CN112980118B

CN112980118B - Fluorine-containing polymer mixture for high moisture permeability and ultra-breathable microporous membrane and its application

Info

Publication number: CN112980118B
Application number: CN202110174835.9A
Authority: CN
Inventors: 吴慧生; 杨颖�; 王爽智; 马静鹏; 赵艳娇; 葛爱雄; 肖文华; 田琨; 徐芳; 王丽芳; 张剑磊; 刘宇飞; 黄嘉俊; 端木琳
Original assignee: System Engineering Center Of Jihua Group Co ltd; Zhejiang Hancheng Technology Co ltd
Current assignee: System Engineering Center Of Jihua Group Co ltd; Zhejiang Hancheng Technology Co ltd
Priority date: 2021-02-07
Filing date: 2021-02-07
Publication date: 2025-01-21
Anticipated expiration: 2041-02-07
Also published as: CN112980118A

Abstract

用于高透湿超透气微孔膜的含氟高分子混合料，由组份A、组份B、组份C和组份D组成的组合物经无剪切式混合得到，其中各组分的质量含量依次为50～90％、3～25％、0～35％、0～3％；组份A为标准比重为2.13～2.18g/m³的高分子量聚四氟乙烯均聚或共聚物分散树脂与含氟离子交换树脂的共混物，其中含氟离子交换树脂与高分子量聚四氟乙烯均聚或共聚物分散树脂的质量比为0.5～10:100；组份B为分子量小于3000、熔点在80℃以下的含氟烷基丙烯酸酯单体或含氟烷基甲基丙烯酸酯单体或二者的混合物；组份C为分子量小于8000、熔点在80℃以下的聚氨酯丙烯酸酯预聚体或无氟烷基丙烯酸酯单体或二者的混合物；组份D为高温自由基引发剂。The fluorine-containing polymer mixture for high moisture permeability and ultra-breathable microporous membrane is obtained by mixing a composition consisting of component A, component B, component C and component D by non-shear mixing, wherein the mass content of each component is 50-90%, 3-25%, 0-35% and 0-3% respectively; component A is a blend of a high molecular weight polytetrafluoroethylene homopolymer or copolymer dispersion resin with a standard specific gravity of 2.13-2.18g/ ^m3 and a fluorine-containing ion exchange resin, wherein the mass ratio of the fluorine-containing ion exchange resin to the high molecular weight polytetrafluoroethylene homopolymer or copolymer dispersion resin is 0.5-10:100; component B is a fluorine-containing alkyl acrylate monomer or a fluorine-containing alkyl methacrylate monomer or a mixture of the two with a molecular weight of less than 3000 and a melting point of less than 80°C; component C is a polyurethane acrylate prepolymer or a fluorine-free alkyl acrylate monomer or a mixture of the two with a molecular weight of less than 8000 and a melting point of less than 80°C; component D is a high-temperature free radical initiator.

Description

Fluorine-containing polymer mixture for high-moisture-permeability super-breathable microporous membrane and application thereof

Technical Field

The application belongs to the technical field of polymer membrane materials, and particularly relates to a fluorine-containing polymer mixture for a high-moisture-permeability super-breathable microporous membrane and application thereof.

Background

The fluorine-containing polymer, especially the homo-polymerization, modification or copolymerization resin of tetrafluoroethylene, has wide application in various fields such as chemical materials, mechano-electronics, aerospace, military protection, novel materials, new energy and the like.

Expanded polytetrafluoroethylene is a fluorine-containing microporous polymer material, has a high microporous structure, and has excellent physical and chemical properties, mechanical properties, waterproof and air permeability and chemical stability, and has been used for manufacturing wire and cable insulation materials, medical instruments, sealing materials, environment-friendly filtration, garment materials and the like since seventies. It is common in industry to prepare dispersion resins by polymerization or copolymerization of tetrafluoroethylene monomer of high purity (> 99.99%) by a dispersion polymerization process. The expanded fluorine-containing microporous membrane material is prepared by using tetrafluoroethylene homo-polymerization dispersion or modified resin with ultrahigh molecular weight and high crystallinity, and is prepared by paste extrusion, deoiling, unidirectional or bidirectional stretching and final shaping, but the microporous membrane is easy to be polluted by oil to lose the waterproofness, and the lubricating oil is inflammable and explosive in the deoiling process, so that the industrial potential safety hazard is easily caused. The invention disclosed in the 80 s by gol in the united states is to coat one side of an expanded polytetrafluoroethylene film with a hydrophilic polyurethane to improve the oil stain resistance of one side thereof, but the air permeability of the film is sacrificed. The invention disclosed in the 90 s by gol in the united states of america is to coat the expanded polytetrafluoroethylene film with a fluoroacrylate emulsion to improve its oil-stain resistance without sacrificing its air permeability. However, the manufacturing process of the product is too complicated, the waterproof and air permeability of the product needs to be improved, and the performance of the product still has room for improvement when the product is applied to spaceflight and navigation.

Chinese patent document CN1373792a discloses a transparent elastomer composition obtained by co-coagulation of a fluororesin fine particle emulsion having an average particle diameter of 20 to 150 nm and an elastomer particle emulsion, wherein the fluororesin fine particles are uniformly and finely dispersed in an elastomer, and since the fluororesin fine particles are uniformly and finely dispersed in the elastomer in advance, an elastomer molded article excellent in mechanical strength, abrasion resistance, transparency and the like can be provided, but such an elastomer composition cannot be expanded into a fluorine-containing microporous film because the fluororesin fine particle diameter is too small and the molecular weight is not high enough. In order to obtain the puffed fluorine-containing microporous material with high strength, the molecular weight of polytetrafluoroethylene is required to be high, the standard specific gravity of general resin is required to be 2.14-2.17, and the average particle size is required to be 180-360 nanometers.

Chinese patent document CN104437126A discloses a preparation method of a super-hydrophobic polytetrafluoroethylene microporous membrane, a membrane prepared by the method and application thereof, CN102294181A discloses a double-polytetrafluoroethylene microporous membrane, polytetrafluoroethylene, super-hydrophobic high polymer (with a number average molecular weight of 5000-250000) such as fluoroalkyl acrylate and flammable and explosive lubricating oil are adopted for mixing together to prepare the membrane, the tensile strength of the obtained membrane is lower than 20MPa, the oil resistance is low (only 3 # oil resistance), and the stain resistance and the water washing resistance of composite membrane fabric are poor.

Chinese patent document CN103158310A discloses a highly oil-repellent waterproof seamless polytetrafluoroethylene expanded plate and a preparation method thereof, wherein polytetrafluoroethylene and flammable and explosive lubricating oil are adopted for preparing a film, and then polyurethane resin coating is added for compounding, the obtained film has no air permeability and no oleophobic property (only resistant to No. 1 oil), and the composite fabric has poor moisture permeability and is uncomfortable to wear.

A preparation method of polytetrafluoroethylene waterproof moisture-permeable fabric enhanced moisture permeability disclosed in China patent document CN104760381A adopts polytetrafluoroethylene and flammable and explosive lubricating oil to prepare a film, and then a microporous polyurethane coating is added, so that the obtained film has low air permeability, no oleophobic property (only resistant to No.1 oil), poor flame retardance and is not suitable for high-end application.

Chinese patent document CN107325238A discloses a fluorine-containing super oleophobic microporous membrane and application thereof, and the microporous membrane has good air permeability, but has room for improvement on moisture permeability.

Chinese patent document CN106977640a discloses a fluorine-containing chlorine-containing conductive polymer single-sided filling composite film, which has poor air permeability and still has room for improvement in moisture permeability.

Disclosure of Invention

In order to solve at least one of the technical problems in the prior art, on one hand, the embodiment of the application discloses a fluorine-containing polymer mixture for a high moisture-penetrability super-breathable microporous membrane, which is prepared by mixing a composition consisting of a component A, a component B, a component C and a component D without shearing, wherein the mass content of each component is 50-90%, 3-25%, 0-35% and 0-3% in sequence;

The component A is a blend of high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin with standard specific gravity of 2.13-2.18 g/m ³ and fluorine-containing ion exchange resin, wherein the mass ratio of the fluorine-containing ion exchange resin to the high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin is 0.5-10:100;

The component B is a fluoroalkyl acrylate monomer or a fluoroalkyl methacrylate monomer or a mixture of the fluoroalkyl acrylate monomer and the fluoroalkyl methacrylate monomer with the molecular weight less than 3000 and the melting point below 80 ℃;

The component C is polyurethane acrylate prepolymer or fluorine-free alkyl acrylate monomer or the mixture of the polyurethane acrylate prepolymer and the fluorine-free alkyl acrylate monomer with the molecular weight of less than 8000 and the melting point of below 80 ℃;

component D is a high temperature free radical initiator.

Further, the fluorine-containing high molecular mixture for the high-moisture-permeability super-breathable microporous membrane disclosed by some embodiments is prepared from ultra-high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin, wherein the standard specific gravity of the high molecular weight polyethylene homo-or copolymer dispersion resin is 2.135-2.165 g/m ³, the melting point of the high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin is 325-350 ℃, and the fluorine-containing ion exchange resin is selected from any one of fluorine-containing anion exchange resin, fluorine-containing cation exchange resin and fluorine-containing double ion exchange resin or any combination thereof.

Some embodiments disclose fluorine-containing polymer mixtures for high moisture permeability super breathable microporous membranes, wherein the polymer side chains of the fluorine-containing ion exchange resin comprise ion exchange groups, the fluorine-containing ion exchange resin comprises any one of fluorine-containing sulfonic acid resin, fluorine-containing carboxylic acid resin, fluorine-containing phosphoric acid resin, fluorine-containing tertiary amine resin, fluorine-containing quaternary amine resin or any combination thereof, and the fluorine-containing monomer of the fluorine-containing ion exchange resin is selected from any one of tetrafluoroethylene, vinylidene fluoride, trifluoroethylene and fluoroethylene or any combination thereof.

The fluorine-containing polymer mixture for the high-moisture-permeability super-breathable microporous membrane disclosed by some embodiments comprises 65-80% of component A, 6-15% of component B, 2-23% of component C and 0-2% of component D in sequence by mass.

Some embodiments disclose fluorine-containing polymer mixtures for high moisture permeable super breathable microporous membranes, component B comprising perfluorobutyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, perfluorooctyl ethyl acrylate, perfluorooctyl ethyl methacrylate, N-methyl perfluorobutyl amine ethyl sulfonate, N-methyl perfluorohexyl amine ethyl sulfonate, N-methyl perfluorooctyl amine ethyl sulfonate, other C5-C16 fluorine-containing alkyl acrylates or methacrylates.

Some embodiments disclose a fluorine-containing polymer mixture for a high moisture-permeable super-breathable microporous membrane, wherein the polyurethane acrylate prepolymer is hot-melt, the melting point of the polyurethane acrylate prepolymer is less than 80 ℃, and the preparation raw materials of the fluorine-containing polymer mixture comprise:

aromatic diisocyanate, aliphatic diisocyanate or 2-3 membered isocyanate;

A polyhydric alcohol with a molecular weight of 600-5000;

wherein the polyol comprises polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyester polyol or polycarbonate polyol.

Some embodiments disclose a fluorine-containing polymer mixture for a high moisture-permeable super-breathable microporous membrane, and the preparation method of the polyurethane acrylate prepolymer comprises the following steps:

Vacuumizing the reaction kettle to remove moisture, adding diisocyanate, heating and stirring;

The temperature in the reaction kettle is increased to 50-150 ℃, and polyol is introduced into the kettle for reaction for 10-180 min, wherein the polyol is polyether-containing polyol or polyester polyol, and the molar ratio of diisocyanate to polyol is 2:1-8:1;

Adding hydroxyalkyl acrylate or hydroxyalkyl methacrylate into a reaction kettle, completely reacting with unreacted isocyanate by hydroxyalkyl, maintaining the reaction temperature at 50-150 ℃, reacting for 10-180 min, cooling and discharging to obtain polyurethane acrylate prepolymer, wherein the mole number of the added hydroxyalkyl acrylate or hydroxyalkyl methacrylate is greater than or equal to that of the unreacted isocyanate.

The fluorine-containing polymer mixture for the high-moisture-permeability super-breathable microporous membrane is disclosed in some embodiments, and the fluorine-free alkyl acrylate is a free-radical polymerizable monomer or a mixed monomer thereof, and specifically comprises hydroxyalkyl acrylate, hydroxyalkyl methacrylate, C5-C20 alkyl acrylate, C4-C20 alkyl methacrylate and C6-C20 vinyl acrylate, wherein the hydroxyalkyl acrylate comprises hydroxyethyl acrylate or hydroxypropyl acrylate, and the hydroxyalkyl methacrylate comprises hydroxyethyl methacrylate or hydroxypropyl methacrylate.

Some embodiments disclose a fluorine-containing polymer mixture for a high moisture permeability and high air permeability microporous membrane, wherein the half-life of a high temperature free radical initiator is between 100 and 250 ℃, and the fluorine-containing polymer mixture specifically comprises dicumyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butylperoxy hexane, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butyl peroxide-3-hexyne and cumene hydroperoxide.

In another aspect, some embodiments disclose the use of a fluorine-containing polymeric mixture for a high moisture vapor permeability and high air permeability microporous membrane, the fluorine-containing polymeric mixture being used to prepare Gao Toushi super air permeability microporous membrane, the preparation method specifically comprising:

mixing the component A, the component B, the component C and the component D according to a set proportion, and blending for a first set time by adopting a mild shearing-free method to obtain a fluorine-containing polymer mixture;

Prepressing the fluorine-containing polymer mixture into a cylindrical pasty mixture;

Extruding the pasty mixture into a rod shape at a first set temperature, and then casting into a strip-shaped mixture;

The ribbon-shaped mixture is longitudinally and rapidly stretched at a second set temperature, then is rapidly and transversely stretched at a third set temperature, and finally is shaped for a second set time at a fourth set temperature, so that the high-moisture-permeability super-breathable microporous membrane is obtained.

Further, some embodiments disclose a composite material prepared from a high moisture-permeability super-breathable microporous membrane prepared from a fluorine-containing polymer mixture, wherein the composite material is obtained by dot-pasting and compounding the high moisture-permeability super-breathable microporous membrane and a textile fabric, the textile fabric is knitted or non-woven fabric, the surface density is 20-180 g/m ², the initial water pressure resistance of the high moisture-permeability super-breathable microporous membrane composite material is more than 100kPa, after washing for 10 times, the water pressure resistance is still more than 60kPa, the moisture permeability is more than 8000g/m ²/d, the air permeability is more than 1mm/s under 300Pa air pressure difference, and after the composite material is dried and bent for 1 ten times at a temperature of-40 ℃, the water pressure resistance is more than 70kPa.

The fluorine-containing high polymer mixture is prepared by mixing a composition consisting of a component A, a component B, a component C and a component D in a shearing-free manner, wherein the mass content of each component is 50-90%, 3-25%, 0-35% and 0-3% in sequence, the component A is a blend of high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin with a standard specific gravity of 2.13-2.18 g/m ³ and fluorine-containing ion exchange resin, the mass ratio of the fluorine-containing ion exchange resin to the high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin is 0.5-10:100, the fluorine-containing ion exchange resin can effectively improve the moisture permeability of a microporous membrane prepared by the fluorine-containing high polymer mixture without damaging the water resistance, the initial moisture permeability of the high moisture-permeable super-breathable microporous membrane prepared by the fluorine-containing high polymer mixture is more than 10000g/m ²/D, the air permeability is more than 2mm/s under 300Pa air pressure difference, the initial oil resistance is at least 5 levels, and the fluorine-containing ion exchange resin can resist high water pressure and harmful liquid and prevent the intrusion of the high molecular weight and the air permeability of the microporous membrane is better than the prior art in the sealing effect. The high-moisture-permeability super-breathable microporous membrane composite material has high waterproof pressure performance, high air permeability and high moisture permeability, has good protective performance on penetrable poisonous and harmful liquid, and the protective clothing made of the high-moisture-permeability super-breathable microporous membrane composite material is light, comfortable and warm-keeping, has excellent protective performance, and can greatly improve the protective combat capability of operators.

Detailed Description

The word "embodiment" as used herein does not necessarily mean that any embodiment described as "exemplary" is preferred or advantageous over other embodiments. Performance index testing in the examples of the present application, unless otherwise specified, was performed using conventional testing methods in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.

Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and other test methods and techniques not specifically mentioned herein are meant to be common to those of ordinary skill in the art.

The terms "substantially" and "about" are used herein to describe small fluctuations. For example, they may refer to less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%. Numerical data presented or represented herein in a range format is used only for convenience and brevity and should therefore be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range. For example, a numerical range of "1-5%" should be interpreted to include not only the explicitly recited values of 1% to 5%, but also include individual values and sub-ranges within the indicated range. Thus, individual values, such as 2%, 3.5% and 4%, and subranges, such as 1% -3%, 2% -4% and 3% -5%, etc., are included in this numerical range. The same principle applies to ranges reciting only one numerical value. Moreover, such an interpretation applies regardless of the breadth of the range or the characteristics being described. The moisture permeability test adopts national standard GB/T12704.1-2009 (calcium chloride, positive cup method), the air permeability test adopts national standard GB/T5453-1997 test method, and the oil resistance test adopts American standard AATCC118-2002 test method.

In this document, including the claims, all conjunctions such as "comprising," including, "" carrying, "" having, "" containing, "" involving, "" containing, "and the like are to be construed as open-ended, i.e., to mean" including, but not limited to. Only the connective "consisting of" and "consisting of" are closed connective words.

Numerous specific details are set forth in the following examples in order to provide a better understanding of the present application. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, devices, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present application.

On the premise of no conflict, the technical features disclosed by the embodiment of the application can be combined at will, and the obtained technical scheme belongs to the disclosure of the embodiment of the application.

In some embodiments, the fluorine-containing polymer mixture for the high moisture-permeable super-breathable microporous membrane is a white opaque mixture, the fluorine-containing polymer mixture is obtained by shearing-free mixing a composition consisting of a component A, a component B, a component C and a component D, wherein the mass content of each component is sequentially 50-90%, 3-25%, 0-35% and 0-3%, the component A is a blend of a high-molecular-weight polytetrafluoroethylene homo-or copolymer dispersion resin with a standard specific gravity of 2.13-2.18 g/m ³ and a fluorine-containing ion exchange resin, the mass ratio of the fluorine-containing ion exchange resin to the high-molecular-weight polytetrafluoroethylene homo-or copolymer dispersion resin is 0.5-10:100, the component B is a fluorine-containing alkyl acrylate monomer or a fluorine-containing alkyl methacrylate monomer or a mixture of the two, the component C is a polyurethane acrylate prepolymer or a fluorine-free alkyl acrylate monomer or a mixture of the two, the molecular weight of the polyurethane acrylate prepolymer or the fluorine-free alkyl acrylate monomer is less than 8000, and the melting point of the polyurethane acrylate monomer is below 80 ℃ and the component D is a high-temperature free radical initiator.

As an alternative embodiment, the high molecular weight polyethylene homo-or copolymer dispersion resin is ultra-high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin, the standard specific gravity is 2.135-2.165 g/m ³, the melting point is 325-350 ℃, and the fluorine-containing ion exchange resin is selected from any one of fluorine-containing anion exchange resin, fluorine-containing cation exchange resin and fluorine-containing double ion exchange resin or any combination thereof.

As an alternative embodiment, the preparation method of the high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin comprises the following steps:

Deionized water and a surfactant are added into a high-pressure reaction kettle, vacuumizing and oxygen discharging are carried out, heating is carried out, and stirring is carried out; as an alternative embodiment, the surfactant is an organic matter containing 6-16 carbons and at least comprises a carboxylic acid or sulfonic acid functional group, and the more preferable surfactant is a perfluorinated surfactant;

When the temperature in the reaction kettle is increased to 50-80 ℃, tetrafluoroethylene with purity higher than 99.999% and optional other comonomers are introduced, wherein the comonomers are selected from any one or any combination of perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, vinylidene fluoride, vinyl fluoride, 3-trifluoropropylene, perfluoro C2-C8 alkyl ethylene and the like, and the volume content of the tetrafluoroethylene in the reaction kettle is generally 95-99.99%;

After the pressure in the reaction kettle reaches 1.1-2.9 Mpa, adding a free radical initiator to start polymerization reaction, wherein the temperature in the reaction kettle is maintained at 70-110 ℃, and the free radical initiator is any one or any combination of sulfate, hydrogen peroxide or organic peroxide as an alternative implementation mode, and the pressure in the reaction kettle is maintained at more than 1.5Mpa in the polymerization reaction process as a more preferred implementation mode;

And continuously reacting until the solid content of the emulsion reaches 20-39%, stopping stirring after the temperature in the kettle is reduced to be lower than 50 ℃, discharging unreacted monomers, and discharging reactants to prepare the ultra-high molecular weight tetrafluoroethylene homo-or copolymer dispersion resin emulsion, wherein the average particle size of primary particles is 180-390 nm, and the average particle size of the preferred primary particles is 220-330 nm.

The ultra-high molecular weight tetrafluoroethylene homo-or copolymer dispersion resin is obtained by coagulating and drying the ultra-high molecular weight tetrafluoroethylene homo-or copolymer dispersion resin emulsion.

The fluorine-containing ion exchange resin is usually used in the form of a fluorine-containing ion exchange resin dispersion to facilitate uniform mixing.

As an alternative embodiment, the polymer side chains of the fluorine-containing ion exchange resin contain ion exchange groups, the fluorine-containing ion exchange resin comprises any one or any combination of fluorine-containing sulfonic acid resin, fluorine-containing carboxylic acid resin, fluorine-containing phosphoric acid resin, fluorine-containing tertiary amine resin and fluorine-containing quaternary amine resin, and the fluorine-containing monomer of the fluorine-containing ion exchange resin is selected from any one or any combination of tetrafluoroethylene, vinylidene fluoride, trifluoroethylene and fluoroethylene.

As an alternative implementation mode, the mass content of the component A, the component B, the component C and the component D which form the fluorine-containing polymer mixture is 65-80%, 6-15%, 2-23% and 0-2% in sequence.

As an alternative embodiment, the component B of the fluorine-containing polymer mixture comprises perfluorobutyl ethyl acrylate CH ₂＝CHCOOC₂H₄C₄F₉, perfluorobutyl ethyl methacrylate CH ₂＝CCH₃COOC₂H₄C₄F₉, perfluorohexyl ethyl acrylate CH ₂＝CHCOOC₂H₄C₆F₁₃, perfluorohexyl ethyl methacrylate CH ₂＝CCH₃COOC₂H₄C₆F₁₃, perfluorooctyl ethyl acrylate CH ₂＝CHCOOC₂H₄C₈F₁₇, perfluorooctyl ethyl methacrylate CH ₂＝CCH₃COOC₂H₄C₈F₁₇, N-methyl perfluorobutyl amine ethyl sulfonate CH ₂＝CHCOOC₂H₄NCH₃SO₂C₄F₉, N-methyl perfluorobutyl amine ethyl sulfonate CH ₂＝CCH₃COOC₂H₄NCH₃SO₂C₄F₉, N-methyl perfluorohexyl amine ethyl sulfonate CH ₂＝CHCOOC₂H₄NCH₃SO₂C₆F₁₃, N-methyl perfluorohexyl amine ethyl sulfonate CH ₂＝CCH₃COOC₂H₄NCH₃SO₂C₆F₁₃, N-methyl perfluorooctyl amine ethyl sulfonate CH ₂＝CHCOOC₂H₄NCH₃SO₂C₈F₁₇, N-methyl perfluorooctyl amine ethyl sulfonate CH ₂＝CCH₃COOC₂H₄NCH₃SO₂C₈F₁₇, and other C5-C16 fluorine-containing alkyl acrylates or methacrylates.

As an alternative embodiment, component B, the fluoroalkyl acrylate monomer or the fluoroalkyl methacrylate monomer or the mixture of both, has a molecular weight of less than 2000.

As an alternative embodiment, the polyurethane acrylate prepolymer is hot melt, its melting point is less than 80 ℃, its preparation raw materials include:

aromatic diisocyanate, aliphatic diisocyanate or 2-3 membered isocyanate;

A polyhydric alcohol with a molecular weight of 600-5000;

As an alternative embodiment, the method for preparing the urethane acrylate prepolymer includes:

As a more preferred embodiment, the melting point of the fluoroalkylacrylate monomer or the fluoroalkylmethacrylate monomer or the mixture of both is less than 50 ℃.

As an alternative embodiment, the molecular weight of the polyol is between 600 and 5000.

As a more preferred embodiment, the molecular weight of the polyol is between 1000 and 3000, and each polyol molecule contains 2 to 3 hydroxyl groups.

As a more preferred embodiment, the molecular weight of the component C polyurethane acrylate prepolymer or the fluorine-free alkyl acrylate monomer or the mixture of the two is less than 5000.

As a more preferred embodiment, the melting point of the component C polyurethane acrylate prepolymer or the non-fluoroalkyl acrylate monomer or the mixture of the two is less than 50 ℃.

As an alternative implementation mode, in the component C polyurethane acrylate prepolymer and the mixture of the fluorine-free alkyl acrylate monomer, the mass content of the polyurethane acrylate prepolymer is 0-70%, and the mass content of the fluorine-free alkyl acrylate monomer is 30-100%.

As an alternative embodiment, the average molecular weight of the fluorine-free alkyl acrylate is less than 1000 and the melting point is less than 80 ℃.

As a more preferred embodiment, the fluorine-free alkyl acrylate has an average molecular weight of less than 600, a melting point of greater than 50 ℃ and an atmospheric boiling point of greater than 160 ℃.

As an alternative embodiment, the fluorine-free alkyl acrylate is a free radical polymerizable monomer or a mixed monomer thereof, and specifically comprises hydroxyalkyl acrylate, hydroxyalkyl methacrylate, C5-C20 alkyl acrylate, C4-C20 alkyl methacrylate and C6-C20 vinyl acrylate, wherein the hydroxyalkyl acrylate comprises hydroxyethyl acrylate or hydroxypropyl acrylate, and the hydroxyalkyl methacrylate comprises hydroxyethyl methacrylate or hydroxypropyl methacrylate, or any combination thereof.

As an optional embodiment, as an optional embodiment, the fluorine-free alkyl acrylate is a free radical polymerizable monomer or a mixed monomer thereof, and the atmospheric boiling point is more than 200 ℃, including isooctyl acrylate, isononyl acrylate, isodecyl acrylate, isoundecyl acrylate, isotridecyl acrylate, vinyl isooctanoate, vinyl neononanoate, vinyl neodecanoate, other C6-C18 alkyl acrylates, other C6-C18 alkyl methacrylates, or any combination thereof.

As an alternative embodiment, the high temperature radical initiator is an organic radical initiator with a half-life of 100-250 degrees. The half-life referred to herein generally means that after 10 hours at a particular temperature, the free radical initiator retains at least half of the active ingredients that are capable of generating free radicals. Typical high temperature radical initiators include dicumyl peroxide (CAS: 80-43-3), 2, 5-dimethyl-2, 5-bis- (t-butylperoxy) hexane (CAS: 78-63-7), di-t-butyl peroxide (CAS: 110-05-4), 2, 5-dimethyl-2, 5-bis (t-butyl peroxide) -3-hexyne (CAS: 1068-27-5), cumene hydroperoxide (CAS: 80-15-9).

In some embodiments, the method of applying the fluoropolymer blend to produce Gao Toushi super-breathable microporous membranes comprises:

(1) Mixing ultra-high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin powder with fluorine-containing ion exchange resin dispersion solution, adopting shearing-free stirring, fully and uniformly mixing, and then placing into a baking oven or a vacuum baking oven to remove volatile substances to obtain a component A;

(2) Uniformly stirring the obtained component A, the component B, the component C and the component D in a shearing-free way, directly pouring the mixture into a blank pressing column barrel, exhausting, and pressing blanks at 20-100 ℃ to prepare a cylindrical pasty mixture blank column, wherein lubricating oil is not added to avoid the danger of inflammability and explosiveness during deoiling;

(3) Extruding the pasty mixture blank column through a push press at 20-100 ℃, and then calendaring the extrudate into strips with the thickness of 50-2000 mu m, preferably 80-800 mu m;

(4) And (3) stretching the strip in one direction or two directions at 100-200 ℃ and performing heat setting at 200-390 ℃ to obtain the high-moisture-permeability super-breathable microporous membrane.

The high moisture permeability super ventilation microporous membrane prepared from the fluorine-containing polymer mixture has the thickness of 0.005-1.5 mm, the surface density of 1-1200 g/m ², the porosity of 30-95%, the tensile strength of more than 20Mpa, the initial oil resistance of at least 5 grades, the moisture permeability of more than 10000g/m ²/d, the ventilation property of more than 2mm/s under 300Pa air pressure difference, the oil resistance of at least 4 grades after washing for 10 times, the moisture permeability of more than 9000g/m ²/d, and the ventilation property of more than 1.5mm/s under 300Pa air pressure difference.

As a more preferable implementation mode, the high-moisture-penetrability super-breathable microporous membrane has the thickness of 0.01-0.08 mm, the surface density of 3-30 g/m ², the porosity of 70-90%, the tensile strength of more than 30MPa and the initial oil resistance of at least 6 levels, and after 10 times of water washing, the oil resistance is at least 5 levels, the moisture penetrability is more than 10000g/m ²/d, and the air permeability is more than 2mm/s under 300Pa air pressure difference.

Some embodiments disclose a high moisture-permeability super-breathable microporous membrane composite material, which is obtained by compounding a high moisture-permeability super-breathable microporous membrane with a textile fabric in a point-to-point manner, wherein the textile fabric is knitted or non-woven fabric, the surface density is 20-180 g/m ², the initial water pressure resistance of the high moisture-permeability super-breathable microporous membrane composite material is more than 100kPa, the water pressure resistance is still more than 60kPa after washing for 10 times, the moisture permeability is more than 8000g/m ²/d, the air permeability is more than 1mm/s under 300Pa air pressure difference, and the water pressure resistance is more than 70kPa after the composite material is dried and bent for 1 ten thousands times at-40 ℃. The composite material is usually a composite fabric and is used for manufacturing special protective clothing. The composite material is compounded with the textile cloth through the high-moisture-permeability and super-air-permeability microporous membrane of the dot-shaped adhesive piece to obtain the composite fabric.

As a more preferable implementation mode, the initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material is greater than 200kPa, the water pressure resistance is greater than 100kPa after washing for 10 times, the moisture permeability is greater than 10000g/m ²/d, and the air permeability is greater than 2mm/s under 300Pa air pressure difference. The sealing effect is better after the water stop strips are adhered to the seam line.

In the embodiment, the performance of the high-moisture-permeability super-breathable microporous membrane and the high-moisture-permeability super-breathable microporous membrane composite material prepared from the fluorine-containing polymer mixture is tested, and the related testing method comprises the following steps:

(1) The water pressure resistance of the high moisture permeability super-breathable microporous membrane and the composite material thereof is tested by adopting a FZ/T01004-2008 method, wherein the outer layer cloth faces water, and the initial water pressure is more than 100kPa;

(2) Washing with a standard washing machine, adding a detergent, drying, repeating for 10 times, wherein the performance requirement is that the water pressure resistance is more than 100kPa;

(3) The mosquito-repellent liquid N, N-diethyl-3-methylbenzamide (CAS# 134-62-3) is a spray fabric with the concentration of more than 95%, and the water pressure is measured after the spray fabric is covered for 3 hours, so that the water pressure is required to be more than 70kPa;

(4) The mosquito-proof liquid sprays the surface cloth, cover after one day, wash (add detergent) +oven dry 3 times, measure the water pressure, require more than 70kPa;

(5) The moisture resistance is achieved, a standard washing machine is used for washing for 50 times continuously, no detergent is added, and finally, the washing machine is dried, and the water pressure is measured, so that the requirement is more than 70kPa;

(6) The low temperature resistance is realized by carrying out dry bending on the composite fabric for 1 ten thousand times at the temperature of-40 ℃ and measuring the water pressure, wherein the water pressure is required to be more than 70kPa;

(7) The air permeability of the composite material is tested according to GB/T5453-1997, the outer layer cloth faces downwards, the speed is higher, and the air permeability is better;

(8) The moisture permeability of the composite material is tested according to the GB/T12704.1-2009 positive cup method, the outer layer cloth faces upwards, and the moisture permeability of the water vapor is required to be more than 8000g/m ²/d. The larger the moisture permeability is, the easier the sweat is discharged;

(9) The moisture permeability of the composite material is tested according to the GB/T12704.1-2009 inverted cup method, the outer layer cloth faces upwards, the moisture permeability of the water vapor is required to be more than 10000g/m ²/d, and the larger the better the moisture permeability, the easier the sweat is discharged.

The technical details are further described below in connection with the examples.

Preparation of component A

Example 1

High molecular weight polytetrafluoroethylene copolymer dispersion resin

Is prepared by taking tetrafluoroethylene and perfluoroethyl vinyl ether as polymerization monomers and ammonium sulfate as an initiator. The preparation method comprises the steps of firstly adding 500L of deionized water, 20Kg of paraffin with high purity and melting point of 50-85 ℃ and 180g of ammonium perfluorooctanoate into a horizontal high-pressure reaction kettle with volume of about 1000 liters, vacuumizing and discharging oxygen in the kettle until the oxygen content is less than 20ppm, heating and stirring, introducing tetrafluoroethylene gas with purity of more than 99.999% into the kettle when the temperature in the kettle is raised to about 70 ℃ to enable the pressure in the kettle to reach about 2.2MPa, then adding 300g of perfluoroethylvinyl ether C ₂F₅-OCF＝CF₂ with purity of more than 98% into the reaction kettle at a speed of 10g/min as a comonomer, simultaneously adding 0.8g of ammonium persulfate dissolved in 500 ml of water in advance as an initiator, starting copolymerization, maintaining the temperature in the kettle at 80-100 ℃, and introducing tetrafluoroethylene gas during the reaction to enable the pressure in the kettle to be maintained at about 2.0MPa. And (3) continuously reacting until the solid content of the emulsion reaches about 30%, reducing the temperature in the kettle to below 50 ℃, stopping stirring, discharging unreacted monomers, reducing the pressure, and discharging reactants to obtain the ultra-high molecular weight polytetrafluoroethylene copolymer dispersion resin emulsion, wherein the average particle size of primary particles is about 280nm. Diluting the emulsion, stirring at high speed, then agglomerating and demulsifying, loading the suspension polymer into a tray, and putting the tray into an oven for drying at 190 ℃ to obtain the high molecular weight polytetrafluoroethylene copolymer dispersion resin. The standard specific gravity of the high molecular weight tetrafluoroethylene copolymer dispersion resin is about 2.149g/m ³, and the melting point peak is 325-350 ℃.

Fluorine-containing ion exchange resin

The preparation method comprises the steps of adding 39000g of purified water and 100g of ammonium perfluorooctanoate into a sealed pre-emulsification reaction kettle A with a volume of about 100 liters at normal temperature, shearing and stirring at a high speed, slowly adding 5000g of fluorine-containing band sulfonyl fluoride liquid phase monomer into the reaction kettle A, mixing the fluorine-containing band sulfonyl fluoride liquid phase monomer with 70% of CF ₂＝CF-OCF₂CFCF₃-O-CF₂CF₂-SO₂ F and 30% of CF ₂＝CF-O-CF₂CF₂-SO₂ F by mass, continuously shearing and stirring at a high speed for about 30 minutes to prepare a prepolymer emulsion, firstly discharging oxygen until the oxygen content in the other reaction kettle B with a volume of about 100 liters is less than 20ppm, adding all the prepolymer emulsion from the reaction kettle A, introducing gas phase mixed monomer into the reaction kettle B, wherein the gas phase mixed monomer consists of 90% of tetrafluoroethylene and 10% of trifluoro chloroethylene by mole ratio, heating to 70 ℃, maintaining the pressure in the kettle at 1.1MPa, adding 2.5g of ammonium persulfate pre-dissolved in 1L of deionized water, and starting free radical polymerization. The ratio of the total weight of the fluorine-containing band sulfonyl fluoride liquid phase monomer to the total weight of the gas phase mixed monomer actually participating in the free radical polymerization reaction is about 4:5, the mass ratio of the total weight of the free radical initiator to the fluorine-containing band sulfonyl fluoride liquid phase monomer is controlled to be 0.05%, the reaction temperature is controlled to be 70-75 ℃, the reaction is carried out for 1 hour, the temperature in the kettle is reduced to room temperature, stirring is stopped, the fluorine-containing and chlorine-containing conductive polymer emulsion is obtained, the average particle size of primary particles is about 100nm, the solid content in the emulsion is about 19%, the obtained fluorine-containing and chlorine-containing conductive polymer emulsion is hydrolyzed by sulfonyl fluoride-SO ₂ F to obtain a fluorine-containing and chlorine-containing band sulfonic acid-SO ₃ H conductive polymer, the specific gravity is about 1.99, the acid equivalent number (meq/g) is about 900, and the normal temperature conductivity of a single film is more than 0.15S/cm after drying. And heating the fluorine-containing and chlorinated sulfonic acid-containing conductive polymer in 75% medical alcohol to 60 ℃ for dissolution to obtain fluorine-containing ion exchange resin alcohol solution with the solid content of about 20%.

Preparation of component A

The high molecular weight polytetrafluoroethylene copolymer dispersion resin prepared in this example 1 was blended with an alcoholic solution of a fluorine-containing ion exchange resin, blended for half an hour with a mild and shearing-free method to give a white opaque mixture, and dried in a vacuum oven at 50 ℃ for 12 hours to remove alcohol to give component A1, wherein the ratio of fluorine-containing ion exchange resin to high molecular weight polytetrafluoroethylene copolymer was 0.5:100.

Example 2

Component A2 was prepared by the method of example 1, wherein the ratio of the fluorine-containing ion exchange resin to the high molecular weight polytetrafluoroethylene copolymer was 5:100.

Example 3

Component A3 was prepared by the method of example 1, wherein the ratio of the fluorine-containing ion exchange resin to the high molecular weight polytetrafluoroethylene copolymer was 10:100.

Comparative example 1

Component A'1 was prepared by the method of example 1, wherein the fluorine-containing ion exchange resin content was 0.

Comparative example 2

Component A'2 was prepared by the method of example 1, wherein the ratio of the fluorine-containing ion exchange resin to the high molecular weight polytetrafluoroethylene copolymer was 15:100.

Preparation of component C

Example 4

Mixtures of urethane acrylate prepolymers and fluorine-free alkyl acrylates

The polyurethane acrylate prepolymer is prepared by heating a jacket to 100 ℃ in a reaction kettle with a volume of about 200L, vacuumizing, flushing nitrogen to dehumidify the reaction kettle, adding 26.2Kg of 4,4' -dicyclohexylmethane diisocyanate HMDI which contains about 200mol-NCO isocyanate, stirring, raising the temperature in the kettle to about 100 ℃, adding 60Kg of polypropylene glycol with a molecular weight of about 2000 which contains about 60mol-OH hydroxyl groups, reacting for about 90min, adding 18.2Kg of hydroxyethyl methacrylate which contains about 140mol-OH hydroxyl groups, maintaining the temperature in the kettle at about 100 ℃, and reacting for about 1h to obtain the polyurethane acrylate prepolymer with viscous liquid, wherein the melting point is lower than 50 ℃.

15Kg of the urethane acrylate prepolymer prepared in example 4 was added at normal temperature and pressure to a stirring vessel having a volume of about 100 liters, followed by addition of 35Kg of isodecyl acrylate (CAS: 1330-61-6), continuous stirring to homogeneity, stopping stirring, and discharging the mixture to obtain a mixture of urethane acrylate prepolymer and fluorine-free alkyl acrylate, the mass ratio of which was 3:7, and which was designated as component C1.

Example 5

Referring to the method of example 4, a mixture of urethane acrylate prepolymer and fluorine-free alkyl acrylate was prepared;

Wherein, in a stirring barrel with a volume of about 100 liters, 25Kg of polyurethane acrylate prepolymer is added at normal temperature and pressure, then 25Kg of isodecyl acrylate (CAS: 1330-61-6) is added, stirring is continuously carried out to be homogeneous, stirring is stopped, the mixture is discharged, the mass ratio of the polyurethane acrylate prepolymer to the fluorine-free alkyl acrylate is 5:5, and the mixture is marked as a component C2.

Preparation of fluorine-containing polymer mixture

Example 6

The component A2 obtained in the example 2, the perfluoroalkyl ethyl acrylate mixture, the component C1 obtained in the example 4 and cumene hydroperoxide are mixed according to a mass ratio of 75:10:14:1, and the mixture is blended for about half an hour by adopting a mild shearing-free method to obtain a fluorine-containing polymer mixture, wherein the standard specific gravity of the mixture is about 1.88g/cm ³, the average molecular weight of the mixture is less than 1000, the melting point is less than 35 ℃, the distribution of perfluoroalkyl groups is 10% C4, 30% C6, 50% C8 and 10% C10, and the cumene peroxide is CAS 80-15-9. The fluoropolymer mixture obtained in example 6 was labeled mixture E1.

Comparative example 3

A fluorine-containing polymer mixture was prepared by the method of example 6, wherein component A was selected from component A '1 obtained in comparative example 1, and the fluorine-containing polymer mixture obtained in comparative example 3 had a standard specific gravity of about 1.89g/cm ³, denoted as E'1.

Example 7

The component A1 obtained in example 1, the perfluoroalkyl ethyl acrylate mixture and cumene hydroperoxide (CAS: 80-15-9) are mixed according to a mass ratio of 85:14:1, and the mixture is blended for about half an hour by adopting a mild shearing-free method, wherein the obtained fluorine-containing polymer mixture does not contain a component C and has a standard specific gravity of about 2.03g/cm ³, wherein the perfluoroalkyl ethyl acrylate mixture has an average molecular weight of less than 1000 and a melting point of less than 30 ℃, and the distribution of perfluoroalkyl groups is 10% C4, 60% C6 and 30% C8. The fluoropolymer mixture obtained in example 7 was labeled mixture E2.

Example 8

The fluorine-containing polymer mixture was prepared by the method of reference example 7, wherein the component A was selected from the component A3 obtained in example 3, and the fluorine-containing polymer mixture obtained did not contain the component C, and the standard specific gravity thereof was about 2.02g/cm ³, and the fluorine-containing polymer mixture obtained in example 8 was labeled as mixture E3.

Comparative example 4

A fluorine-containing polymer mixture was prepared by the method of reference example 7, wherein component A was selected from component A '1 obtained in comparative example 1, and the fluorine-containing polymer mixture obtained did not contain component C, and had a standard specific gravity of about 2.04g/cm ³, which was designated as mixture E'2.

Example 9

The component A2 obtained in example 2, the perfluoroalkyl ethyl acrylate mixture, the component C2 obtained in example 5 and cumene hydroperoxide (CAS: 80-15-9) are mixed in a mass ratio of 65:11:23:1 and blended for about half an hour by a mild shear-free method to obtain a fluorine-containing polymer mixture with a standard specific gravity of about 1.83g/cm ³, wherein the perfluoroalkyl ethyl acrylate mixture has an average molecular weight of less than 1000 and a melting point of less than 35 ℃ and a distribution of perfluoroalkyl groups of 10% C4, 30% C6, 50% C8 and 10% C10. The fluoropolymer mixture obtained in this example 9 was labeled as mixture E4.

Comparative example 5

A fluorine-containing polymer mixture was prepared by the method of reference example 9, wherein component A was selected from A '1 obtained in comparative example 1, and the specific gravity of the obtained fluorine-containing polymer mixture was about 1.84g/cm ³, which was designated as mixture E'3.

Example 10

The component A2 obtained in example 1, the perfluoroalkyl ethyl acrylate mixture, isodecyl acrylate (CAS: 1330-61-6) and cumene hydroperoxide (CAS: 80-15-9) are mixed in a mass ratio of 78:10:11:1 and blended for about half an hour by a mild, shear-free method to obtain a fluorine-containing polymer mixture having a standard specific gravity of about 1.97g/cm ³, wherein the perfluoroalkyl ethyl acrylate mixture has an average molecular weight of less than 1000 and a melting point of less than 35 ℃, and a distribution of perfluoroalkyl groups of 10% C4, 60% C6 and 30% C8. The fluoropolymer mixture obtained in example 10 was labeled mixture E5.

Comparative example 6

A fluorine-containing polymer mixture was prepared by the method of reference example 10, wherein component A was A '2 obtained in comparative example 2, and the fluorine-containing polymer mixture obtained had a standard specific gravity of 1.97g/cm ³ and was labeled as mixture E'4.

Preparation of high-moisture-permeability super-breathable microporous membrane by using fluorine-containing polymer mixture

Example 11

Prepressing the mixture E1 obtained in example 6 into a cylindrical paste-like mixture;

extruding the paste mixture into a rod shape by a pusher at about 70 ℃ and then casting into a ribbon-like mixture having a thickness of about 0.45 mm and a width of about 180 mm;

the tape mix was rapidly stretched in the machine direction about 4 times at about 130 ℃, then in the transverse direction about 12 times at about 180 ℃, and finally set at about 370 ℃ for about 11 seconds to obtain a highly moisture permeable, super breathable microporous membrane, designated M1.

The thickness of the high moisture permeability super ventilation microporous membrane M1 is about 0.037mm, the width is about 1800mm, the specific gravity is about 15g/M ², the porosity is about 82-85%, the tensile strength is greater than 20MPa, the ventilation performance is about 3.9mm/s under 300Pa air pressure, and the moisture permeability is about 11000g/M ²/d.

Comparative example 7

Reference example 11 a high moisture permeable, super breathable microporous membrane was prepared, wherein the fluorine-containing polymer blend was selected from E '1 obtained in comparative example 3, and the resulting high moisture permeable, super breathable microporous membrane was labeled M'1.

The thickness of the high moisture permeability super ventilation microporous membrane M'1 is about 0.036mm, the width is about 1800mm, the specific gravity is about 15g/M ², the porosity is about 80-83%, the tensile strength is greater than 20MPa, the ventilation property is about 3.6mm/s under 300Pa air pressure, and the moisture permeability is about 8000g/M ²/d.

The test results of example 11 and comparative example 7 show that the microporous membrane M1 prepared from the fluorine-containing polymer blend containing the fluorine-containing ion exchange resin has a much larger moisture permeability than the microporous membrane M'1 prepared from the fluorine-containing polymer blend not containing the fluorine-containing ion exchange resin, but the increase in moisture permeability does not impair the air permeability thereof, which is an unexpected technical effect of the prior art.

Example 12

Prepressing the mixture E2 obtained in example 7 into a cylindrical paste-like mixture;

the tape mix was rapidly stretched in the machine direction about 4 times at about 140 ℃, then in the transverse direction about 12 times at about 190 ℃, and finally set at about 370 ℃ for about 11 seconds to obtain a highly moisture permeable, super breathable microporous membrane, labeled M2.

The thickness of the high moisture permeability super ventilation microporous membrane M2 is about 0.031mm, the width is about 1800mm, the specific gravity is about 15g/M ², the porosity is about 86-89%, the tensile strength is greater than 25MPa, the ventilation property is about 4.8mm/s under 300Pa air pressure, and the moisture permeability is about 9200g/M ²/d.

Example 13

A high moisture permeable super breathable microporous membrane was prepared in reference example 12, wherein the fluorine-containing polymer blend was selected from blend E3 obtained in example 8, and the resulting moisture permeable super breathable microporous membrane was labeled M3.

The thickness of the high-moisture-permeability super-breathable microporous membrane M3 is about 0.030mm, the width is about 1800mm, the specific gravity is about 15g/M ², the porosity is about 88-90%, the tensile strength is greater than 25MPa, the air permeability is about 5.6mm/s under 300Pa air pressure, and the moisture permeability is about 13500g/M ²/d.

Comparative example 8

A high moisture permeable, super breathable microporous membrane was prepared in reference example 12, wherein the fluorine-containing polymer blend was selected from blend E '2 obtained in comparative example 4, and the resulting moisture permeable, super breathable microporous membrane was designated M'2.

The thickness of the high moisture permeability super ventilation microporous membrane M'2 is about 0.031mm, the width is about 1800mm, the specific gravity is about 15g/M ², the porosity is about 86-89%, the tensile strength is greater than 25MPa, the ventilation property is about 4.6mm/s under 300Pa air pressure, and the moisture permeability is about 8500g/M ²/d.

The test results of examples 12, 13 and comparative example 8 show that the microporous membranes M2, M3 prepared from the fluorine-containing polymer blend containing the fluorine-containing ion exchange resin had a much larger moisture permeability than the microporous membrane M'2 prepared from the fluorine-containing polymer blend containing no fluorine-containing ion exchange resin, and that the moisture permeability of the microporous membrane increased with the increase in the content thereof within a reasonable range of the content of the fluorine-containing ion exchange resin, but the increase in the moisture permeability of the microporous membrane did not significantly impair the air permeability thereof, which was an unexpected technical effect of the prior art.

Example 14

A high moisture permeable super breathable microporous membrane was prepared in reference example 12, wherein the fluorine-containing polymer blend was selected from blend E4 obtained in example 9, resulting in a high moisture permeable super breathable microporous membrane labeled M4.

The high moisture permeability super breathable microporous membrane M4 has a thickness of about 0.038mm, a breadth of about 1800mm, a specific gravity of about 16g/M ², a porosity of about 79 to 82%, a moisture permeability of about 3.8mm/s under an air pressure of 300Pa, and a moisture permeability of about 10500g/M ²/d.

Comparative example 9

Reference example 12 a high moisture permeable, super breathable microporous membrane was prepared, wherein the fluorine-containing polymeric mixture was selected from the mixture E '3 obtained in comparative example 5, resulting in a high moisture permeable, super breathable microporous membrane labeled M'3.

The high moisture permeability super breathable microporous membrane M'3 has a thickness of about 0.039mm, a breadth of about 1800mm, a specific gravity of about 16g/M ², a porosity of about 76-80%, a moisture permeability of about 3.3mm/s under 300Pa air pressure, and a moisture permeability of about 7600g/M ²/d.

The test results of example 14 and comparative example 9 show that the microporous membrane M4 prepared from the fluorine-containing polymer blend containing the fluorine-containing ion exchange resin has a much larger moisture permeability than the microporous membrane M'3 prepared from the fluorine-containing polymer blend not containing the fluorine-containing ion exchange resin, but the increase in moisture permeability does not impair the air permeability thereof, which is an unexpected technical effect of the prior art.

Example 15

Prepressing the mixture E5 obtained in example 10 into a cylindrical paste-like mixture;

The tape mix was rapidly stretched in the machine direction about 4 times at about 140 ℃, then in the transverse direction about 12 times at about 190 ℃, and finally set at about 370 ℃ for about 12 seconds to obtain a highly moisture permeable, super breathable microporous membrane, labeled M5.

The thickness of the high moisture permeability super ventilation microporous membrane M5 is about 0.032mm, the width is about 1800mm, the specific gravity is about 15g/M ², the porosity is about 86-89%, the tensile strength is greater than 20MPa, the ventilation property is about 5.2mm/s under 300Pa air pressure, and the moisture permeability is about 12000g/M ²/d.

Comparative example 10

Reference example 15 a high moisture permeable, super breathable microporous membrane was prepared, wherein the fluorine-containing polymeric mixture was selected from the mixture E '4 obtained in comparative example 6, resulting in a high moisture permeable, super breathable microporous membrane labeled M'4.

The thickness of the high moisture permeability super ventilation microporous membrane M'4 is about 0.030mm, the width is about 1800mm, the specific gravity is about 16g/M ², the porosity is about 79-82%, the tensile strength of the membrane is greater than 20MPa, the ventilation property is about 6.8mm/s under 300Pa air pressure, and the moisture permeability is about 15000g/M ²/d.

The test results of example 15 and comparative example 10 show that the microporous membrane M'4 prepared from the fluorine-containing polymer mixture having the fluorine-containing ion exchange resin content exceeding the reasonable range has a larger moisture permeability than the microporous membrane M5 prepared from the fluorine-containing polymer mixture having the fluorine-containing ion exchange resin range, but the air permeability is remarkably increased while the moisture permeability is increased, resulting in a decrease in the waterproof performance. Therefore, the content of the fluorine-containing ion exchange resin is within a reasonable range, so that the moisture permeability can be effectively improved without affecting the waterproof performance of the fluorine-containing ion exchange resin, and the moisture permeability and the waterproof performance of the microporous membrane are considered, so that the technical effects unexpected in the prior art are obtained.

Preparation of composite material by using high-moisture-permeability super-breathable microporous membrane

Example 16

The high moisture-permeability and super-breathable microporous membrane M1 obtained in the example 11 is compounded with nylon 6 plain weave cloth through dot polyurethane laminating glue points, wherein the surface density of the nylon 6 plain weave cloth is 96g/M ², and the high moisture-permeability and super-breathable microporous membrane composite material is obtained and marked as F1.

The initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F1 is greater than 200kPa, the water pressure resistance is still greater than 100kPa after washing for 10 times, the initial membrane surface oil resistance is 7 grades, the membrane surface oil resistance is still 6 grades after washing for 10 times, the air permeability is about 3.2mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 9500g/m ²/d, the sealing effect of a water stop strip attached to a sewing line is good, and all performance indexes meet the standards of waterproof and breathable clothing fabrics.

Comparative example 11

Preparing a high moisture-permeable and super-breathable microporous membrane composite material according to reference example 16, wherein the high moisture-permeable and super-breathable microporous membrane obtained in comparative example 7 is selected as the high moisture-permeable and super-breathable microporous membrane M '1, and the obtained high moisture-permeable and super-breathable microporous membrane composite material is marked as F'1;

The initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F'1 is greater than 200kPa, the water pressure resistance is still greater than 100kPa after washing for 10 times, the initial membrane surface oil resistance is 7 grades, the membrane surface oil resistance is still 6 grades after washing for 10 times, the air permeability is about 2.8mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 7000g/m ²/d, the sealing effect of a water stop strip attached to a sewing line is good, and the moisture permeability is poor.

From the test results of example 16 and comparative example 11, it is understood that the microporous membrane composite F1 prepared from the fluorine-containing polymer blend containing the fluorine-containing ion exchange resin had a much larger moisture permeability than the microporous membrane composite F'1 prepared from the fluorine-containing polymer blend containing no fluorine-containing ion exchange resin, but the increase in moisture permeability did not impair the water pressure resistance, which was an unexpected technical effect of the prior art.

Example 17

Preparing a high-moisture-permeability and super-air-permeability microporous membrane composite material according to reference example 16, wherein the high-moisture-permeability and super-air-permeability microporous membrane obtained in example 12 is selected as the high-moisture-permeability and super-air-permeability microporous membrane M2, and the obtained high-moisture-permeability and super-air-permeability microporous membrane composite material is marked as F2;

the initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F2 is greater than 200kPa, the water pressure resistance is still greater than 150kPa after washing for 10 times, the initial membrane surface oil resistance is 8 grades, the membrane surface oil resistance is still 7 grades after washing for 10 times, the air permeability is about 4.3mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 8300g/m ²/d, the sealing effect of a water stop strip attached to a sewing line is good, and all performance indexes meet the standards of waterproof and breathable clothing fabrics.

Example 18

Preparing a high-moisture-permeability and super-air-permeability microporous membrane composite material according to reference example 16, wherein the high-moisture-permeability and super-air-permeability microporous membrane obtained in example 13 is selected, and the obtained high-moisture-permeability and super-air-permeability microporous membrane composite material is marked as F3;

The initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F3 is greater than 200kPa, the water pressure resistance is still greater than 150kPa after washing for 10 times, the initial membrane surface oil resistance is 8 grades, the membrane surface oil resistance is still 7 grades after washing for 10 times, the air permeability is about 5.1mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 12500g/m ²/d, the sealing effect of a water stop strip attached to a sewing line is good, and all performance indexes meet the standards of waterproof and breathable clothing fabrics.

Comparative example 12

Preparing a high moisture-permeable and super-breathable microporous membrane composite material according to reference example 16, wherein the high moisture-permeable and super-breathable microporous membrane obtained in comparative example 8 is selected as the high moisture-permeable and super-breathable microporous membrane M '2, and the obtained high moisture-permeable and super-breathable microporous membrane composite material is marked as F'2;

The initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F'2 is greater than 200kPa, the water pressure resistance is still greater than 150kPa after washing for 10 times, the initial membrane surface oil resistance is 8 grades, the membrane surface oil resistance is still 7 grades after washing for 10 times, the air permeability is about 4.1mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 7500g/m ²/d, the sealing effect of a water stop strip attached to a sewing line is good, and all performance indexes meet the standards of waterproof and breathable clothing fabric.

From the test results of examples 17, 18 and comparative example 12, it is understood that the microporous membrane composites F2, F3 prepared from the fluorine-containing polymer blend containing the fluorine-containing ion exchange resin had a much larger moisture permeability than the microporous membrane composite F'2 prepared from the fluorine-containing polymer blend containing no fluorine-containing ion exchange resin, but the increase in moisture permeability did not impair the water pressure resistance, which was an unexpected technical effect in the prior art.

Example 19

Preparing a high-moisture-permeability and super-air-permeability microporous membrane composite material according to reference example 16, wherein the high-moisture-permeability and super-air-permeability microporous membrane obtained in example 14 is selected, and the obtained high-moisture-permeability and super-air-permeability microporous membrane composite material is marked as F4;

The initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F4 is greater than 200kPa, the water pressure resistance is still greater than 100kPa after washing for 10 times, the initial membrane surface oil resistance is 7 grades, the membrane surface oil resistance is still 5 grades after washing for 10 times, the tensile strength is greater than 20MPa, the air permeability is about 3.5mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 9600g/m ²/d, the sealing effect of a water stop strip attached to a sewing line is good, and all performance indexes meet the waterproof and breathable garment fabric standard.

Comparative example 13

Preparing a high moisture-permeable and super-breathable microporous membrane composite material according to reference example 16, wherein the high moisture-permeable and super-breathable microporous membrane obtained in comparative example 9 is selected as the high moisture-permeable and super-breathable microporous membrane M '3, and the obtained high moisture-permeable and super-breathable microporous membrane composite material is marked as F'3;

The initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F'3 is greater than 200kPa, the water pressure resistance is still greater than 100kPa after washing for 10 times, the initial membrane surface oil resistance is 7 grades, the membrane surface oil resistance is still 5 grades after washing for 10 times, the tensile strength is greater than 20MPa, the air permeability is about 2.9mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 6800g/m ²/d, and the sealing effect of the water stop strip attached to the sewing line is good.

The test results of example 19 and comparative example 13 show that the microporous membrane composite F4 prepared from the fluorine-containing polymer blend containing the fluorine-containing ion exchange resin has a much larger moisture permeability than the microporous membrane composite F'3 prepared from the fluorine-containing polymer blend not containing the fluorine-containing ion exchange resin, but the increase in moisture permeability does not impair the water pressure resistance, which is an unexpected technical effect of the prior art.

Example 20

Preparing a high-moisture-permeability and super-air-permeability microporous membrane composite material according to reference example 17, wherein the high-moisture-permeability and super-air-permeability microporous membrane obtained in example 15 is selected as the high-moisture-permeability and super-air-permeability microporous membrane M5, and the obtained high-moisture-permeability and super-air-permeability microporous membrane composite material is marked as F5;

The initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F5 is greater than 200kPa, the water pressure resistance is still greater than 100kPa after washing for 10 times, the initial membrane surface oil resistance is 7 grades, the membrane surface oil resistance is still 6 grades after washing for 10 times, the tensile strength is greater than 20MPa, the air permeability is about 4.8mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 11000g/m ²/d, the sealing effect of a water stop strip attached to a sewing line is good, and all performance indexes meet the waterproof and breathable garment fabric standard.

Comparative example 14

Preparing a high moisture-permeable and super-breathable microporous membrane composite material according to reference example 16, wherein the high moisture-permeable and super-breathable microporous membrane obtained in comparative example 10 is selected as the high moisture-permeable and super-breathable microporous membrane M '4, and the obtained high moisture-permeable and super-breathable microporous membrane composite material is marked as F'4;

The initial water pressure resistance of the high-moisture-permeability super-breathable microporous membrane composite material F'4 is greater than 200kPa, the water pressure resistance is less than 100kPa after washing for 10 times, the initial membrane surface oil resistance is 7 grades, the membrane surface oil resistance is still 6 grades after washing for 10 times, the air permeability is about 6.1mm/s under 300Pa air pressure, the moisture permeability (calcium chloride, positive cup method) is about 13500g/m ²/d, the sealing effect of a water stop strip attached to a sewing line is good, the air permeability and the moisture permeability are extremely excellent, and the water pressure resistance performance does not meet the waterproof and breathable garment fabric standard.

The test results of example 20 and comparative example 14 show that the moisture permeability of the microporous membrane composite material F'4 prepared from the fluorine-containing polymer mixture with the fluorine-containing ion exchange resin content exceeding the reasonable range is larger than that of the microporous membrane composite material F5 prepared from the fluorine-containing polymer mixture with the fluorine-containing ion exchange resin range, but the water pressure resistance is obviously reduced while the moisture permeability is increased, and the waterproof and breathable garment fabric standard is not met. Therefore, the content of the fluorine-containing ion exchange resin is within a reasonable range, so that the moisture permeability of the microporous membrane composite material can be effectively improved without affecting the waterproof performance of the microporous membrane composite material, and the moisture permeability and the waterproof performance of the microporous membrane composite material are considered, so that the technical effects unexpected in the prior art are obtained.

The technical details disclosed in the technical scheme and the embodiment of the application are only illustrative of the inventive concept of the application and are not limiting to the technical scheme of the application, and all the technical details disclosed in the application have the same inventive concept as the application, and are within the protection scope of the claims of the application.

Claims

1. The fluorine-containing polymer mixture for the high-moisture-permeability super-breathable microporous membrane is characterized in that a composition consisting of a component A, a component B, a component C and a component D is obtained by non-shearing mixing, wherein the mass content of each component is 50-90%, 3-25%, 0-35% and 0-3% in sequence;

The component A is a blend of high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin with standard specific gravity of 2.13-2.18 g/m ³ and fluorine-containing ion exchange resin, wherein the mass ratio of the fluorine-containing ion exchange resin to the high molecular weight polytetrafluoroethylene homo-or copolymer dispersion resin is 0.5-10:100, the high molecular side chain of the fluorine-containing ion exchange resin contains ion exchange groups, and the fluorine-containing ion exchange resin is a conductive high polymer containing fluorine and chlorine-containing sulfonic acid-SO ₃ H;

The preparation method of the fluorine-containing chlorine-containing conductive polymer with sulfonic acid-SO ₃ H comprises the following steps:

Mixing a fluorine-containing band sulfonyl fluoride liquid phase monomer with a gas phase mixed monomer, and polymerizing to obtain a fluorine-containing chlorine-containing conductive polymer emulsion, wherein the total weight ratio of the fluorine-containing band sulfonyl fluoride liquid phase monomer to the gas phase mixed monomer is 4:5, the fluorine-containing band sulfonyl fluoride liquid phase monomer is formed by mixing 70% of CF ₂＝CF-OCF₂CF(CF₃)-O-CF₂CF₂-SO₂ F by mass and 30% of CF ₂＝CF-O-CF₂CF₂-SO₂ F by mass, and the gas phase mixed monomer consists of 90% of tetrafluoroethylene and 10% of chlorotrifluoroethylene by mole ratio;

The fluorine-containing and chlorine-containing conductive polymer emulsion is hydrolyzed by sulfonyl fluoride-SO ₂ F to obtain a fluorine-containing and chlorine-containing conductive polymer with sulfonic acid-SO ₃ H;

The component B is a fluoroalkyl acrylate monomer or a fluoroalkyl methacrylate monomer or a mixture of the fluoroalkyl acrylate monomer and the fluoroalkyl methacrylate monomer, wherein the molecular weight of the fluoroalkyl acrylate monomer or the fluoroalkyl methacrylate monomer is less than 3000, and the melting point of the fluoroalkyl acrylate monomer or the fluoroalkyl methacrylate monomer is below 80 ℃;

component D is a high temperature free radical initiator.

2. The fluorine-containing polymer mixture for a high-moisture-permeability and super-breathable microporous membrane according to claim 1, wherein the high-molecular-weight polyethylene homo-or copolymer dispersion resin is an ultra-high-molecular-weight polytetrafluoroethylene homo-or copolymer dispersion resin, the standard specific gravity of which is 2.135-2.165 g/m ³, and the melting point of which is 325-350 ℃.

3. The fluorine-containing polymer mixture for the high-moisture-permeability and super-breathable microporous membrane according to claim 1, wherein the mass content of the component A, the component B, the component C and the component D is 65-80%, 6-15%, 2-23% and 0-2% in sequence.

4. The fluorine-containing polymer mixture for a high moisture-permeable and super breathable microporous membrane according to claim 1, wherein the component B comprises perfluorobutyl ethyl acrylate, perfluorobutyl ethyl methacrylate, perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, perfluorooctyl ethyl acrylate, perfluorooctyl ethyl methacrylate, N-methyl perfluorobutyl amine ethyl sulfonate, N-methyl perfluorohexyl amine ethyl sulfonate, N-methyl perfluorooctyl amine ethyl sulfonate.

5. The fluorine-containing polymer mixture for a high moisture-permeable and super breathable microporous membrane according to claim 1, wherein the polyurethane acrylate prepolymer is hot melt and has a melting point of less than 80 ℃, and the preparation raw materials thereof comprise:

aromatic diisocyanates, aliphatic diisocyanates;

A polyhydric alcohol with a molecular weight of 600-5000;

6. The fluorine-containing polymer mixture for a high moisture-permeable and super breathable microporous membrane according to claim 5, wherein the preparation method of the polyurethane acrylate prepolymer comprises the following steps:

The temperature in the reaction kettle is increased to 50-150 ℃, and polyol is introduced into the kettle for reaction for 10-180 min, wherein the polyol is polyether polyol or polyester polyol, and the molar ratio of diisocyanate to polyol is 2:1-8:1;

7. The fluorine-containing polymer mixture for a high moisture-permeable and super breathable microporous membrane according to claim 1, wherein the fluorine-free alkyl acrylate is a free-radically polymerizable monomer or a mixed monomer thereof, and comprises hydroxyalkyl acrylate, hydroxyalkyl methacrylate, C5-C20 alkyl acrylate, C4-C20 alkyl methacrylate, and C6-C20 vinyl acrylate, wherein the hydroxyalkyl acrylate comprises hydroxyethyl acrylate or hydroxypropyl acrylate, and the hydroxyalkyl methacrylate comprises hydroxyethyl methacrylate or hydroxypropyl methacrylate.

8. The fluorine-containing polymer mixture for the high-moisture-permeability and super-breathable microporous membrane according to claim 1, wherein the half-life of the high-temperature free radical initiator is measured at a temperature of 100-250 ℃, and the fluorine-containing polymer mixture specifically comprises dicumyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butylperoxy hexane, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butyl peroxide-3-hexyne and cumene hydroperoxide.

9. The application of the fluorine-containing polymer mixture for the high-moisture-permeability super-breathable microporous membrane according to any one of claims 1 to 8, wherein the fluorine-containing polymer mixture is applied to preparation of Gao Toushi super-breathable microporous membranes, and the preparation method specifically comprises the following steps: