Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor

• US 11,136,424 B2
• Filed: 04/04/2018
• Issued: 10/05/2021
• Est. Priority Date: 04/18/2017
• Status: Active Grant

• Current Assignee: Zhejiang Hyproof Technology Co., Ltd.
• Original Assignee: Zhejiang Hyproof Technology Co., Ltd.
• Inventors: Wu, Huisheng, Yang, Ying
• Primary Examiner(s): Kopec, Mark
• Assistant Examiner(s): Thomas, Jaison P
• Application Number:
  US16/605,668
• Publication Number:
  US 20200131290A1
• Time in Patent Office: 1,280 Days
• CPC Class Codes: B32B 2250/20 All layers being fibrous or filamentary
• CPC Class Codes: B32B 2260/021 Fibrous or filamentary layer layers of natural mineral fibres or particles being impregnated in a plastic substance B32B19/02
• CPC Class Codes: B32B 2260/046 Synthetic resin
• CPC Class Codes: B32B 2262/0238 Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: B32B 2262/0246 Acrylic resin fibres
• CPC Class Codes: B32B 2262/0253 Polyolefin fibres vinyl or acrylic copolymers B32B2262/0223 or B32B2262/0246
• CPC Class Codes: B32B 2262/0261 Polyamide fibres
• CPC Class Codes: B32B 2262/0269 Aromatic polyamide fibres
• CPC Class Codes: B32B 2262/0284 Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
• CPC Class Codes: B32B 2262/106 Carbon fibres, e.g. graphite fibres
• CPC Class Codes: B32B 2264/105 Metal
• CPC Class Codes: B32B 2264/108 Carbon, e.g. graphite particles
• CPC Class Codes: B32B 2307/202 Conductive
• CPC Class Codes: B32B 2307/54 Yield strength; Tensile strength
• CPC Class Codes: B32B 2307/548 Creep
• CPC Class Codes: B32B 2307/714 Inert, i.e. inert to chemical degradation, corrosion
• CPC Class Codes: B32B 2307/718 Weight, e.g. weight per square meter
• CPC Class Codes: B32B 2307/724 Permeability to gases, adsorption
• CPC Class Codes: B32B 2307/7265 Non-permeable
• CPC Class Codes: B32B 2307/732 Dimensional properties
• CPC Class Codes: B32B 2457/18 : Fuel cells
• CPC Class Codes: B32B 3/26 : characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids foam layer B32B5/18; layer of synthetic resin characterised by fillers that create voids or cavities B32B27/205; characterised by an apertured layer
• CPC Class Codes: B32B 5/26 : another layer next to it also being fibrous or filamentary relative arrangement of fibres or filaments of different layers B32B5/12
• CPC Class Codes: B32B 7/12 : using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C08F 214/222 : with fluorinated vinyl ethers
• CPC Class Codes: C08F 214/242 : with fluorinated vinyl ethers
• CPC Class Codes: C08F 214/262 : with fluorinated vinyl ethers
• CPC Class Codes: C08F 216/1475 : Monomers containing sulfur and oxygen
• CPC Class Codes: C08F 261/06 : on to polymers of unsaturated ethers
• CPC Class Codes: C08J 2327/12 : containing fluorine atoms
• CPC Class Codes: C08J 2429/10 : Homopolymers or copolymers of unsaturated ethers C08J2435/08 takes precedence
• CPC Class Codes: C08J 5/18 : Manufacture of films or sheets
• CPC Class Codes: C08J 9/42 : with macromolecular compounds
• CPC Class Codes: C09D 127/00 : Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
• CPC Class Codes: D01D 5/0023 : the material being a polymer melt
• CPC Class Codes: D01D 5/003 : the material being a polymer solution or dispersion D01D5/0053 takes precedence
• CPC Class Codes: D01D 5/06 : Wet spinning methods D01D5/0046 takes precedence
• CPC Class Codes: D01D 5/08 : Melt spinning methods D01D5/0023 takes precedence
• CPC Class Codes: D01D 5/18 : by means of rotating spinnerets
• CPC Class Codes: D01F 6/32 : comprising halogenated hydrocarbons as the major constituent
• CPC Class Codes: D01F 6/38 : comprising unsaturated nitriles as the major constituent
• CPC Class Codes: D01F 9/22 : from polyacrylonitriles
• CPC Class Codes: D06M 17/10 : Polyurethanes polyurea

Abstract

Disclosed are a method for a preparing fluorine- and chlorine-containing conductive polymer resin, a single-side or double-side filled composite film prepared using the fluorine- and chlorine-containing conductive polymer resin, and a method for preparing the film. The fluorine- and chlorine-containing conductive polymer single-side or double-side filled composite film comprises a microporous film skeleton and the fluorine- and a chlorine-containing conductive polymer resin. The composite film is mechanically stronger, more waterproof, more impervious to water and toxic and harmful chemicals, and more moisture permeability. When applied to biochemical protective clothing, it can greatly enhance the combat effectiveness of the soldiers because it is light and more impervious to water and toxic and harmful chemicals, brings about comfort, and keeps the soldiers warm. When applied to fuel cells, it can provide better electrical properties due to its high conductivity and can allow the fuel, such as hydrogen or alcohol, to burn more completely.

Claims

1. A method for preparing a fluorine- and chlorine-containing conductive polymer resin, comprising:

adding, to a reaction vessel, 1%-20% by weight of a fluorine-containing sulfonyl fluoride liquid phase monomer which is capable of free radical polymerization, 79%-98% by weight of purified water, and 0.01%-1% by weight of a fluorine-containing surfactant, and stirring the mixture at a high speed to give a prepolymer emulsion;

introducing, into the reaction vessel, a gaseous monomer mixture of (i) one or both of tetrafluoroethylene and vinylidene fluoride and (ii) chlorotrifluoroethylene under a reaction pressure of 5 kg/cm² or more, introducing a radical initiator, and allowing the reaction to proceed at a temperature of 20-120°

C., under a reaction pressure of 5-25 kg/cm², for 15-180 min to give the reaction product which is an emulsion of a fluorine- and chlorine-containing sulfonyl fluoride polymer, wherein the fluorine-containing sulfonyl fluoride liquid phase monomer and the gaseous monomer mixture that participate in the radical polymerization are at a ratio ranging from 1;

3 to 3;

1 by weight, and the radical initiator added to the reaction vessel and the fluorine-containing sulfonyl fluoride liquid phase monomer are at a ratio ranging from 0.01% to 3.0% by weight; and

hydrolyzing the emulsion of the fluorine- and chlorine-containing sulfonyl fluoride polymer, and then condensing, washing and drying the hydrolysate to give a fluorine- and chlorine-containing conductive polymer resin.

2. The method according to claim 1, wherein the fluorine-containing sulfonyl fluoride liquid phase monomer includes one or more of CF₂═

CF—

O—

R_f—

SO₂F, CF₂═

CF—

O—

R_f1—

O—

R_f2—

SO₂F and CF₂═

CF—

CF₂—

O—

R_f3—

SO₂F, wherein R_f, R_f1, and R_f2 are fluorine-containing alkyl groups having 1 to 6 carbon atoms, and R_f3 is a fluorine-containing alkyl group having 0 to 5 carbon atoms.

3. The method according to claim 1, wherein when the fluorine- and chlorine-containing conductive polymer resin applies to batteries, the fluorine-containing sulfonyl fluoride liquid phase monomer consists of 0%-80% by weight of CF₂═

CF—

O—

CF₂CF₂—

SO₂F, 20%-99% by weight of CF₂═

CF—

O—

CF₂CF(CF₃)—

O—

CF₂CF₂—

SO₂F, 0%-20% by weight of CF₂═

CF—

CF₂—

O—

SO₂F, and 0%-80% by weight of CF₂═

CF—

CF₂—

O—

CF₂CF₂—

SO₂F.

4. The method according to claim 1, wherein when the fluorine- and chlorine-containing conductive polymer resin applies to nuclear and biochemical protective films, the fluorine-containing sulfonyl fluoride liquid phase monomer consists of 0%-80% by weight of CF₂═

CF—

O—

CF₂CF₂—

SO₂F, 0%-20% by weight of CF₂═

CF—

O—

CF₂CF(CF₃)—

O—

CF₂CF₂—

SO₂F, 20%-100% by weight of CF₂═

CF—

CF₂—

O—

SO₂F, and 0%-80% by weight of CF₂═

CF—

CF₂—

O—

CF₂CF₂—

SO₂F.

5. The method according to claim 1, wherein the fluorine-containing sulfonyl fluoride liquid phase monomer contains a fluorine-containing sulfonyl fluoride-free reagent, the ratio of the weight of which to the weight of the fluorine-containing sulfonyl fluoride monomer is less than or equal to 30%.

6. The method according to claim 5, wherein the fluorine-containing sulfonyl fluoride-free reagent includes one or more of a fluorine-containing alkyl group, a fluorine-containing alkyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, 3,3,3-trifluoropropene, and perfluoroalkylethylene.

7. The method according to claim 1, wherein the gaseous monomer mixture comprises 25%-90% by mol of tetrafluoroethylene, 0%-70% by mol of vinylidene fluoride, and 5%-50% by mol of chlorotrifluoroethylene.

8. A fluorine- and chlorine-containing conductive polymer single-side filled composite film, comprising a microporous film skeleton and the fluorine- and a chlorine-containing conductive polymer resin prepared using the method according to claim 1, wherein more than 85% by volume of the pores in a single side of the microporous film skeleton are filled with the fluorine- and chlorine-containing conductive polymer resin.

9. A method for preparing the fluorine- and chlorine-containing conductive polymer single-side filled composite film according to claim 8, comprising:

filling the pores in a single side of the microporous film skeleton with the fluorine- and chlorine-containing conductive polymer resin in a coating or immersing way to give a composite material; and

drying the composite material.

10. The method according to claim 9, wherein the ratio of the weight of the microporous film skeleton to the weight of the fluorine- and chlorine-containing conductive polymer resin ranges from 25:

75 to 75;

25.

11. The method according to claim 9, wherein the microporous film skeleton is prepared by

subjecting, to melt spinning or wet spinning, one of a hot meltable fluorine-containing, or fluorine- and chlorine-containing resin, a fluorine- and chlorine-containing conductive polymer resin, a carbon fiber precursor, polyimide, polyamide, polyester, aramid, and polyetherketone, collecting an irregular net of microporous structures, and subjecting the net to heat setting.

12. The method according to claim 9, wherein the pores in a single side of the microporous film skeleton are filled with the fluorine- and chlorine-containing conductive polymer resin and one or more of activated charcoal powder, graphite powder, graphene, and rare metal powder.

13. The method according to claim 9, wherein the weight of one or more of activated charcoal powder, graphite powder, graphene, and rare metal powder does not exceed 25% of the weight of the fluorine- and chlorine-containing conductive polymer resin.

14. The method according to claim 9, wherein an sulfonic acid or carboxylic acid equivalent weight (meq/g) of the fluorine- and chlorine-containing conductive polymer resin ranges from 400 to 1,600.

15. A fluorine- and chlorine-containing conductive polymer double-side filled composite film, comprising a microporous film skeleton and a fluorine- and chlorine-containing conductive polymer resin prepared using the method according to claim 1, wherein more than 60% by volume of the pores in two sides of the microporous film skeleton are filled with the fluorine- and chlorine-containing conductive polymer resin.

16. A method for preparing the fluorine- and chlorine-containing conductive polymer double-side filled composite film according to claim 15, comprising:

filling the pores in two sides of the microporous film skeleton with the fluorine- and chlorine-containing conductive polymer resin in a coating or immersing way to give a composite material, and drying the composite material.

17. The method according to claim 16, wherein the ratio of the weight of the microporous film skeleton to the weight of the fluorine- and chlorine-containing conductive polymer resin ranges from 5:

95 to 40;

60.

18. The method according to claim 16, wherein the microporous film skeleton is prepared by

subjecting, to melt spinning or wet spinning, one of a hot meltable fluorine-containing, or fluorine- and chlorine-containing resin, a fluorine- and chlorine-containing conductive polymer resin, a carbon fiber precursor, polyimide, polyamide, polyester, aramid, and polyetherketone, collecting an irregular net of microporous structures, and subjecting the net to heat setting.

19. The method according to claim 18, wherein the hot meltable fluorine-containing, or fluorine- and chlorine-containing resin includes one or more of hot meltable polytetrafluoroethylene copolymer, polychlorotrifluoroethylene or copolymer thereof, and polyvinylidene fluoride or copolymer thereof.

20. The method according to claim 18, wherein an acid equivalent weight (meq/g) of the fluorine- and chlorine-containing conductive polymer resin ranges from 400 to 1,500.

21. The method according to claim 16, wherein the pores in two sides of the microporous film skeleton are filled with the fluorine- and chlorine-containing conductive polymer resin and one or more of activated charcoal powder, graphite powder, graphene, and rare metal powder.

22. The method according to claim 16, wherein the weight of one or more of activated charcoal powder, graphite powder, graphene, and rare metal powder does not exceed 25% of the weight of the fluorine- and chlorine-containing conductive polymer resin.

23. The method according to claim 1, wherein the fluorine-containing sulfonyl fluoride liquid phase monomer includes one or more of CF₂═

CF—

O—

CF₂CF₂—

SO₂F, CF₂═

CF—

O—

CF₂CF(CF₃)—

O—

CF₂CF₂—

SO₂F, CF₂═

CF—

CF₂—

O—

SO₂F and CF₂═

CF—

CF₂—

O—

CF₂CF₂—

SO₂F.