WO2023050554A1 - 一种复合材料 - Google Patents

一种复合材料 Download PDF

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Publication number
WO2023050554A1
WO2023050554A1 PCT/CN2021/134235 CN2021134235W WO2023050554A1 WO 2023050554 A1 WO2023050554 A1 WO 2023050554A1 CN 2021134235 W CN2021134235 W CN 2021134235W WO 2023050554 A1 WO2023050554 A1 WO 2023050554A1
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composite material
composite
spinning
chlorosulfonated polyethylene
mass fraction
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PCT/CN2021/134235
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English (en)
French (fr)
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叶孔萌
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江苏青昀新材料科技有限公司
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Priority to JP2022556113A priority Critical patent/JP2024506225A/ja
Publication of WO2023050554A1 publication Critical patent/WO2023050554A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/11—Flash-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins

Definitions

  • the invention relates to the technical field of flash spinning, in particular to a composite material prepared by using the flash spinning technology.
  • the project team started the flash evaporation project in 2018, and has generated sales so far. It mainly uses polyethylene as raw material, and performs flash spinning after solvent dissolution. Compared with traditional products, the flash evaporation material prepared , which can be applied in a wider range. At the same time, it aims at the technical problems of poor shrinkage and low tear strength existing in the existing flash materials, and also has the technical problems of poor anti-mildew and antibacterial effects. Through the improvement of spinning polymer raw materials, as well as the selection of spinning solvent and spinning temperature, the performance of the flash material can be improved to expand its application range.
  • the purpose of the present invention is to overcome the deficiencies of the prior art and provide a composite material prepared by flash evaporation technology.
  • a kind of composite material it is characterized in that, the raw material of composite material comprises polyethylene,
  • the shrinkage rate R is 0.2 to 0.7;
  • the standard heat shrinkage strength ⁇ r is 0.5 ⁇ 3.5N/mm 2 ;
  • Shrinkage rate R [(L 0 -L 1 )/L0]
  • Mildew resistance level is less than level 2;
  • L0 is the initial length of the sample, (unit: mm);
  • S is the initial cross-sectional area of the sample, (unit is mm 2 );
  • L1 is the length of the sample after heat shrinkage, (unit: mm);
  • F r heat shrinkage force, (unit is N);
  • the shrinkage rate R of the composite material ranges from 0.2 to 0.3.
  • the shrinkage rate R of the composite material ranges from 0.3 to 0.4.
  • the shrinkage rate R of the composite material ranges from 0.4 to 0.5.
  • the shrinkage rate R of the composite material ranges from 0.5 to 0.6.
  • the shrinkage rate R of the composite material ranges from 0.6 to 0.7.
  • the standard thermal shrinkage strength ⁇ r of the composite material is 0.5-1.5N/mm 2 .
  • the standard thermal shrinkage strength ⁇ r of the composite material is 1.5-2.5N/mm 2 .
  • the standard thermal shrinkage strength ⁇ r of the composite material is 2.5-3.5N/mm 2 .
  • a composite material with a standard tear strength P of 7-12KN/m A composite material with a standard tear strength P of 7-12KN/m.
  • F is the average tear force, (in N);
  • d is the thickness of the sample, (in mm).
  • the standard tear strength P of the composite material is 7-8.5KN/m.
  • the standard tear strength P of the composite material is 8.5-10KN/m.
  • the standard tear strength P of the composite material is 10-12KN/m.
  • a kind of composite material the anti-mildew grade of the composite material is 0 grade.
  • the anti-mildew grade of the composite material is grade 1.
  • a composite material the raw material of the composite material also includes composite chlorosulfonated polyethylene; the mass fraction of the composite chlorosulfonated polyethylene in the mixture of the composite chlorosulfonated polyethylene and polyethylene is 6-8%.
  • Composite chlorosulfonated polyethylene is composed of porous boron nitride nanosheets of cuprous oxide/zinc borate, compatibilizer and chlorosulfonated polyethylene particles, among which, porous boron nitride nanosheets of cuprous oxide/zinc borate
  • the mass fraction in chlorosulfonated polyethylene is 11-13%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 180-240°C, and the flash-spun fibers are laid, and finally heated by a hot roller.
  • Composite materials prepared by the flash method were obtained after the pressing process.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller perform hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 5 to 10°C; and Both T up and T down are less than 135°C.
  • the tangent lines on both sides of the upper heating roller form an ⁇ angle, and the ⁇ angle is 100-140°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene.
  • the mass fraction of the spinning raw material in the spinning solution is 10-15%.
  • the spinning solvent is selected from aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, unsaturated hydrocarbons, halogenated hydrocarbons, alcohols, esters, ethers, ketones, nitriles, amides, and fluorocarbons several mixtures.
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, and 1,1,1,3,3-pentafluorobutane.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then copper sulfate and zinc sulfate are respectively added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, first Carry out the first step of calcination, the temperature of the first step of calcination is 130-150°C, the time of the first step of calcination is 0.5-1 hour, and then the temperature is raised for the second step of calcination, the temperature of the second step of calcination is 550-700°C, the second step of calcination The first calcination time is 1 to 2 hours, and the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, and then ground, and then the third step of calcination is carried out; the third step of calcination temperature is 400 ⁇ 500°C, the calcining time of the third step is 2 to
  • the mass fraction of the porous boron nitride nanosheet boron nitride in the sodium hydroxide solution is 5-20%, and the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 1-15%; the boron nitride has a porous layered structure,
  • the purpose of alkali treatment on the surface is for the subsequent adsorption of metal ions in the mixed solution of copper sulfate and zinc sulfate;
  • the specific surface of porous boron nitride nanosheets is 400-2500m 2 /g,
  • the nano sheet has mesopores of 0.3-15nm; the micropores of 0.5-1.5nm have a total pore volume of 0.2-2.4ml/g, wherein the mesopores account for 20-90% of the total pore volume.
  • the purpose of the first step of calcination in the present application is mainly to produce zinc oxide, and the purpose of the second step of calcination is
  • the mass ratio of copper sulfate and zinc sulfate is 1:2-1:5.
  • the mass ratio of the zinc sulfate to the porous boron nitride nanosheet is 1:2-1:5.
  • the mass fraction of the primary material in the boric acid solution is 3-6%.
  • the mass fraction of boric acid in the boric acid solution is 10-20%.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particle is 11-13%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.5-1%.
  • the antifungal and antibacterial functional material is zinc borate doped with cuprous oxide loaded on the boron nitride matrix, and the zinc borate doped with cuprous oxide is used to stab the cell wall of microorganisms to have both antifungal and antibacterial effects.
  • Porous boron nitride Nanosheets have large specific surface area and porous characteristics, so they have slow-release anti-mold and anti-bacterial effects. This application has better anti-mildew and anti-bacterial effect than simple raw materials (cuprous oxide and zinc borate).
  • ⁇ T is greater than 10°C
  • the stress of the fibrous tissue is large, the shrinkage rate is large, the shrinkage strength is large, and the tear strength is small.
  • the ⁇ angle is greater than 140°, the surface area of the coated hot roller is small, the heat setting time of the roller surface is short, and the stress release is insufficient, so the shrinkage rate and shrinkage strength become larger, while the tear strength becomes smaller.
  • Chlorosulfonated polyethylene is a white or yellow elastomer, soluble in aromatic hydrocarbons and chlorinated hydrocarbons, insoluble in fats and alcohols, only swellable but not soluble in ketones and ethers, and has excellent ozone resistance and atmospheric aging resistance , chemical corrosion resistance, etc., good physical and mechanical properties, aging resistance, heat resistance and low temperature resistance, oil resistance, flame resistance, wear resistance. Because of its good elasticity, it can improve the shrinkage performance of the product, which is one of the important factors for this application to select this raw material. At the same time, it is soluble in aromatic hydrocarbons and chlorinated hydrocarbons.
  • the raw material polyethylene for flash spinning of this application Dissolution in spinning solvents is similar.
  • a production method of flash spinning modified functional material which comprises the technical scheme of:
  • the spinning raw material is dissolved in the spinning solvent for dispersing and dissolving to obtain the spinning liquid, the mass fraction of the spinning raw material in the spinning liquid is 11.5-13.5%; then the spinning liquid is flash-spun at 185-250°C Lay the flash-spun fiber into the web, and finally pass the heat-pressing process through the hot roller to obtain the flash-spun modified functional material;
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller perform hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 5 to 10°C; and Both T up and T down are less than 135°C.
  • the tangent lines on both sides of the upper heating roller form an ⁇ angle, and the ⁇ angle is 100-140°.
  • the raw materials for spinning are composite chlorosulfonated polyethylene and polypropylene; the mass fraction of the composite chlorosulfonated polyethylene in the mixture of the composite chlorosulfonated polyethylene and polypropylene is 6-8%.
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, and 1,1,1,3,3-pentafluorobutane.
  • chlorosulfonated polyethylene can improve the shrinkage performance of the product, and the addition of cuprous oxide/zinc borate porous boron nitride nanosheets can significantly improve the long-lasting antibacterial and antifungal effects of the product. Therefore, it has a wide range of applications.
  • Fig. 3 is a hot pressing schematic diagram of the hot roller of the present application.
  • the initial size and length of the sample is L 0 (in centimeters), and the initial cross-sectional area of the sample is S (in square millimeters).
  • the size of the sample after thermal shrinkage is L 1 (in centimeters)
  • the maximum thermal shrinkage force is F r (in Newtons)
  • the maximum force that occurs during the cooling process is represented by F c (in Newtons) .
  • the standard heat shrinkage strength of the sample is obtained Shrinkage strength.
  • the bacteria used in the mildew test were Aspergillus niger CGMCC 3.5487, Chaetomium globosa CGMCC 3.3601, Penicillium fungus CGMCC3.3875, Trichoderma viride CGMCC 3.2941;
  • Anti-mold performance Constant temperature and humidity environment parameters 28°C ⁇ 1°C, 90% ⁇ 2%; cultivation time 28 days.
  • the bacteria used in the antibacterial test were Staphylococcus aureus, Klebsiella pneumoniae and Escherichia coli
  • the antibacterial rate (that is, the bacteriostatic rate) means that more than 95% have antibacterial properties, and when it is greater than 99%, it has better antibacterial function.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw material is dissolved in the spinning solvent to disperse and dissolve to obtain the spinning solution; then the spinning solution is flash-spun at 200°C, and the flash fiber is laid, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller 1 and the lower hot roller 2 perform hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 6°C; and Both T up and T down are less than 135°C.
  • the tangent lines on both sides of the upper heating roller form an ⁇ angle, and the ⁇ angle is 120°, wherein the ⁇ angle is specifically shown in FIG. 3 .
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 6%.
  • the mass fraction of spinning raw material in spinning solution is 12%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then copper sulfate and zinc sulfate are respectively added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, first Carry out the first step of calcination, the temperature of the first step of calcination is 130-150°C, the time of the first step of calcination is 0.5-1 hour, and then the temperature is raised for the second step of calcination, the temperature of the second step of calcination is 550-700°C, the second step of calcination The first calcination time is 1 to 2 hours, and the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, and then ground, and then the third step of calcination is carried out; the third step of calcination temperature is 400 ⁇ 500°C, the calcining time of the third step is 2 to
  • the mass fraction of the porous boron nitride nanosheet boron nitride in the sodium hydroxide solution is 6%, and the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 5%.
  • the mass ratio of copper sulfate and zinc sulfate is 1:2.
  • the mass ratio of zinc sulfate to porous boron nitride nanosheets is 1:2.
  • the mass fraction of the primary substance in the boric acid solution is 3%.
  • the mass fraction of boric acid in the boric acid solution is 12%.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 11%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.5%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 205°C, and the flash fibers are laid, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 7° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 122°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 6.5%.
  • the mass fraction of the spinning raw material in the spinning solution is 12.5%
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then copper sulfate and zinc sulfate are respectively added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, first Carry out the first step of calcination, the temperature of the first step of calcination is 130-150°C, the time of the first step of calcination is 0.5-1 hour, and then the temperature is raised for the second step of calcination, the temperature of the second step of calcination is 550-700°C, the second step of calcination The first calcination time is 1 to 2 hours, and the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, and then ground, and then the third step of calcination is carried out; the third step of calcination temperature is 400 ⁇ 500°C, the calcining time of the third step is 2 to
  • the mass fraction of the porous boron nitride nanosheet boron nitride in the sodium hydroxide solution is 8%, and the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 5%.
  • the mass ratio of copper sulfate and zinc sulfate is 1:2.5.
  • the mass ratio of zinc sulfate to porous boron nitride nanosheets is 1:2.5.
  • the mass fraction of the primary substance in the boric acid solution is 3.5%.
  • the mass fraction of boric acid in the boric acid solution is 12%.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 11.5%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.6%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then copper sulfate and zinc sulfate are respectively added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, first Carry out the first step of calcination, the temperature of the first step of calcination is 130-150°C, the time of the first step of calcination is 0.5-1 hour, and then the temperature is raised for the second step of calcination, the temperature of the second step of calcination is 550-700°C, the second step of calcination The first calcination time is 1 to 2 hours, and the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, and then ground, and then the third step of calcination is carried out; the third step of calcination temperature is 400 ⁇ 500°C, the calcining time of the third step is 2 to
  • the mass fraction of the porous boron nitride nanosheet boron nitride in the sodium hydroxide solution is 10%, and the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 5%.
  • the mass ratio of copper sulfate and zinc sulfate is 1:3.5.
  • the mass ratio of zinc sulfate to porous boron nitride nanosheets is 1:3.5.
  • the mass fraction of the primary substance in the boric acid solution is 5%.
  • the mass fraction of boric acid in the boric acid solution is 12%.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 12%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.7%.
  • Example 3 The product of Example 3 is placed in a normal temperature environment for 1 year, specifically, the temperature is 25 ⁇ 2°; the humidity is (60 ⁇ 5)%RH.
  • the anti-mildew grade of the sample tested again is grade 1, the anti-bacterial rate is 98.2%, and the decline in anti-bacterial and anti-mildew properties is low, playing a long-term anti-bacterial and anti-mildew effect.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent to disperse and dissolve to obtain the spinning solution; then the spinning solution is flash-spun at 215°C, and the flash fibers are laid, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 126°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7.5%.
  • the mass fraction of the spinning raw material in the spinning solution is 13.5%
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then copper sulfate and zinc sulfate are respectively added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, first Carry out the first step of calcination, the temperature of the first step of calcination is 130-150°C, the time of the first step of calcination is 0.5-1 hour, and then the temperature is raised for the second step of calcination, the temperature of the second step of calcination is 550-700°C, the second step of calcination The first calcination time is 1 to 2 hours, and the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, and then ground, and then the third step of calcination is carried out; the third step of calcination temperature is 400 ⁇ 500°C, the calcining time of the third step is 2 to
  • the mass fraction of porous boron nitride nanosheet boron nitride in the sodium hydroxide solution is 12%, and the mass fraction of sodium hydroxide in the sodium hydroxide solution is 5%.
  • the mass ratio of copper sulfate and zinc sulfate is 1:4.
  • the mass ratio of zinc sulfate to porous boron nitride nanosheets is 1:4.
  • the mass fraction of the primary substance in the boric acid solution is 5%.
  • the mass fraction of boric acid in the boric acid solution is 12%.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 12.5%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.8%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 220°C, the flash fiber is laid, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 128°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 8%.
  • the mass fraction of spinning raw material in spinning solution is 14%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then copper sulfate and zinc sulfate are respectively added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, first Carry out the first step of calcination, the temperature of the first step of calcination is 130-150°C, the time of the first step of calcination is 0.5-1 hour, and then the temperature is raised for the second step of calcination, the temperature of the second step of calcination is 550-700°C, the second step of calcination The first calcination time is 1 to 2 hours, and the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, and then ground, and then the third step of calcination is carried out; the third step of calcination temperature is 400 ⁇ 500°C, the calcining time of the third step is 2 to
  • the mass fraction of the porous boron nitride nano sheet boron nitride in the sodium hydroxide solution is 5-20%, and the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 5%.
  • the mass ratio of copper sulfate and zinc sulfate is 1:5.
  • the mass ratio of zinc sulfate to porous boron nitride nanosheets is 1:5.
  • the mass fraction of the primary substance in the boric acid solution is 6%.
  • the mass fraction of boric acid in the boric acid solution is 12%.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 13%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.8%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the composite chlorosulfonated polyethylene particles are composed of cuprous oxide, zinc borate, compatibilizer and chlorosulfonated polyethylene particles; wherein, the mixture of cuprous oxide, zinc borate and porous boron nitride nanosheets is compounded
  • the mass fraction in chlorosulfonated polyethylene particles is 12%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.7%.
  • the mass ratio of cuprous oxide and zinc borate is 1:3.5.
  • the mass ratio of zinc borate to porous boron nitride nanosheets is 1:3.5.
  • the product of this comparative example 1 is placed in a normal temperature environment for 1 year, specifically, the temperature is 25 ⁇ 2°; the humidity is (60 ⁇ 5)%RH.
  • the anti-mold grade of the sample tested again is 4 grades, and the antibacterial rate is 78.2%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then zinc sulfate is added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, the first step is carried out first Calcination, the calcination temperature of the first step is 130-150°C, the calcination time of the first step is 0.5-1 hour, and then the temperature is raised for the second step calcination, the calcination temperature of the second step is 550-700°C, and the calcination time of the second step is After 1-2 hours, the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, then ground, and then the third step is calcined; the third step calcining temperature is 400-500°C, the The three-step calcination time is 2 to 4 hours to obtain zinc borate/porous boron nitride nanosheets; finally,
  • the mass fraction of the porous boron nitride nanosheet boron nitride in the sodium hydroxide solution is 10%, and the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 5%.
  • the mass ratio of zinc sulfate to porous boron nitride nanosheets is 1:3.5.
  • the mass fraction of the primary substance in the boric acid solution is 5%.
  • the mass fraction of boric acid in the boric acid solution is 12%.
  • the mass fraction of zinc borate/porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 12%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.7%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 8%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller Composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 ° C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 9%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 10.5%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 13.5%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 14.5%.
  • the SEM figure of the contrast product the SEM of embodiment 3 is Fig. 1;
  • the SEM of comparative example 7 is Fig. 2.
  • the porous boron nitride nanosheets of cuprous oxide/zinc borate are high, it can be seen from SEM test Figure 3 that the content of the final product is relatively high, and the expected purpose cannot be achieved.
  • Figure 1 of the SEM of Example 3 the distribution is uniform and no agglomeration occurs.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 16%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller Composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then copper sulfate and zinc sulfate are respectively added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, first Carry out the first step of calcination, the temperature of the first step of calcination is 130-150°C, the time of the first step of calcination is 0.5-1 hour, and then the temperature is raised for the second step of calcination, the temperature of the second step of calcination is 550-700°C, the second step of calcination The first calcination time is 1 to 2 hours, and the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, and then ground, and then the third step of calcination is carried out; the third step of calcination temperature is 400 ⁇ 500°C, the calcining time of the third step is 2 to
  • the mass fraction of the porous boron nitride nanosheet boron nitride in the sodium hydroxide solution is 10%, and the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 5%.
  • the mass ratio of copper sulfate and zinc sulfate is 1:0.5.
  • the mass ratio of zinc sulfate to porous boron nitride nanosheets is 1:3.5.
  • the mass fraction of the primary substance in the boric acid solution is 5%.
  • the mass fraction of boric acid in the boric acid solution is 12%.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 12%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.7%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles comprises the following steps:
  • the porous boron nitride nanosheets are dispersed in the sodium hydroxide solution by microwave stirring for alkali treatment, then copper sulfate and zinc sulfate are respectively added to the sodium hydroxide solution, the mixture is obtained by filtration and separation, and then ground, first Carry out the first step of calcination, the temperature of the first step of calcination is 130-150°C, the time of the first step of calcination is 0.5-1 hour, and then the temperature is raised for the second step of calcination, the temperature of the second step of calcination is 550-700°C, the second step of calcination The first calcination time is 1 to 2 hours, and the primary product is prepared; secondly, the primary product is added to the boric acid solution, then filtered and separated, and then ground, and then the third step of calcination is carried out; the third step of calcination temperature is 400 ⁇ 500°C, the calcining time of the third step is 2 to
  • the mass fraction of the porous boron nitride nanosheet boron nitride in the sodium hydroxide solution is 10%, and the mass fraction of the sodium hydroxide in the sodium hydroxide solution is 5%.
  • the mass ratio of copper sulfate and zinc sulfate is 1:1.
  • the mass ratio of zinc sulfate to porous boron nitride nanosheets is 1:3.5.
  • the mass fraction of the primary substance in the boric acid solution is 5%.
  • the mass fraction of boric acid in the boric acid solution is 12%.
  • the mass fraction of cuprous oxide/zinc borate porous boron nitride nanosheets in the composite chlorosulfonated polyethylene particles is 12%.
  • the mass fraction of the compatibilizer in the composite chlorosulfonated polyethylene particles is 0.7%.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller Composite material is obtained.
  • the hot roller is subjected to the hot pressing process, specifically, the upper hot roller and the lower hot roller are hot pressed, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 13° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles is the same as in Example 3.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 2° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles is the same as in Example 3.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller Composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 ° C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 150°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles is the same as in Example 3.
  • a method for producing a composite material comprising the technical proposal of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller composite material is obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 90°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles is the same as in Example 3.
  • a production method of flash spinning modified functional material which comprises the technical scheme of:
  • the spinning raw material is dissolved in the spinning solvent to disperse and dissolve to obtain the spinning solution; then the spinning solution is flash-spun at 200°C, and the flash fiber is laid, and finally the hot-pressing process is carried out by a hot roller Finally, flash spinning modified functional materials are obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 6° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 120°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polypropylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polypropylene is 6%.
  • the mass fraction of spinning raw material in spinning solution is 12%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles is the same as in Example 1.
  • a production method of flash spinning modified functional material which comprises the technical scheme of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 210°C, and the flash fiber is laid out, and finally the hot-pressing process is carried out by a hot roller Finally, flash spinning modified functional materials are obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 7° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 122°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 7%.
  • the mass fraction of spinning raw material in spinning solution is 13%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles is the same as in Example 3.
  • a production method of flash spinning modified functional material which comprises the technical scheme of:
  • the spinning raw materials are dissolved in the spinning solvent for dispersion and dissolution to obtain the spinning solution; then the spinning solution is flash-spun at 220°C, the flash fiber is laid, and finally the hot-pressing process is carried out by a hot roller Finally, flash spinning modified functional materials are obtained.
  • the hot roller performs the hot pressing process, specifically, the upper hot roller and the lower hot roller carry out hot pressing, and the absolute value ⁇ T of the difference between the surface temperature T of the upper hot roller and the surface temperature T of the lower hot roller is 8° C.; and T are less than 135 °C.
  • the tangent lines on both sides of the upper heat roller form an ⁇ angle, and the ⁇ angle is 124°.
  • the raw material for spinning is composite chlorosulfonated polyethylene and polyethylene; the mass fraction of composite chlorosulfonated polyethylene in the mixture of composite chlorosulfonated polyethylene and polyethylene is 8%.
  • the mass fraction of spinning raw material in spinning solution is 14%;
  • the spinning solvent is a mixture of 1-pentene, trichlorofluoromethane, dichloromethane, cyclopentane, 2,3 dihydrodecafluoropentane, 1,1,1,3,3-pentafluorobutane; weight The ratio is 6:5:4:3:1:1.
  • the preparation method of the composite chlorosulfonated polyethylene particles is the same as in Example 5.

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Abstract

一种复合材料，其特征在于，复合材料的原料包含聚乙烯；收缩率R为0.2～0.7；标准热缩强度σ r为0.5～3.5N/mm 2；防霉等级为小于2级。本申请具有良好的收缩性能，且具有较佳的抗菌防霉效果，因此具有广泛的应用。

Description

一种复合材料 【技术领域】
本发明涉及闪蒸纺丝技术领域，具体的说，是一种利用闪蒸技术制备的复合材料。
【背景技术】
我国以及全世界对新型流行性病毒的防护服研发还远远不够。开发抗菌抗病毒防护服、可重复使用的防护服、高阻隔高舒适高强力的防护材料成为众多科研机构、企业的研发重点。闪蒸纺丝技术是美国杜邦科学家在上世纪60年代发明的，是一种制备高技术非织造布的方法，用这种方法制备的非织造布面料同时综合了纸张、薄膜和布料的特点，具有质轻、高强、防水、透气、耐撕裂、耐穿刺等特点，应用范围较广，尤其适合应用在个人防护、医疗包装、国防、建筑、印刷等领域。但该技术较为复杂，而且产品主要从美国进口，我国亟需在该领域进行突破。本项目组从2018年开始对闪蒸项目开始立项，到目前产生销售额，主要以聚乙烯为原料，通过是溶剂溶解后进行闪蒸纺丝，所制备的闪蒸材料，与传统产品相比，可应用的范围更广。同时针对现有闪蒸材料存在的收缩性较差，以及撕裂强度低的技术问题，另外还存在防霉和抗菌效果不佳的技术问题。通过纺丝聚合物原料的改进，以及纺丝溶剂和纺丝温度的选择，来改善闪蒸材料的性能，以扩大其应用范围。
【发明内容】
本发明的目的在于克服现有技术的不足，提供一种复合材料，由闪蒸技术制备。
本发明的目的是通过以下技术方案来实现的：
一种复合材料，其特征在于，复合材料的原料包含聚乙烯，
收缩率R为0.2～0.7；
标准热缩强度σ r为0.5～3.5N/mm 2；
收缩率R＝[(L 0-L 1)/L0]；
标准热缩强度为σ r＝[F r/S]*[实际克重/50g/m 2]；
防霉等级为小于2级；
公式中的符号分别为：
L 0为试样初始长度，(单位为mm)；
S为试样的初始截面积，(单位为mm 2)；
L 1为试样热收缩后的长度，(单位为mm)；
F r为热缩力，(单位为N)；
复合材料的收缩率R的范围为0.2～0.3。
复合材料的收缩率R的范围为0.3～0.4。
复合材料的收缩率R的范围为0.4～0.5。
复合材料的收缩率R的范围为0.5～0.6。
复合材料的收缩率R的范围为0.6～0.7。
复合材料的标准热缩强度σ r为0.5～1.5N/mm 2。
复合材料的标准热缩强度σ r为1.5～2.5N/mm 2。
复合材料的标准热缩强度σ r为2.5～3.5N/mm 2。
一种复合材料，标准撕裂强度P为7～12KN/m。
P＝[F/d]*[实际克重/50g/m 2]；
F为平均撕裂力，(单位为N)；
d为试样的厚度，(单位为mm)。
复合材料的标准撕裂强度P为7～8.5KN/m。
复合材料的标准撕裂强度P为8.5～10KN/m。
复合材料的标准撕裂强度P为10～12KN/m。
一种复合材料，复合材料的防霉等级为0级。
复合材料的防霉等级为1级。
一种复合材料，复合材料的原料还包含复合氯磺化聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为6～8％。
复合氯磺化聚乙烯由氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂和氯磺化聚乙烯粒子组成，其中，氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯中的质量分数为11～13％。
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在180～240℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到闪蒸法制备的复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为5～10℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为100～140°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯。
纺丝原料在纺丝液中的质量分数为10～15％。
纺丝溶剂选自芳香烃类、脂族烃类、脂环烃类、不饱和烃类、卤化烃类、醇类、酯类、醚类、酮类、腈类、酰胺、碳氟化合物类中的几种混合物。
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再分别将硫酸铜和硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到氧化亚铜/硼酸锌的多孔氮化硼纳米片；最后，将氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为5～20％，氢氧化钠溶液中氢氧化钠的质量分数为1～15％；氮化硼具有多孔层状结构，作为吸附载体，在表面进行碱处理目的是为了后续与硫酸铜和硫酸锌的混合溶液中的金属离子的吸附；多孔氮化硼纳米片的比表面为400～2500m 2/g，多孔氮化硼纳米片具有0.3～15nm的介孔；具有0.5～1.5nm的微孔总孔容为0.2～2.4ml/g，其中介孔占总孔容的20～90％。本申请的第一步煅烧的目的主要是生产氧化锌，第二步煅烧的目的主要是生成氧化亚铜。这是分段煅烧的目的，主要是为了生成不同产物。
硫酸铜和硫酸锌的质量比为1:2～1:5。
硫酸锌与多孔氮化硼纳米片的质量比为1:2～1:5。
初级物在硼酸溶液中的质量分数为3～6％。
硼酸溶液中的硼酸质量分数为10～20％。
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为11～13％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.5～1％。
防霉抗菌功能材料为在氮化硼基体上负载参杂氧化亚铜的硼酸锌，利用参杂氧化亚铜的硼酸锌通过刺人微生物的细胞壁从而兼具防霉和抗菌功效，多孔氮化硼纳米片具有较大的比表面积和多孔特点，因此具有缓慢释放防霉和抗菌功效。本申请比单纯的原料(氧化亚铜和硼酸锌)混合具有更佳的防霉抗菌效果。当氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯中的质量分数较低时，其分布趋向于均匀状态，且在复合氯磺化聚乙烯中之间互相接触的概率变低，因此可以显著承受一定的撕裂力，吸收较多的应力作 用，且可以降低最终产品在受力时聚合物的分子之间的运动，对裂纹的产生起到延缓功能，对提高最终产品的撕裂强度等性能产生明显正向影响。当氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯中的质量分数较高时，其本身容易产生局部团聚现象而产生，破坏了产品的均衡分布结构，导致性能变差，从而达不到预期的目的。这是本申请选择氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为11～13％的范围的原因。对于热压工艺的参数，当ΔT大于10℃，因为两面烫光温度差异大，纤维组织应力大，收缩率变大，收缩强度变大；撕裂强度变小。当α角大于140°，包覆热辊的面面积少，辊面热定型时间短，应力释放不充分，因此收缩率和收缩强度变大，而撕裂强度变小。
氯磺化聚乙烯为白色或黄色弹性体，能溶解于芳香烃及氯代烃不溶于脂肪及醇中，在酮和醚中只能溶胀不能溶解，有优异的耐臭氧性、耐大气老化性、耐化学腐蚀性等，较好的物理机械性能、耐老化性能、耐热及耐低温性、耐油性、耐燃性、耐磨性。其由于具有良好的弹性，因此可以改善产品的收缩性能，这是本申请选择此原料的重要因素之一，同时其溶解于芳香烃及氯代烃，本申请的闪蒸纺丝的原料聚乙烯溶解在纺丝溶剂相似。
一种闪纺改性功能材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液，纺丝原料在纺丝液中的质量分数为11.5～13.5％；然后纺丝液在185～250℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到闪纺改性功能材料；
热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为5～10℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为100～140°。
纺丝原料为复合氯磺化聚乙烯以及聚丙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚丙烯的混合物中的质量分数为6～8％。
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物。
与现有技术相比，本发明的积极效果是：
本申请加入氯磺化聚乙烯可以改善产品的收缩性能，加入氧化亚铜/硼酸锌的多孔氮化硼纳米片，可以显著改善产品的持久抗菌防霉效果。因此具有广泛的应用。
【附图说明】
图1实施例3的产品的SEM图；
图2对比例7的产品的SEM图；
图3本申请的热辊的热压示意图；
附图中的标记为：1上热辊，2下热辊。
【具体实施方式】
以下提供本发明一种复合材料的具体实施方式。
一、收缩率R和标准热缩强度σ r的测试：
收缩率和热缩强度的测试参见国标GB/T 34848-2017(热收缩薄膜性能试验方法)，其测试的基本的过程为：
试样初始尺寸长度为L 0(单位为厘米)，试样的初始截面积为S(单位为平方毫米)，试样在加热后，当达到最大热收缩力后再冷却至40℃温度后，试样热收缩后的尺寸为L 1(单位为厘米)，最大热收缩力为F r(单位为牛顿)，在冷却过程中出现的最大力为冷缩力用F c(单位为牛顿)表示。对于样品，取10个样进行求平均，然后再化归法，根据公式：标准热缩强度为σ r＝[F r/S]*[实际克重/50g/m 2]；得到样品的标准热缩强度。
二、标准撕裂强度P的测试：
撕裂强度的测试参见标准GB/T16578.1-2008/ISO6363-1:1983(塑料薄膜和薄片，耐撕裂性能大的测定第一部分：裤形撕裂法)，其测试的基本的过程为：
在200mm/min的试验速度下，使裂纹贯穿样品所需的平均力用F表示，对于样品，取10个样进行求平均。然后再化归法，根据公式：标准撕裂强度P＝[F/d]*[实际克重/50g/m 2]；F为平均撕裂力(单位为牛顿)；d为试样的厚度(单位为毫米)。
三、白度W的测试：
白度的测试，参见国标GB/T22880-2008(纸和纸板CIE白度的测定，D65/10°室外日光)，在标准规定的条件下，通过测量CIE三刺激值得到白度。
四、防霉等级AMA的测试：
防霉等级的测试，参见标准GB/T 24346-2009(纺织品防霉性能的评价)，具体的测试条件为：
防霉测试所用的菌种为黑曲霉CGMCC 3.5487、球毛壳霉CGMCC 3.3601、绳状青霉CGMCC3.3875、绿色木霉CGMCC 3.2941；
防霉性能恒温恒湿环境参数：28℃±1℃，90％±2％；培养时间28天。
五、抗菌率A的测试：
抗菌率的测试，参见标准GB/T 20944.2-2007(纺织品抗菌性能的评价第2部分：吸收法)具体的测试条件为：
抗菌测试所用的菌种为金黄色葡萄球菌，肺炎克雷白球菌以及大肠杆菌
培养条件：37℃±2℃，90％±2％；培养时间18-24小时。
抗菌率(即为抑菌率)表示，95％以上具有抗菌性能，当大于99％时具有较佳的抗菌功能。
实施例1
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在200℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊1和下热辊2进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为6℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为120°，其中α角具体如图3所示。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为6％。
纺丝原料在纺丝液中的质量分数为12％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再分别将硫酸铜和硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到氧化亚铜/硼酸锌的多孔氮化硼纳米片；最后，将氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为6％，氢氧化钠 溶液中氢氧化钠的质量分数为5％。
硫酸铜和硫酸锌的质量比为1:2。
硫酸锌与多孔氮化硼纳米片的质量比为1:2。
初级物在硼酸溶液中的质量分数为3％。
硼酸溶液中的硼酸质量分数为12％。
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为11％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.5％。
本实施例1的产品测试性能数据见表1。
实施例2
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在205℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为7℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为122°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为6.5％。
纺丝原料在纺丝液中的质量分数为12.5％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再分别将硫酸铜和硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到氧化亚铜/硼酸锌的多孔氮化硼纳米片；最后，将氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为8％，氢氧化钠溶液中氢氧化钠的质量分数为5％。
硫酸铜和硫酸锌的质量比为1:2.5。
硫酸锌与多孔氮化硼纳米片的质量比为1:2.5。
初级物在硼酸溶液中的质量分数为3.5％。
硼酸溶液中的硼酸质量分数为12％。
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为11.5％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.6％。
本实施例2的产品测试性能数据见表1。
实施例3
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再分别将硫酸铜和硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到氧化亚铜/硼酸锌的多孔氮化硼纳米片；最后，将氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为10％，氢氧化钠溶液中氢氧化钠的质量分数为5％。
硫酸铜和硫酸锌的质量比为1:3.5。
硫酸锌与多孔氮化硼纳米片的质量比为1:3.5。
初级物在硼酸溶液中的质量分数为5％。
硼酸溶液中的硼酸质量分数为12％。
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为12％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.7％。
本实施例3的产品测试性能数据见表1。
对本实施例3的产品进行放置在常温环境中1年，具体为温度为25±2°；湿度为湿度(60±5)％RH。再次测试样品的防霉等级为1级，抗菌率为98.2％，抗菌和防霉性能下降较低，起到长期具有抗菌防霉功效。
实施例4
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在215℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为126°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7.5％。
纺丝原料在纺丝液中的质量分数为13.5％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再分别将硫酸铜和硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到氧化亚铜/硼酸锌的多孔氮化硼纳米片；最后，将氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为12％，氢氧化 钠溶液中氢氧化钠的质量分数为5％。
硫酸铜和硫酸锌的质量比为1:4。
硫酸锌与多孔氮化硼纳米片的质量比为1:4。
初级物在硼酸溶液中的质量分数为5％。
硼酸溶液中的硼酸质量分数为12％。
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为12.5％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.8％。
本实施例4的产品测试性能数据见表1。
实施例5
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在220℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为128°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为8％。
纺丝原料在纺丝液中的质量分数为14％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再分别将硫酸铜和硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到氧化亚铜/硼酸锌的多孔氮化硼纳米片；最后，将氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为5～20％，氢氧化钠溶液中氢氧化钠的质量分数为5％。
硫酸铜和硫酸锌的质量比为1:5。
硫酸锌与多孔氮化硼纳米片的质量比为1:5。
初级物在硼酸溶液中的质量分数为6％。
硼酸溶液中的硼酸质量分数为12％。
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为13％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.8％。
本实施例5的产品测试性能数据见表1。
对比例1
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子，由氧化亚铜，硼酸锌，相容剂以及氯磺化聚乙烯粒子组成；其中，氧化亚铜，硼酸锌以及多孔氮化硼纳米片的混合物在复合氯磺化聚乙烯粒子中的质量分数为12％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.7％。
氧化亚铜和硼酸锌的质量比为1:3.5。
硼酸锌与多孔氮化硼纳米片的质量比为1:3.5。
本对比例1的产品测试性能数据见表1。
对本对比例1的产品进行放置在常温环境中1年，具体为温度为25±2°；湿度为湿度(60±5)％RH。再次测试样品的防霉等级为4级，抗菌率为78.2％，抗菌和防霉性能下降非常明显，不再具有抗菌防霉功效。
对比例2
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝 液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再将硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到硼酸锌/多孔氮化硼纳米片；最后，将硼酸锌/多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为10％，氢氧化钠溶液中氢氧化钠的质量分数为5％。
硫酸锌与多孔氮化硼纳米片的质量比为1:3.5。
初级物在硼酸溶液中的质量分数为5％。
硼酸溶液中的硼酸质量分数为12％。
硼酸锌/多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为12％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.7％。
本对比例2的产品测试性能数据见表1。
对比例3
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例3，区别仅仅在于：
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为8％。
本对比例3的产品测试性能数据见表1。
对比例4
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例3，区别仅仅在于：
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为9％。
本对比例4的产品测试性能数据见表1。
对比例5
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺 化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例3，区别仅仅在于：
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为10.5％。
本对比例5的产品测试性能数据见表1。
对比例6
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例3，区别仅仅在于：
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为13.5％。
本对比例6的产品测试性能数据见表1。
对比例7
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例3，区别仅仅在于：
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为14.5％。
对照产品的SEM图，实施例3的SEM为图1；对比例7的SEM为图2。当氧化亚铜/硼酸锌的多孔氮化硼纳米片较高时，通过SEM测试图3可以看出，其在最终产品含量较高，起不到预期的目的。而通过实施例3的SEM的图1可以看出，其分布均匀，没有发生团聚现象。
本对比例7的产品测试性能数据见表1。
对比例8
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例3，区别仅仅在于：
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为16％。
本对比例8的产品测试性能数据见表1。
对比例9
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再分别将硫酸铜和硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到氧化亚铜/硼酸锌的多孔氮化硼纳米片；最后，将氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为10％，氢氧化钠溶液中氢氧化钠的质量分数为5％。
硫酸铜和硫酸锌的质量比为1:0.5。
硫酸锌与多孔氮化硼纳米片的质量比为1:3.5。
初级物在硼酸溶液中的质量分数为5％。
硼酸溶液中的硼酸质量分数为12％。
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为12％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.7％。
本对比例9的产品测试性能数据见表1。
对比例10
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其包含的具体步骤为：
首先将多孔氮化硼纳米片通过微波搅拌的方式分散在氢氧化钠溶液中进行碱处理，再分别将硫酸铜和硫酸锌加入到氢氧化钠溶液中，过滤分离得到混合物，再进行研磨，先进行第一步煅烧，第一步煅烧温度为130～150℃，第一步煅烧时间为0.5～1小时，然后再升温进行第二步煅烧，第二步煅烧温度为550～700℃，第二步煅烧时间为1～2小时，制备得到初级物；其次，将初级物再加入到硼酸溶液中，再进行过滤分离，再进行研磨，然后进行第三步煅烧；第三步煅烧温度为400～500℃，第三步煅烧时间为2～4小时，得到氧化亚铜/硼酸锌的多孔氮化硼纳米片；最后，将氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂与氯磺化聚乙烯粒子进行熔融挤出造粒得到复合氯磺化聚乙烯。
多孔氮化硼纳米片氮化硼在氢氧化钠溶液中的质量分数为10％，氢氧化钠溶液中氢氧化钠的质量分数为5％。
硫酸铜和硫酸锌的质量比为1:1。
硫酸锌与多孔氮化硼纳米片的质量比为1:3.5。
初级物在硼酸溶液中的质量分数为5％。
硼酸溶液中的硼酸质量分数为12％。
氧化亚铜/硼酸锌的多孔氮化硼纳米片在复合氯磺化聚乙烯粒子中的质量分数为12％。
相容剂在复合氯磺化聚乙烯粒子中的质量分数为0.7％。
本对比例10的产品测试性能数据见表1。
对比例11
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为13℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺 化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其同实施例3。
本对比例11的产品测试性能数据见表1。
对比例12
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为2℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其同实施例3。
本对比例12的产品测试性能数据见表1。
对比例13
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为150°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其同实施例3。
本对比例13的产品测试性能数据见表1。
对比例14
一种复合材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到复合材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为90°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，其同实施例3。
本对比例14的产品测试性能数据见表1。
实施例6
一种闪纺改性功能材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在200℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到闪纺改性功能材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为6℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为120°。
纺丝原料为复合氯磺化聚乙烯和聚丙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚丙烯的混合物中的质量分数为6％。
纺丝原料在纺丝液中的质量分数为12％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例1。
本实施例11的产品测试性能数据见表1。
实施例7
一种闪纺改性功能材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝 液在210℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到闪纺改性功能材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为7℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为122°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为7％。
纺丝原料在纺丝液中的质量分数为13％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例3。
本实施例7的产品测试性能数据见表1。
实施例8
一种闪纺改性功能材料的生产方法，其包含的技术方案为：
首先将纺丝原料溶解在纺丝溶剂中进行分散溶解得到纺丝液；然后纺丝液在220℃下进行闪蒸纺丝，将闪蒸纤维进行铺网，最后再通过热辊进行热压工艺后得到闪纺改性功能材料。热辊进行热压工艺，具体为上热辊和下热辊进行热压，上热辊的表面温度T 上和下热辊的表面温度T 下的差的绝对值ΔT为8℃；且T 上和T 下均小于135℃。上热辊的两面切线形成α角，α角为124°。
纺丝原料为复合氯磺化聚乙烯和聚乙烯；复合氯磺化聚乙烯在复合氯磺化聚乙烯和聚乙烯的混合物中的质量分数为8％。
纺丝原料在纺丝液中的质量分数为14％；
纺丝溶剂为1-戊烯，三氯氟甲烷，二氯甲烷，环戊烷，2,3二氢十氟戊烷，1,1,1,3,3-五氟丁烷的混合物；重量比为6:5:4:3:1:1。
所述的复合氯磺化聚乙烯粒子的制备方法，同实施例5。
本实施例8的产品测试性能数据见表1。
表1产品的测试数据表
Figure PCTCN2021134235-appb-000001
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改进和润饰， 这些改进和润饰也应视为本发明的保护范围内。

Claims (16)

  1. 一种复合材料，其特征在于，复合材料的原料包含聚乙烯；收缩率R为0.2～0.7；标准热缩强度σ r为0.5～3.5N/mm 2；防霉等级为小于2级；其中：收缩率R＝[(L 0-L 1)/L0]；标准热缩强度为σ r＝[F r/S]*[实际克重/50g/m 2]；公式中的符号分别为：L 0为试样初始长度；S为试样的初始截面积；L 1为试样热收缩后的长度；F r为热缩力。
  2. 如权利要求1所述的一种复合材料，其特征在于，复合材料的收缩率R的范围为0.2～0.3。
  3. 如权利要求1所述的一种复合材料，其特征在于，复合材料的收缩率R的范围为0.3～0.4。
  4. 如权利要求1所述的一种复合材料，其特征在于，复合材料的收缩率R的范围为0.4～0.5。
  5. 如权利要求1所述的一种复合材料，其特征在于，复合材料的收缩率R的范围为0.5～0.6。
  6. 如权利要求1所述的一种复合材料，其特征在于，复合材料的收缩率R的范围为0.6～0.7。
  7. 如权利要求1所述的一种复合材料，其特征在于，复合材料的标准热缩强度为0.5～1.5N/mm 2。
  8. 如权利要求1所述的一种复合材料，其特征在于，复合材料的标准热缩强度为1.5～2.5N/mm 2。
  9. 如权利要求1所述的一种复合材料，其特征在于，复合材料的标准热缩强度为2.5～3.5N/mm 2。
  10. 如权利要求1所述的一种复合材料，其特征在于，复合材料的标准撕裂强度P为7～12KN/m；其中：P＝[F/d]*[实际克重/50g/m 2]；公式中的符号分别为：F为平均撕裂力；d为试样的厚度。
  11. 如权利要求10所述的一种复合材料，其特征在于，复合材料的标准撕裂强度P为7～8.5KN/m。
  12. 如权利要求10所述的一种复合材料，其特征在于，复合材料的标准撕裂强度P为8.5～10KN/m。
  13. 如权利要求10所述的一种复合材料，其特征在于，复合材料的标准撕裂强度P为10～12KN/m。
  14. 如权利要求1所述的一种复合材料，其特征在于，复合材料的防霉等级为0级。
  15. 如权利要求1所述的一种复合材料，其特征在于，复合材料的防霉等级为1级。
  16. 如权利要求1所述的一种复合材料，其特征在于，复合材料的原料还包含复合氯磺化聚乙烯；复合氯磺化聚乙烯由氧化亚铜/硼酸锌的多孔氮化硼纳米片，相容剂和氯磺化聚乙烯粒子组成。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0357364A2 (en) * 1988-08-30 1990-03-07 E.I. Du Pont De Nemours And Company A process for flash-spinning dry polymeric plexifilamentary film-fibril strands
CN1042741A (zh) * 1988-08-31 1990-06-06 纳幕尔杜邦公司 聚合物丛丝的闪蒸纺丝
JPH05295613A (ja) * 1992-04-15 1993-11-09 Asahi Chem Ind Co Ltd 改良フラッシュ紡糸方法
DE60021925T2 (de) * 2000-12-14 2006-05-24 E.I. Du Pont De Nemours And Co., Wilmington Flash-spinnen von polycyclopenten
JP2007077519A (ja) * 2005-09-13 2007-03-29 Mitsui Chemicals Inc 抗菌性の繊維の集合体、その製造方法および用途
CN103757735A (zh) * 2013-12-26 2014-04-30 江苏神泰科技发展有限公司 一种高模量聚乙烯纤维的制备方法
CN110387053A (zh) * 2019-08-09 2019-10-29 广东安德力新材料有限公司 抗菌防霉母粒的制备工艺、抗菌防霉型交联热收缩膜及其制备工艺
CN111016374A (zh) * 2019-12-08 2020-04-17 国网江苏省电力有限公司滨海县供电分公司 用于干式变压器绕包的绝缘膜

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5435559B2 (ja) * 2009-10-08 2014-03-05 独立行政法人物質・材料研究機構 超薄窒化ホウ素ナノシートの製造方法
CN102513083A (zh) * 2011-12-13 2012-06-27 吉林省兰舍硅藻新材料有限公司 一种硅藻土负载纳米氧化锌复合粉体材料的制备方法
CN108872204B (zh) * 2018-04-27 2020-12-01 中国科学院兰州化学物理研究所 一种二维多孔石墨烯/氧化亚铜复合材料的制备和应用
CN109137121A (zh) * 2018-08-18 2019-01-04 宁波高新区诠宝绶新材料科技有限公司 一种矿山用铒掺杂抗静电风筒布的制作方法
CN109295537B (zh) * 2018-09-28 2021-10-22 温州亚迦布科技有限公司 一种柔韧耐磨抗菌扁丝及其拉丝工艺
CN109868518B (zh) * 2019-02-18 2020-10-23 浙江千禧龙纤特种纤维股份有限公司 一种抑菌型超高分子量聚乙烯纤维的生产方法
CN111118642A (zh) * 2019-12-19 2020-05-08 安徽诚德刷业有限公司 一种工业用刷的耐磨刷丝制造工艺

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0357364A2 (en) * 1988-08-30 1990-03-07 E.I. Du Pont De Nemours And Company A process for flash-spinning dry polymeric plexifilamentary film-fibril strands
CN1042741A (zh) * 1988-08-31 1990-06-06 纳幕尔杜邦公司 聚合物丛丝的闪蒸纺丝
JPH05295613A (ja) * 1992-04-15 1993-11-09 Asahi Chem Ind Co Ltd 改良フラッシュ紡糸方法
DE60021925T2 (de) * 2000-12-14 2006-05-24 E.I. Du Pont De Nemours And Co., Wilmington Flash-spinnen von polycyclopenten
JP2007077519A (ja) * 2005-09-13 2007-03-29 Mitsui Chemicals Inc 抗菌性の繊維の集合体、その製造方法および用途
CN103757735A (zh) * 2013-12-26 2014-04-30 江苏神泰科技发展有限公司 一种高模量聚乙烯纤维的制备方法
CN110387053A (zh) * 2019-08-09 2019-10-29 广东安德力新材料有限公司 抗菌防霉母粒的制备工艺、抗菌防霉型交联热收缩膜及其制备工艺
CN111016374A (zh) * 2019-12-08 2020-04-17 国网江苏省电力有限公司滨海县供电分公司 用于干式变压器绕包的绝缘膜

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