook, Waggoner, James Ross
• Primary Examiner(s): Copenheaver, Blaine
• Assistant Examiner(s): RUDDOCK, ULA CORINNA
• Application Number:
  US09/101,118
• Time in Patent Office: 847 Days
• Field of Search: 442/59, 442/327, 524/463, 524/466, 524/473, 264/13, 264/205, 264/211.4
• US Class Current: 524/463
• CPC Class Codes: D01D 5/11 Flash-spinning
• CPC Class Codes: D01F 6/32 comprising halogenated hydrocarbons as the major constituent
• CPC Class Codes: D01F 6/46 of polyolefins
• CPC Class Codes: D01F 6/52 of polymers of unsaturated carboxylic acids or unsaturated esters
• CPC Class Codes: D01F 6/90 of polyamides
• CPC Class Codes: D01F 6/92 of polyesters

Abstract

A flash-spun material comprised of at least 20% partially fluorinated hydrocarbon polymers in which between 10% and 70% of the total number of hydrogen atoms in each hydrocarbon polymer are replaced by fluorine atoms. The partially fluorinated hydrocarbon polymers is preferably comprised of at least 80% by weight of polymerized monomer units selected from ethylene, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride and vinyl fluoride. The flash-spun material may be a plexifilamentary strand or a microcellular foam. Also provided is a process for producing flash-spun material from partially fluorinated hydrocarbon polymers in a solvent and a solution from which such polymers may be flash-spun.

Claims

1. A process for the production of flash-spun material comprised of at least 20% partially fluorinated hydrocarbon polymers wherein between 10% and 70% of the total number of hydrogen atoms in each of said partially fluorinated hydrocarbon polymers are replaced by fluorine atoms, which comprises the steps of:

forming a spin solution of said partially fluorinated hydrocarbon polymers in a solvent, said spin solution having a cloud point pressure of less than 50 MPa at temperatures in the range of 150°

C. to 280°

C., said solvent having an atmospheric boiling point between 0°

C. and 150°

C., and being selected from the group consisting of alcohols, ketones, acetates, carbonates, chlorinated hydrocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, perfluoroethers, and cyclic hydrocarbons having five to twelve carbon atoms, said partially fluorinated hydrocarbon polymer being selected from the group consisting of

polymers comprised of 40% to 70% by weight of polymerized monomer units of tetrafluoroethylene and 10% to 60% by weight of polymerized monomer units of ethylene,

polymers comprised of 40% to 70% by weight of polymerized monomer units of chlorotrifluoroethylene and 10% to 60% by weight of polymerized monomer units of ethylene,

polymers comprised of at least 80% by weight of a homopolymer of vinylidene fluoride,

polymers comprised of at least 80% by weight of a homopolymer of vinyl fluoride; and

spinning said spin solution at a pressure that is greater than the autogenous pressure of the spin solution into a region of substantially lower pressure and at a temperature at least 50°

C. higher than the atmospheric boiling point of the solvent.

2. The process of claim 1 wherein said spin solution is spun at a pressure below the cloud point pressure of the spin solution to form plexifilamentary film-fibril strands.

3. The process of claim 1 wherein said spin solution is spun at a pressure above the cloud point pressure of the spin solution to form a foam.

4. A flash-spun material comprised of at least 20% partially fluorinated hydrocarbon polymers wherein

between 10% and 70% of the total number of hydrogen atoms in each of said partially fluorinated hydrocarbon polymers are replaced by fluorine atoms,

between 40% and 70% by weight of said partially fluorinated hydrocarbon polymers are comprised of polymerized monomer units of tetrafluoroethylene, and

between 10% to 60% by weight of said partially fluorinated hydrocarbon polymers are comprised of polymerized monomer units of ethylene.

8. The flash-spun material of claim 4, 5, 6 or 7 wherein said flash-spun material is a plexifilamentary strand having a surface area, measured by the BET nitrogen adsorption method, greater than 2 m² /g comprising a three dimensional integral plexus of semicrystalline, polymeric, fibrous elements, said elements being coextensively aligned with the network axis and having the structural configuration of oriented film-fibrils, said film-fibrils having a mean film thickness of less than 4 microns and a median width of less than 25 microns.

9. A plexifilamentary pulp material comprised of the plexifilamentary strand of claim 8 wherein each of said film-fibrils has an average length of less than 3 mm.

10. The flash-spun material of claim 4, 5, 6 or 7 wherein said flash-spun material is a microcellular foam comprising substantially polyhedral cells of polymeric material having thin film-like cell walls with a mean thickness of less than 4 microns between adjoining cells.

5. A flash-spun material comprised of at least 20% partially fluorinated hydrocarbon polymers wherein

between 10% and 70% of the total number of hydrogen atoms in each of said partially fluorinated hydrocarbon polymers are replaced by fluorine atoms,

between 40% and 70% by weight of said partially fluorinated hydrocarbon polymers are comprised of polymerized monomer units of chlorotrifluoroethylene, and

between 10% to 60% by weight of said partially fluorinated hydrocarbon polymers are comprised of polymerized monomer units of ethylene.

6. A flash-spun material comprised of at least 20% partially fluorinated hydrocarbon polymers wherein between 10% and 70% of the total number of hydrogen atoms in each of said partially fluorinated hydrocarbon polymers are replaced by fluorine atoms, and at least 80% by weight of said partially fluorinated hydrocarbon polymers are comprised of a homopolymer of vinylidene fluoride.

7. A flash-spun material comprised of at least 20% partially fluorinated hydrocarbon polymers wherein between 10% and 70% of the total number of hydrogen atoms in each of said partially fluorinated hydrocarbon polymers are replaced by fluorine atoms, and at least 80% by weight of said partially fluorinated hydrocarbon polymers are comprised of a homopolymer of vinyl fluoride.