Fluoropolymer fibre

• US 10,364,514 B2
• Filed: 07/15/2014
• Issued: 07/30/2019
• Est. Priority Date: 07/15/2013
• Status: Expired due to Fees

• Current Assignee: Solvay SA (Solvac SA)
• Original Assignee: Solvay SA (Solvac SA)
• Inventors: Abusleme, Julio A., Besana, Giambattista, Bassi, Mattia, Hamon, Christine, Gualandi, Chiara, Focarete, Maria Letizia, Zucchelli, Andrea
• Primary Examiner(s): Mulcahy, Peter D.
• Application Number:
  US14/905,443
• Publication Number:
  US 20160160392A1
• Time in Patent Office: 1,841 Days
• CPC Class Codes: B01D 67/0079 Manufacture of membranes comprising organic and inorganic components
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 71/32 containing fluorine atoms
• CPC Class Codes: B01D 71/76 Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 rubbers in general B01D71/24
• CPC Class Codes: C08F 214/18 Monomers containing fluorine
• CPC Class Codes: D01D 5/003 the material being a polymer solution or dispersion D01D5/0053 takes precedence
• CPC Class Codes: D01D 5/0038 the fibre formed by solvent evaporation, i.e. dry electro-spinning
• CPC Class Codes: D01F 1/10 Other agents for modifying properties
• CPC Class Codes: D01F 6/32 comprising halogenated hydrocarbons as the major constituent
• CPC Class Codes: D01F 6/48 of polymers of halogenated hydrocarbons
• CPC Class Codes: D02J 1/00 Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers modifying only the surface D02J3/00
• CPC Class Codes: D04H 1/4318 Fluorine series
• CPC Class Codes: D04H 1/728 by electro-spinning electro-spinning methods and apparatus D01D5/0007
• CPC Class Codes: D10B 2321/042 polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
• CPC Class Codes: D10B 2321/08 polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
• CPC Class Codes: D10B 2401/06 Load-responsive characteristics
• CPC Class Codes: D10B 2401/061 elastic
• CPC Class Codes: D10B 2401/16 antistatic; conductive
• CPC Class Codes: D10B 2505/00 Industrial
• CPC Class Codes: D10B 2505/04 Filters
• CPC Class Codes: H01M 10/052 : Li-accumulators
• CPC Class Codes: H01M 10/0525 : Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 50/426 : Fluorocarbon polymers
• CPC Class Codes: H01M 50/44 : Fibrous material
• CPC Class Codes: H01M 50/454 : comprising a non-fibrous layer and a fibrous layer superimposed on one another
• CPC Class Codes: H01M 50/491 : Porosity
• CPC Class Codes: H01M 50/497 : Ionic conductivity
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

The present invention pertains to a process for manufacturing one or more fluoropolymer fibers, said process comprising the following steps: (i) providing a liquid composition [composition (C1)] comprising: —at least one fluoropolymer comprising at least one hydroxyl end group [polymer (F_OH)L and —a liquid medium comprising at least one organic solvent [solvent (S)]; (ii) contacting the composition (C1) provided in step (i) with at least one metal compound [compound (M)] of formula (I) here below: X_4−mAY_m (I) wherein X is a hydrocarbon group, optionally comprising one or more functional groups, m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, and Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, thereby providing a liquid composition [composition (C2)]; (iii) submitting to at least partial hydrolysis and/or polycondensation the composition (C2) provided in step (ii) thereby providing a liquid composition [composition (C3)] comprising at least one fluoropolymer hybrid organic/inorganic composite; (iv) processing the composition (C3) provided in step (iii) by electrospinning thereby providing one or more fluoropolymer fibers; (v) drying the fluoropolymer fiber(s) provided in step (iv); and (vi) optionally, submitting to compression the fluoropolymer fiber(s) provided in step (v) at a temperature comprised between 50° C. and 300° C. The invention also pertains to a process for the manufacture of said fluoropolymer fiber(s) and to uses of said fluoropolymer fiber(s) in various applications.

Claims

1. A process for manufacturing one or more fluoropolymer fibres, said process comprising:

contacting a liquid composition (C1) comprising;

at least one fluoropolymer comprising at least one hydroxyl end group [polymer (F_OH)], and

a liquid medium comprising at least one organic solvent (S);

with at least one metal compound (M) of formula (I);

X<sub>4−

m</sub>AY_m 

 

(I)

wherein X is a hydrocarbon group, optionally comprising one or more functional groups, m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, and Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, thereby providing a liquid composition (C2);

submitting composition (C2) to at least partial hydrolysis and/or polycondensation, thereby providing a liquid composition (C3) comprising at least one fluoropolymer hybrid organic/inorganic composite;

processing composition (C3) by electrospinning, thereby providing one or more fluoropolymer fibres;

drying the fluoropolymer fibre(s), thereby providing one or more dried fluoropolymer fibres; and

optionally, submitting to compression the dried fluoropolymer fibre(s) at a temperature comprised between 50°

C. and 300°

C., thereby providing compressed fluoropolymer fibres.

2. The process according to claim 1, wherein polymer (F_OH) comprises recurring units derived from at least one fluorinated monomer and at least one comonomer comprising at least one hydroxyl end group [comonomer (MA)].

3. The process according to claim 2, wherein comonomer (MA) is at least one comonomer of formula (II-A):

4. The process according to claim 1, wherein polymer (F_OH) is selected from the group consisting of:

polymers (F_OH-1) comprising recurring units derived from at least one comonomer (MA) as defined above, from at least one per(halo)fluoromonomer selected from tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE), and from at least one hydrogenated monomer selected from ethylene, propylene and isobutylene, optionally containing one or more additional comonomers; and

polymers (F_OH-2) comprising recurring units derived from at least one comonomer (MA) as defined above, from vinylidene fluoride (VDF), and, optionally, from one or more fluorinated monomers different from VDF.

5. The process according to claim 1, wherein composition (C2) is obtainable by reacting at least a fraction of the hydroxyl group(s) of the polymer(s) (F_OH) with at least a fraction of the hydrolysable group(s) Y of the compound(s) (M), said composition (C2) comprising:

at least one grafted fluoropolymer [polymer (Fg)] comprising pendant groups of formula -AY<sub>m−

1</sub>X<sub>4−

m</sub>, wherein X is a hydrocarbon group, optionally comprising one or more functional groups, m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, and Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group,

a liquid medium comprising at least one organic solvent (S), and

optionally, residual amounts of at least one compound (M) of formula (I);

X<sub>4−

m</sub>AY_m 

 

(I)

wherein X is a hydrocarbon group, optionally comprising one or more functional groups, m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, and Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group.

6. The process according to claim 1, wherein the one or more fluoropolymer fibres are assembled, thereby providing either a bundle of fluoropolymer fibres or a fluoropolymer mat.

7. A fluoropolymer fibre obtainable by the process according to claim 1.

9. A fluoropolymer mat obtainable by the process according to claim 1.

10. The fluoropolymer mat according to claim 9, comprising fluoropolymer fibres and/or bundles of fluoropolymer fibres, dried fluoropolymers fibres and/or bundles of dried fluoropolymers fibres or compressed fluoropolymers fibres and/or bundles of compressed fluoropolymers fibres as provided in claim 1.

11. The fluoropolymer mat according to claim 10, wherein said fluoropolymer mat is a non-woven fabric.

12. The fluoropolymer mat according to claim 9, wherein said fluoropolymer mat has a porosity ranging from 10% to 90%, based on the total volume of the fluoropolymer mat.

13. A multilayer assembly comprising:

at least one fluoropolymer mat according to claim 9, and

at least one substrate layer,

wherein at least one surface of said fluoropolymer mat is adhered to at least one surface of said substrate layer.

14. An electrochemical device comprising the fluoropolymer mat according to claim 9.

15. A filtration membrane comprising the fluoropolymer mat according to claim 9.

16. An electrochemical device comprising the multilayer assembly according to claim 13.

17. A filtration membrane comprising the multilayer assembly according to claim 13.

18. The fluoropolymer mat according to claim 12, wherein said fluoropolymer mat has a porosity ranging from 50% to 70%, based on the total volume of the fluoropolymer mat.

8. A fluoropolymer fibre comprising:

at least one fluoropolymer hybrid organic-inorganic composite comprising fluoropolymer domains consisting of chains obtainable by the polymer (Fg) and inorganic domains consisting of residues obtainable by the compound (M),

optionally, at least one compound (M) of formula (I);

X<sub>4−

m</sub>AY_m 

 

(I)

wherein X is a hydrocarbon group, optionally comprising one or more functional groups, m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, and Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, and

optionally, at least one derivative obtainable by at least partial hydrolysis and/or polycondensation of at least one compound (M) of formula (I).

19. The fluoropolymer fibre of claim 8, wherein the fluoropolymers fibre consists of:

at least one fluoropolymer hybrid organic-inorganic composite consisting of fluoropolymer domains consisting of chains obtainable by the polymer (Fg) and inorganic domains consisting of residues obtainable by the compound (M),

optionally, at least one compound (M) of formula (I) here below;

X<sub>4−

m</sub>AY_m 

 

(I)

wherein X is a hydrocarbon group, optionally comprising one or more functional groups, m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, and Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, and

optionally, at least one derivative obtainable by at least partial hydrolysis and/or polycondensation of at least one compound (M) of formula (I).