CN111155190B - Preparation method and application of porous sheet capable of blocking UV and VOC - Google Patents
Preparation method and application of porous sheet capable of blocking UV and VOC Download PDFInfo
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- CN111155190B CN111155190B CN202010047387.1A CN202010047387A CN111155190B CN 111155190 B CN111155190 B CN 111155190B CN 202010047387 A CN202010047387 A CN 202010047387A CN 111155190 B CN111155190 B CN 111155190B
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- metal
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- porous sheet
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- 230000000903 blocking effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- -1 salt compound Chemical class 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 15
- 239000000516 sunscreening agent Substances 0.000 claims abstract description 15
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 12
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001413 amino acids Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 235000021466 carotenoid Nutrition 0.000 claims description 3
- 150000001747 carotenoids Chemical class 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
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- 229920001282 polysaccharide Polymers 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- 230000006750 UV protection Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
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- OCLXJTCGWSSVOE-UHFFFAOYSA-N ethanol etoh Chemical compound CCO.CCO OCLXJTCGWSSVOE-UHFFFAOYSA-N 0.000 description 1
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- 239000012982 microporous membrane Substances 0.000 description 1
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- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- D01F6/50—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 polyalcohols, polyacetals or polyketals
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/02—Layered materials
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/10—Impermeable to liquids, e.g. waterproof; Liquid-repellent
-
- 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
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2400/00—Functions or special features of garments
- A41D2400/26—UV light protection
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention discloses a preparation method of a porous sheet material capable of blocking UV and VOC, which comprises the following steps: uniformly dissolving a high molecular polymer in a solvent, adding a metal salt compound, and uniformly stirring to obtain the metal-high molecular spinning solution; preparing a metal-polymer composite sheet from the prepared metal-polymer spinning solution by adopting an electrostatic spinning method; dissolving a metal salt compound and a ligand in water, adding a natural non-toxic sunscreen agent, uniformly mixing, adding the metal-polymer composite sheet prepared in the step S2, soaking, cooling to room temperature after soaking, washing with a solvent for several times, and drying to obtain the porous sheet capable of blocking UV and VOC. The porous sheet material has excellent characteristics of blocking ultraviolet rays and VOC, is green and safe, is not easy to lose efficacy, and can be widely applied to various articles for daily use such as clothes, masks and the like.
Description
Technical Field
The invention belongs to the technical field of functional composite materials, and particularly relates to a preparation method and application of a porous sheet capable of blocking UV and VOC.
Background
It is well known that exposure to uv radiation for extended periods of time can cause permanent damage to the human body, for example: premature aging of the skin, the production of melanin spots, wrinkles, thinning, poor skin elasticity, vasodilation, and the appearance of skin cancer. The commercial sunscreen products have inevitable side effects regardless of the physical or chemical sunscreen agents, and have potential hazard risk to the health of human body or environment ecology, for example, although the commercial color-changing mask can absorb UV (ultraviolet) light, the chemical molecules of the commercial color-changing mask have potential hazard to the human body, so that the use of natural and nontoxic sunscreen agents to prepare non-woven fabrics becomes the mainstream of research on sunscreen materials.
The components such as sulfated polysaccharide, carotenoid and mycosporine-like amino acid extracted from the seaweed are natural and nontoxic, have the function of absorbing UVA (Ultraviolet Radiation A, Ultraviolet band with wavelength of 320-400 nm) and UVB (Ultraviolet Radiation B, Ultraviolet band with wavelength of 290-320 nm), are prepared into the anti-UV non-woven fabric, and can be applied to various anti-UV living goods such as clothes, masks and the like. For example, patent publication No. TW 1644701B provides an ultraviolet-proof mask, which has a certain ultraviolet-proof function by spraying or coating a natural non-toxic sunscreen agent for ultraviolet absorption on its surface cloth, but the ultraviolet-proof layer formed on the non-woven fabric by spraying or coating is easily removed during use to cause failure.
In addition, as for the mask, a single ultraviolet protection function cannot meet daily travel requirements, and various Volatile Organic Compounds (VOCs) are filled in the environment due to automobile exhaust, surrounding building decoration, waste combustion, power plants, steel works, industrial waste gas emission, and the like, so that the VOCs in the environment strongly stimulate the respiratory system, central nervous system, and mucosal system of a human, causing severe stimulation, and even more severe, causing canceration of normal cells, and thus, there is an urgent need for a mask having a function of blocking VOCs in the environment. Therefore, the invention patent with the Chinese patent publication No. CN 106108175B provides a high-efficiency anti-haze and organic pollutant mask and a preparation method thereof, and the mask which can block PM2.5, has the functions of antibiosis and high-efficiency treatment of organic pollutants is prepared by taking a microporous membrane as a base material, but the mask does not have the function of anti-UV absorption, so that the outdoor application is limited.
Therefore, it is necessary to develop a porous sheet that can block UV and VOC, and that has a stable structure and is not easily deteriorated when used.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a porous sheet material capable of blocking UV and VOC.
The second purpose of the invention is to provide a porous sheet material which can block UV and VOC and is prepared by the method.
The third purpose of the invention is to provide a mask prepared by the porous sheet material capable of blocking UV and VOC.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the first aspect of the invention provides a preparation method of a porous sheet material capable of blocking UV and VOC, which comprises the following steps:
s1 preparation of metal-polymer spinning solution
Uniformly dissolving a high molecular polymer in a solvent, stirring for 8-24h at 50-80 ℃, and uniformly dispersing to obtain a high molecular polymer solution, wherein the mass fraction of the high molecular polymer is 1-20%;
taking 10mL of high molecular polymer solution, adding 1-5g of metal salt compound, and uniformly stirring to obtain the metal-high molecular spinning solution;
s2 preparation of Metal-Polymer composite sheet
Preparing the metal-polymer spinning solution prepared in the step S1 into a metal-polymer composite sheet by adopting an electrostatic spinning method, wherein the electrostatic spinning parameters are as follows: inner diameter of the needle head: 0.7 mm; electric heating lamp: 150 ℃; a hot air fan: 85 ℃; ambient temperature: 35 ℃; needle head distance collecting plate: 10 cm; voltage: 15-30 kV; syringe flow rate: 0.01 mL/min;
s3 preparation of porous sheet capable of blocking UV and VOC
Dissolving a metal salt compound and a ligand in water according to a molar ratio of 2:1, adding a natural non-toxic sunscreen agent, uniformly mixing until the concentration of the natural non-toxic sunscreen agent is 0.1-30g/L, adding the metal-polymer composite sheet prepared in the step S2, soaking for 1-72 hours at the temperature of 5-110 ℃, cooling to room temperature, washing for several times by using a solvent, and drying to obtain the porous sheet capable of blocking UV and VOC.
Further, the metal salt compound is one of zinc nitrate, zinc sulfate, zinc hydroxide, ferric chloride, aluminum chloride hexahydrate, aluminum sulfate octadecahydrate, aluminum nitrate nonahydrate, ferric nitrate, chromium chloride, copper nitrate, copper sulfate, copper hydroxide, zirconium tetrachloride and zirconium oxychloride.
Further, the polymerization degree of the high molecular polymer is 2000-8000, and the high molecular polymer is mainly one of polyacrylonitrile, polyvinyl alcohol, polyacrylic acid, polylactic acid, polycaprolactone, polytetrafluoroethylene and polymethyl methacrylate.
Further, the solvent is one or more of water, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide and ethanol.
Further, the ligand is one or more of 2-methylimidazole, terephthalic acid, isophthalic acid and fumaric acid.
Further, the natural nontoxic sunscreen agent is one or more of sulfated polysaccharide, carotenoid and mycosporine amino acid.
Further, the metal salt compound is zinc nitrate; the high molecular polymer is polyvinyl alcohol; the solvent is N, N-dimethylformamide; the ligand is terephthalic acid.
Further, in step S1, the mass ratio of the high molecular polymer, the solvent, and the metal salt compound is 1:9: 2.
According to a second aspect of the present invention, there is provided a porous sheet capable of blocking UV and VOC, which is prepared by the above method, and has a thickness of 0.1 to 0.5 mm.
The third aspect of the invention provides a mask prepared from the porous sheet capable of blocking UV and VOC, which comprises a mask body and ear hanging ropes arranged on two sides of the mask body; the mask body sequentially comprises a skin-friendly layer, a filter layer and a waterproof layer from inside to outside, and a porous sheet capable of blocking UV and VOC is arranged in the waterproof layer.
Compared with the prior art, the invention has the following beneficial effects and advantages:
(1) the metal salt compound is added into the spinning solution prepared by the invention and is firstly combined with the high molecular polymer to form a complex solution, and then electrostatic spinning is carried out to prepare the metal-high molecular composite sheet, compared with the design that the high molecular polymer solution is firstly subjected to electrostatic spinning to form the high molecular sheet and then the metal is combined, the structure of the metal-high molecular composite sheet is firmer and more stable;
(2) the metal-polymer composite sheet material is soaked in the immersion liquid to form a metal-polymer porous sheet material, the natural non-toxic sun-screening agent is coordinated on metal, so that the porous sheet material with the ultraviolet-proof function is formed, the size of pores can be controlled by a metal salt compound in the immersion liquid, the pores cannot be filled with the natural non-toxic sun-screening agent and can not adsorb VOC, and a ligand in the immersion liquid can be complexed with the metal in the metal-polymer composite sheet material, so that the stability of the porous sheet material is further improved, and the collapse of the pores is prevented;
(3) the metal-polymer porous sheet material has excellent characteristics of ultraviolet ray and VOC (volatile organic compounds) blocking, is green and safe, is not easy to lose efficacy, and can be widely applied to various articles for daily use such as clothes, masks and the like.
Drawings
FIG. 1 is an overall schematic view of a Zn-PVA composite sheet according to example 1 of the present invention;
FIG. 2 is an SEM image of a porous UV and VOC blocking sheet of example 1 of the present invention;
FIG. 3 is a FTIR spectrum of example 1 of the present invention;
FIG. 4 is a nitrogen adsorption isotherm plot of the finished product of example 1 of the present invention;
FIG. 5 is a hole distribution diagram of the product of example 1 of the present invention;
FIG. 6 is a graph of the UV absorption of the finished product of example 1 of the present invention;
fig. 7 is a schematic view of the entire structure of the mask of embodiment 2 of the present invention;
fig. 8 is a schematic view of a waterproof layer structure according to example 2 of the present invention;
reference numerals: mask body 1, ear hang rope 2, close skin layer 3, filter layer 4, waterproof layer 5, can block UV and VOC's porous sheet 6.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to the accompanying drawings and preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The existing uvioresistant non-woven fabric achieves the uvioresistant function by spraying or coating chemical materials for resisting ultraviolet absorption on the surface cloth, and can be applied to the inner layer and the outer layer of a mask, for example, the commercially available color-changing mask can absorb UV light but chemical molecules of the color-changing mask have potential harm to human bodies, and the existing uvioresistant non-woven fabric does not have the function of blocking VOC in the environment, so that the application is limited; in addition, the uv-resistant layer formed on the nonwoven fabric by spraying or coating is prone to fail due to falling off during use.
In order to solve the problems, the invention provides a porous sheet material capable of blocking UV and VOC, wherein a natural sunscreen component is doped in a metal-polymer composite sheet material to form the porous sheet material, so that the porous sheet material has the function of blocking UV and VOC, and is green, safe and durable.
The present invention will be further described with reference to specific examples.
The raw materials used in the examples of the present invention are shown in table 1 below, but not limited thereto:
TABLE 1
In Table 1, Sigma-Aldrich is the abbreviation of Sigma Aldrich, USA; merck is an abbreviation from Merck, Germany; wherein, the self-extraction method of mycosporine-like amino acid comprises the following steps:
pulverizing 10g Sargassum powder, adding 1000mL 90% methanol, stirring at room temperature for 5 hr, concentrating at 65 deg.C under reduced pressure to 30mL, standing to volatilize liquid, and naturally drying to obtain mycosporine-like amino acid.
The apparatus used in the examples of the present invention is shown in table 2, but not limited thereto:
TABLE 2
In table 2, Thermo Scientific is abbreviated as sammer feishel science and technology, usa; JASCO is short for Japan Spectroscopy Co., Ltd; mettler Toledo is short for Mettler-Torlando, Switzerland.
Example 1
A preparation method of a porous sheet material capable of blocking UV and VOC comprises the following steps:
s1 preparation of Zn-PVA spinning solution
Adding 1.0g of PVA into 9.0g of 9.0g N, N-dimethylformamide, stirring for 24 hours at 80 ℃ to uniformly disperse the PVA, adding 2.0g of zinc nitrate, and stirring uniformly to obtain the Zn-PVA spinning solution.
S2, preparation of Zn-PVA composite sheet
3mL of the Zn-PVA spinning solution prepared in the step S1 was used to prepare a Zn-PVA composite sheet having a thickness of 0.325mm and an area of 5cm × 5cm by electrospinning, as shown in FIG. 1.
Wherein the electrostatic spinning parameters are set as follows:
inner diameter of the needle head: 0.7 mm; electric heating lamp: 150 ℃; a hot air fan: 85 ℃; ambient temperature: 35 ℃; needle head distance collecting plate: 10 cm; voltage: 30 kV; syringe flow rate: 0.01 mL/min.
S3 preparation of porous sheet capable of blocking UV and VOC
0.5949g of zinc nitrate and 0.166g of terephthalic acid are mixed and dissolved in 50mL of N, N-dimethylformamide to prepare a soaking solution;
soaking 100mg of the Zn-PVA composite sheet prepared in the step S2 in 60mL of immersion liquid to form a porous sheet, then adding 0.1M mycosporine amino acid, reacting at 50 ℃ for 24h, cooling to room temperature after the reaction is finished, washing with water for several times, and drying to obtain a finished product of the porous sheet capable of blocking UV and VOC.
The finished product prepared in step S3 was characterized as follows:
FIG. 2 is a SEM photograph of the product of this example 1;
FIG. 3 is a FTIR spectrum of the product of example 1, wherein the solid line represents mycosporine-like amino acid at wavenumber of 1700cm -1 The peak is C ═ O absorption peak, when the peak is coordinated with the metal in the Zn-PVA composite sheet (namely the finished product of the example 1), the absorption peak disappears, which shows that the Zn-PVA composite sheet and mycosporine-like amino acid are combined together in a bonding mode in the example 1, so the structure is relatively stable;
FIG. 4 is a graph showing the nitrogen adsorption isotherm of the final product of example 1, from which a BET specific surface area of 162.4m was calculated 2 /g；
As shown in fig. 5, which is a distribution diagram of the pores of the finished product of example 1, it can be seen that the finished product of example 1 is a porous material, and can absorb different VOCs.
Comparative example 1
A preparation method of an anti-UV composite sheet comprises the following steps:
s1 preparation of PVA spinning solution
1.0g of PVA was added to 9.0g of 9.0g N, N-dimethylformamide and stirred at 80 ℃ for 24 hours to disperse the PVA uniformly, giving a PVA spinning solution.
S2 preparation of PVA sheet
3mL of the PVA spinning solution prepared in step S1 was electrospun to obtain a PVA sheet having a thickness of 0.325mm and an area of 5 cm. times.5 cm.
Wherein the electrostatic spinning parameters are set as follows:
inner diameter of the needle head: 0.7 mm; electric heating lamp: 150 ℃; a hot air fan: 85 ℃; ambient temperature: 35 ℃; needle head distance collecting plate: 10 cm; voltage: 30 kV; syringe flow rate: 0.01 mL/min.
S3 preparation of UV-resistant composite sheet
0.1g of mycosporine-like amino acid and 10g of adhesive (Nanbao resin) are mixed and sprayed on the surface of the PVA sheet prepared in the step S2, and after drying at 50 ℃, the PVA sheet is cooled to room temperature, so that a finished product of the anti-UV composite sheet is obtained.
Performance testing
(1) VOC adsorption test
100mg of the finished products prepared in example 1 and comparative example 1 were taken out and left to stand in a VOC atmosphere for 30 minutes (ethanol EtOH, Acetone Acetone, toluene tolumene, isopropanol IPA as vapor), the change in weight value after putting of the finished products prepared in example 1 and comparative example 1 was measured by an electronic balance and compared with commercially available activated carbon (available from Showa chemical Co., Ltd., 500g), and the results are shown in Table 3, in which the value in Table 3 is the amount of VOC adsorbable per gram of the product.
TABLE 3
| Ethanol | Acetone (II) | Isopropanol (I-propanol) | Toluene | |
| Example 1(mg/g) | 1157.8 | 724.4 | 996.3 | 732.7 |
| COMPARATIVE EXAMPLE 1(mg/g) | 0 | 6.4 | 5.5 | 7.6 |
| Activated carbon (mg/g) | 238.6 | 284.3 | 298.3 | 133.7 |
As can be seen from table 3, the composite sheet of comparative example 1 has almost no ability to adsorb VOC, whereas the porous sheet of the present invention has a much higher adsorption ability to VOC than commercially available activated carbon, indicating that the porous sheet prepared by the method of the present invention has an excellent adsorption ability to VOC.
(2) UV resistance test
Taking the finished products of example 1 and comparative example 1 of 1cm × 1cm, and measuring by using a UV spectrometer, the measurement range is 200-800nm, as shown in FIG. 6, compared with the material made of the high molecular polymer without metal coordination, example 1 has absorption in the wavelength range of 260-420nm, and comparative example 1 has absorption only in the wavelength range of 330-420 nm, it is confirmed that both example 1 and comparative example 1 have UV resistance, and the UV resistance of example 1 is much stronger than that of comparative example 1, indicating that the porous sheet prepared by the method of the present invention has excellent UV resistance.
Example 2
Fig. 7 shows a mask made of the porous sheet material capable of blocking UV and VOC prepared in example 1, which includes a mask body 1, wherein two sides of the mask body 1 are respectively provided with an ear hanging rope 2, and when the mask is used, a user fixes the mask body 1 at the ear and nose positions through the ear hanging ropes 2.
Further, the mask body 1 sequentially comprises a skin-friendly layer 3, a filter layer 4 and a waterproof layer 5 from inside to outside, wherein the skin-friendly layer 3 is made of composite fiber materials and can absorb grease and sweat so as to avoid the problem of skin allergy or discomfort when a user wears the mask; the filter layer 4 is used for filtering large particle molecules in the air; the waterproof layer 5 is used for preventing water splashing or saliva so as to protect the dryness of the mask body 1.
Further, a porous sheet 6 capable of blocking UV and VOC is coated in the waterproof layer 5, as shown in fig. 8, to block UV rays of the outside sunlight and VOC in the air.
Claims (5)
1. A preparation method of a porous sheet material capable of blocking UV and VOC is characterized by comprising the following steps:
s1 preparation of metal-polymer spinning solution
Uniformly dissolving a high molecular polymer in a solvent, stirring for 8-24h at 50-80 ℃, and uniformly dispersing to obtain a high molecular polymer solution, wherein the mass fraction of the high molecular polymer is 1-20%;
taking 10mL of high molecular polymer solution, adding 1-5g of metal salt compound, and uniformly stirring to obtain the metal-high molecular spinning solution;
wherein the degree of polymerization of the high molecular polymer is 2000-8000, and is selected from one of polyacrylonitrile, polyvinyl alcohol, polyacrylic acid, polylactic acid, polycaprolactone, polytetrafluoroethylene and polymethyl methacrylate,
the solvent is one or more of water, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide and ethanol,
the metal salt compound is one of zinc nitrate, zinc sulfate, zinc hydroxide, ferric chloride, aluminum chloride hexahydrate, aluminum sulfate octadecahydrate, aluminum nitrate nonahydrate, ferric nitrate, chromium chloride, copper nitrate, copper sulfate, copper hydroxide, zirconium tetrachloride and zirconium oxychloride,
s2 preparation of Metal-Polymer composite sheet
Preparing a metal-polymer composite sheet from the metal-polymer spinning solution prepared in the step S1 by adopting an electrostatic spinning method;
s3 preparation of porous sheet capable of blocking UV and VOC
Dissolving a metal salt compound and a ligand in water according to a molar ratio of 2:1, adding a natural non-toxic sunscreen agent, uniformly mixing until the concentration of the natural non-toxic sunscreen agent is 0.1-30g/L, adding the metal-polymer composite sheet prepared in the step S2, soaking for 1-72 hours at the temperature of 5-110 ℃, cooling to room temperature, washing for several times by using a solvent, and drying to obtain the porous sheet capable of blocking UV and VOC,
wherein the ligand is one or more of 2-methylimidazole, terephthalic acid, isophthalic acid and fumaric acid,
the natural nontoxic sunscreen agent is one or more of sulfated polysaccharide, carotenoid and mycosporine-like amino acid.
2. The method of claim 1, wherein the metal salt compound is zinc nitrate; the high molecular polymer is polyvinyl alcohol; the solvent is N, N-dimethylformamide; the ligand is terephthalic acid.
3. The method as claimed in claim 1, wherein the mass ratio of the high molecular polymer, the solvent and the metal salt compound in step S1 is 1:9: 2.
4. The porous sheet capable of blocking UV and VOC produced by the method of any one of claims 1-3, wherein the thickness of the porous sheet is 0.1-0.5 mm.
5. A mask made of the porous sheet material of claim 4, comprising a mask body and ear hanging strings provided on both sides of the mask body; the mask body sequentially comprises a skin-friendly layer, a filter layer and a waterproof layer from inside to outside, and a porous sheet capable of blocking UV and VOC is arranged in the waterproof layer.
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