CN116905241B - Cold-proof thermal fabric with self-heating effect and preparation method thereof - Google Patents
Cold-proof thermal fabric with self-heating effect and preparation method thereof Download PDFInfo
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- CN116905241B CN116905241B CN202310740764.3A CN202310740764A CN116905241B CN 116905241 B CN116905241 B CN 116905241B CN 202310740764 A CN202310740764 A CN 202310740764A CN 116905241 B CN116905241 B CN 116905241B
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- acrylic fiber
- ethanol
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- fabric
- self
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- 239000004744 fabric Substances 0.000 title claims abstract description 134
- 238000010438 heat treatment Methods 0.000 title claims abstract description 88
- 230000000694 effects Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 168
- 238000002156 mixing Methods 0.000 claims abstract description 104
- 229910026551 ZrC Inorganic materials 0.000 claims abstract description 85
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims abstract description 85
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 60
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 52
- -1 polypropylene Polymers 0.000 claims abstract description 43
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000835 fiber Substances 0.000 claims abstract description 33
- 239000004964 aerogel Substances 0.000 claims abstract description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 27
- 239000004743 Polypropylene Substances 0.000 claims abstract description 26
- 229920001155 polypropylene Polymers 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 21
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 21
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 20
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- ARLJCLKHRZGWGL-UHFFFAOYSA-N ethenylsilicon Chemical class [Si]C=C ARLJCLKHRZGWGL-UHFFFAOYSA-N 0.000 claims abstract description 13
- HRNDFHCRWHCDNZ-UHFFFAOYSA-N C(C)O.C(C1=CC=CC=C1)(=O)C1=CC=CC=C1 Chemical compound C(C)O.C(C1=CC=CC=C1)(=O)C1=CC=CC=C1 HRNDFHCRWHCDNZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 226
- 238000003756 stirring Methods 0.000 claims description 128
- 238000001035 drying Methods 0.000 claims description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- 239000006185 dispersion Substances 0.000 claims description 67
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 34
- 239000004965 Silica aerogel Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 31
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 27
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 21
- 239000012965 benzophenone Substances 0.000 claims description 21
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 21
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 20
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 20
- 229910000077 silane Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 230000001678 irradiating effect Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- 239000000413 hydrolysate Substances 0.000 claims description 11
- 238000006011 modification reaction Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 238000009965 tatting Methods 0.000 claims description 10
- 238000009941 weaving Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000011056 performance test Methods 0.000 description 8
- 239000004753 textile Substances 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 229920002239 polyacrylonitrile Polymers 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 230000002269 spontaneous effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical group C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
-
- 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
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- 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
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
- D06N3/0038—Polyolefin fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
-
- 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
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/065—Insulating
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a cold-proof thermal fabric with self-heating effect and a preparation method thereof. The method comprises the following steps: the pretreated acrylic fiber sequentially reacts with amino modified nano zirconium carbide and N, N-dimethyl-1, 3-propanediamine respectively to obtain tertiary amino acrylic fiber; reacting tertiary aminated acrylic fiber with bromo-n-butane to obtain quaternized acrylic fiber; blending the quaternized acrylic fiber and the polypropylene fiber to obtain a modified acrylic blended fabric, and dipping the modified acrylic blended fabric in a benzophenone ethanol solution to obtain a modified acrylic blended fabric subjected to dipping treatment; the hydrophobic modified vinyl silicon dioxide aerogel is prepared by taking tetraethoxysilane, vinyl triethoxysilane and trimethylchlorosilane as raw materials, and the modified acrylic fiber blended fabric subjected to the dipping treatment is subjected to grafting reaction with acrylate prepolymer and the hydrophobic modified vinyl silicon dioxide aerogel under the irradiation of ultraviolet light, so that the cold-proof thermal fabric with self-heating effect is obtained.
Description
Technical Field
The invention relates to the field of functional textile materials, in particular to a cold-proof thermal fabric with self-heating effect and a preparation method thereof.
Background
Cold-proof and warm-keeping is an important issue of people's living attention in winter, the cold-proof and warm-keeping fabrics on the market at present are roughly divided into two types, one type is active warm-keeping fabrics, and the heat balance of a human body is realized by absorbing or storing heat emitted by solar energy, electric energy, chemical energy and the like; the other is the passive warm-keeping fabric, and the cold-proof warm-keeping function is realized by adding static air and blocking heat radiation to reduce heat loss.
Chinese patent CN106120012B discloses a self-heating polyester fiber and a preparation method thereof, wherein the self-heating inorganic powder and a curing agent diluent are mixed to prepare a heating auxiliary agent for polyester spinning, and the heating auxiliary agent is sprayed on the surface of a polyester precursor to obtain the self-heating polyester fiber, so that the self-heating polyester fiber is simple in process and low in cost, but the self-heating inorganic powder is hydrophilic, has poor compatibility with hydrophobic polyester and is easy to be washed by water to lose efficacy, and on the other hand, the heating effect of the self-heating inorganic powder depends on sunlight and is greatly influenced by weather; chinese patent CN115044999B discloses a cold-proof and warm-keeping composite polyamide functional fiber, a knitted fabric and a preparation method thereof, wherein soluble zinc salt, phenol and formaldehyde are used as raw materials to prepare nano zinc doped carbonaceous aerogel, a dispersing agent and polyamide slices, the nano zinc doped carbonaceous aerogel, the dispersing agent and the polyamide slices are mixed to prepare a cold-proof functional master batch, the cold-proof functional master batch and the polyamide are melt extruded, the cold-proof and warm-keeping composite polyamide functional fiber is prepared through a melt spinning method, and the heat conductivity of the fiber is reduced through introducing aerogel, so that the warm-keeping effect of the fiber is improved, but the moisture absorption and the heat emitting effect of the polyamide are poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides the cold-proof thermal fabric with the self-heating effect and the preparation method thereof, solves the problems that the self-heating powder has poor compatibility with the fabric and is easy to be disabled by washing, and improves the thermal effect of the fabric.
In order to achieve the above purpose, the invention provides a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
step (1) placing acrylic fiber in deionized water, boiling off, drying to obtain pretreated acrylic fiber, mixing amino modified nano zirconium carbide with deionized water, performing ultrasonic dispersion to obtain amino modified nano zirconium carbide dispersion, adding the pretreated acrylic fiber into the amino modified nano zirconium carbide dispersion, reacting, adding N, N-dimethyl-1, 3-propylene diamine, continuing the reaction, separating, purifying and drying after the reaction to obtain tertiary acrylic fiber;
step (2) mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, reacting, separating, purifying and drying to obtain quaternary amino acrylic fiber;
step (3) blending the quaternized acrylic fiber and the polypropylene fiber to obtain warp yarn and weft yarn respectively, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
Step (4) dipping the modified acrylic fiber blended fabric in benzophenone ethanol solution to obtain the dipped modified acrylic fiber blended fabric;
mixing the acrylic ester prepolymer, the silicon dioxide aerogel dispersion liquid and the tripropylene glycol diacrylate, coating the mixture on the surface of the modified acrylic fiber blended fabric subjected to the dipping treatment, irradiating with ultraviolet light, washing and drying to obtain the cold-proof thermal fabric with the self-heating effect.
Preferably, in the step (1): the mass ratio of the acrylic fiber to the deionized water is 5:50, the boiling-off temperature is 80-90 ℃, and the boiling-off time is 20-40min; the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5 (50-60), and the reaction conditions are as follows: reacting for 4-6h at 85-95 ℃, and continuing the reaction under the following conditions: reacting at 85-95 deg.c for 4.5-5.5 hr.
Preferably, the conditions of the ultrasonic dispersion are: ultrasonic treatment is carried out at 20-40kHz for 20-40min.
Preferably, the amino modified nano zirconium carbide in the step (1) is prepared by the following steps: mixing an aminopropyl triethoxy silane coupling agent and a 90wt% ethanol water solution according to the mass ratio of (0.5-1.5), stirring and hydrolyzing at room temperature to obtain a silane hydrolysate, mixing nano zirconium carbide and the 50wt% ethanol water solution according to the mass ratio of (1.5-3.5), regulating the pH value to be 5, performing ultrasonic dispersion to obtain a nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion, reacting, separating, purifying and drying to obtain amino modified nano zirconium carbide;
Wherein, the mass ratio of the silane hydrolysate to the nano zirconium carbide dispersion liquid is 1:1, and the reaction conditions are as follows: reacting at 70-80 deg.c for 2-3 hr.
Preferably, the ultrasonic dispersion conditions are: ultrasonic treatment is carried out for 45-75min at the frequency of 20-40kHz, and the drying conditions are as follows: drying at 70-80deg.C for 4-6 hr.
Preferably, in the step (2): the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5 (15-25): (30-50), and the reaction conditions are as follows: reacting for 5-7h at 75-85 ℃, and drying under the following conditions: drying at 70-80deg.C for 4-6 hr.
Preferably, in the step (3): the mass ratio of the quaternized acrylic fiber to the polypropylene fiber in the warp yarn is 75:25, the mass ratio of the quaternized acrylic fiber to the polypropylene fiber in the weft yarn is 70:30, the warp density of the modified acrylic blended fabric is 300-400 yarns/10 cm, and the weft density is 360-450 yarns/10 cm.
Preferably, in the step (4): the content of Benzophenone (BP) in the benzophenone ethanol solution is 2-4wt%, the mass ratio of acrylate prepolymer to silicon dioxide aerogel dispersion liquid to tripropylene glycol diacrylate is (70-80): 10-20): 10, and the ultraviolet irradiation condition is: and irradiating with ultraviolet light of lambda=365 nm for 15-25min.
Preferably, the acrylate prepolymer in the step (4) is prepared by the following steps: mixing ethanol, methyl methacrylate, butyl acrylate and styrene, adding benzophenone, stirring, and irradiating with ultraviolet light to obtain an acrylate prepolymer;
Wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is (30-40), the mass ratio of 20-24 to 8-16 to 4-8 to 0.5-1, and the ultraviolet irradiation conditions are as follows:
and irradiating with ultraviolet light of lambda=365 nm for 20-30s.
Preferably, the silica aerogel dispersion in the step (4) is prepared by the following steps: mixing the hydrophobic modified vinyl silica aerogel and ethanol, and performing ultrasonic dispersion to obtain a silica aerogel dispersion liquid;
the mass ratio of the hydrophobic modified vinyl silicon dioxide aerogel to the ethanol is (3-7) (7-13), and the ultrasonic conditions are as follows: ultrasonic treatment is carried out at 20-40kHz for 60-120min.
Preferably, the hydrophobically modified vinyl silica aerogel is prepared by the following steps: mixing ethyl orthosilicate, vinyl triethoxysilane and ethanol water solution, adjusting the pH value to 4, heating for hydrolysis, adding N, N-dimethylformamide, adjusting the pH value to 8 by adding ammonia water solution after mixing, continuously stirring for 5min, standing, adding ethanol for aging, adding N-hexane solvent for solvent exchange after aging, adding trimethylchlorosilane for modification reaction, drying, crushing and sieving to obtain hydrophobic modified vinyl silicon dioxide aerogel;
The mass ratio of the tetraethoxysilane to the vinyl triethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is as follows: 210 (10-20), 360-440, 18-22, 22-32, the mass ratio of ethanol and water in the ethanol aqueous solution is 325-365, 35-75, the standing time is 1-2h, the aging time is 12-18h, the ethanol is replaced every 4-6h, and the solvent exchange conditions are as follows: adding n-hexane immersed gel, and performing solvent exchange twice, wherein the time length of each time is 6-8h, and the modification reaction conditions are as follows: reacting for 22-26h at normal temperature.
Preferably, the drying conditions are: drying at 50deg.C for 4 hr, drying at 80deg.C for 3 hr, and drying at 120deg.C for 2 hr.
Preferably, the mesh number of the screen is 600 mesh.
Preferably, the invention discloses the cold-proof thermal fabric with the self-heating effect, which is prepared by the preparation method of the cold-proof thermal fabric with the self-heating effect.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the surface of the nano zirconium carbide powder is modified by an aminosilane coupling agent, amino is introduced, the amino is used as an amination reagent to react with cyano of polyacrylonitrile to generate amide, so that the hydrophilicity of the polyacrylonitrile and the compatibility of the nano zirconium carbide are increased, the polyacrylonitrile is subjected to quaternization modification, the hydrophilicity of the polyacrylonitrile is improved, the moisture absorption and heat generation performances and antistatic performances of the polyacrylonitrile are increased, and meanwhile, the nano zirconium carbide has excellent photo-thermal conversion performance, solar energy can be converted into heat energy, and excellent spontaneous heat performance is provided for the fabric; the polypropylene fiber and the hydrophilically modified polyacrylonitrile are selected for blending, and the excellent moisture-conducting performance of the polypropylene fiber is utilized to lead out the water vapor emitted by a human body, thereby ensuring the dryness of the fabric,
2. The vinyl silane coupling agent and the methyl silane coupling agent are used for carrying out hydrophobic modification on the silicon dioxide aerogel, alkenyl is introduced, and the silicon dioxide aerogel and the acrylic ester are coated on the surface of the fabric through ultraviolet irradiation to form a coating, so that the heat insulation performance of the fabric is improved, the silicon dioxide aerogel and the acrylic ester coating have good transparency, and solar energy can be absorbed by nano zirconium carbide through the coating to generate heat energy; the silica aerogel has lower heat conductivity, and can reduce the heat conductivity of the fabric when being used as a coating of the fabric, prevent heat loss and play a role in keeping warm.
Drawings
FIG. 1 is a flow chart of a preparation process of the cold-proof thermal fabric with self-heating effect;
FIG. 2 is a schematic representation of the reaction of silica aerogel, methyl methacrylate, styrene, butyl acrylate, tripropylene glycol diacrylate under UV irradiation in accordance with the present invention;
FIG. 3 is a bar graph showing the results of the spontaneous heat performance test of the cold-proof thermal fabrics with spontaneous heat effect prepared in examples 1 to 5 and comparative examples 1 to 3 according to the present invention;
FIG. 4 is a bar graph showing the results of antistatic performance test of cold-proof thermal fabrics with self-heating efficacy prepared in examples 1-5 and comparative examples 1-3 according to the present invention;
Fig. 5 is a bar graph showing the results of the moisture absorption and quick drying performance test of the cold-proof thermal fabrics with self-heating effect prepared in examples 1 to 5 and comparative examples 1 to 3 according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
(1) Uniformly mixing an aminopropyl triethoxy silane coupling agent and a 90wt% ethanol water solution according to the mass ratio of 0.5:50, stirring for 4 hours at room temperature to obtain a silane hydrolysate, uniformly mixing nano zirconium carbide and the 50wt% ethanol water solution according to the mass ratio of 1.5:50, adding acetic acid to adjust pH to be less than 5, performing ultrasonic dispersion for 75 minutes at 20kHz frequency to obtain a nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion according to the mass ratio of 1:1, heating to 70 ℃ under stirring, maintaining the temperature of 70 ℃ for stirring and reacting for 3 hours, wherein the stirring speed is 150r/min, filtering, washing filter residues by using water and ethanol in sequence, and drying for 6 hours at 70 ℃ to obtain amino modified nano zirconium carbide;
(2) Adding acrylic fiber into deionized water, boiling off the acrylic fiber and the deionized water for 40 minutes at 80 ℃ according to the mass ratio of 5:50, filtering, and drying the acrylic fiber for 6 hours at 60 ℃ to obtain pretreated acrylic fiber; mixing amino modified nano zirconium carbide and deionized water, and performing ultrasonic dispersion at 20kHz for 40min to obtain amino modified nano zirconium carbide dispersion; adding the pretreated acrylic fiber into amino modified nano zirconium carbide dispersion liquid, heating to 85 ℃ under stirring, keeping the temperature of 85 ℃ for stirring reaction for 6 hours, keeping the stirring speed at 180r/min, adding N, N-dimethyl-1, 3-propanediamine after the reaction, keeping the temperature of 85 ℃ and the stirring speed at 180r/min for continuous reaction for 5.5 hours, filtering after the reaction, washing filter residues with deionized water, and drying at 60 ℃ for 8 hours to obtain tertiary amino acrylic fiber;
wherein the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5:50;
(3) Uniformly mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, heating to 75 ℃ under stirring, maintaining the temperature of 75 ℃ for stirring reaction for 7 hours, wherein the stirring speed is 180r/min, filtering after the reaction, washing filter residues with ethanol, and drying at 70 ℃ for 6 hours to obtain quaternary amino acrylic fiber;
Wherein the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5:15:30;
(4) Uniformly stirring tetraethoxysilane, vinyl triethoxysilane and ethanol aqueous solution at a stirring speed of 150r/min, adding 1mol/L hydrochloric acid aqueous solution to adjust the pH value to 4, heating to 36 ℃, stirring and hydrolyzing for 10 hours, adding N, N-dimethylformamide, uniformly mixing, adding 1mol/L ammonia aqueous solution to adjust the pH value to 8, continuously stirring for 5 minutes, stopping stirring, standing for 1 hour to form gel, adding ethanol immersed gel, aging for 12 hours, replacing ethanol every 4 hours, adding N-hexane, immersing gel, exchanging solvents for two times, exchanging for 6 hours each time, adding trimethylchlorosilane, carrying out modification reaction on the mixture, reacting for 22 hours at normal temperature, drying for 4 hours at 50 ℃ after the reaction, drying for 3 hours at 80 ℃, drying for 2 hours at 120 ℃, crushing and sieving with a 600-mesh sieve to obtain hydrophobic modified vinyl silica aerogel;
wherein the mass ratio of the tetraethoxysilane to the vinyl triethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is 210:10:360:18:22, and the mass ratio of the ethanol to the water in the ethanol aqueous solution is 325:35;
(5) Blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 75:25 to obtain warp yarns; blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 70:30 to obtain weft yarn, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
the warp density of the modified acrylic fiber blended fabric is 300 roots/10 cm, and the weft density is 360 roots/10 cm;
(6) Mixing ethanol, methyl methacrylate, butyl acrylate and styrene uniformly, adding benzophenone, and irradiating for 20s under ultraviolet light with lambda=365 nm at a stirring speed of 150r/min to obtain an acrylate prepolymer; uniformly mixing the hydrophobic modified vinyl silicon dioxide aerogel and ethanol according to the mass ratio of 3:7, and performing ultrasonic dispersion for 120min at the frequency of 20kHz to obtain silicon dioxide aerogel dispersion liquid; dipping the modified acrylic fiber blended fabric in 2wt% of benzophenone ethanol solution for 3 hours, and taking out to obtain the dipped modified acrylic fiber blended fabric; uniformly mixing acrylate prepolymer, silica aerogel dispersion liquid and tripropylene glycol diacrylate, and coating the mixture on the surface of the dipped modified acrylic fiber blended fabric, wherein the coating amount is 10g/m 2 Ultraviolet at λ=365 nm After being irradiated for 15min under light, the fabric is soaked and washed for 1 time by acetone, soaked and washed for two times, and dried for 8 hours at 60 ℃ to obtain the cold-proof thermal fabric with self-heating effect;
wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is 40:24:8:8:0.5, and the mass ratio of the acrylate prepolymer to the silica aerogel dispersion to the tripropylene glycol diacrylate is 80:10:10.
Example 2
The embodiment discloses a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
(1) Uniformly mixing an aminopropyl triethoxy silane coupling agent and a 90wt% ethanol water solution according to a mass ratio of 1:50, stirring for 4.5 hours at room temperature to obtain a silane hydrolysate, uniformly mixing nano zirconium carbide and the 50wt% ethanol water solution according to a mass ratio of 2:50, adding acetic acid to adjust pH to be less than 5, performing ultrasonic dispersion at a frequency of 30kHz for 60 minutes to obtain a nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion according to a mass ratio of 1:1, heating to 75 ℃ under stirring, keeping the temperature of 75 ℃ for stirring and reacting for 2.5 hours, wherein the stirring speed is 150r/min, filtering, washing filter residues by using water and ethanol in sequence, and drying for 5 hours at 75 ℃ to obtain amino modified nano zirconium carbide;
(2) Adding acrylic fiber into deionized water, boiling off the acrylic fiber for 30 minutes at 85 ℃ according to the mass ratio of the acrylic fiber to the deionized water of 5:50, filtering, and drying the acrylic fiber for 5 hours at 65 ℃ to obtain pretreated acrylic fiber; mixing amino modified nano zirconium carbide and deionized water, and performing ultrasonic dispersion for 30min at the frequency of 30kHz to obtain amino modified nano zirconium carbide dispersion; adding the pretreated acrylic fiber into amino modified nano zirconium carbide dispersion liquid, heating to 90 ℃ under stirring, keeping the temperature of 90 ℃ for stirring reaction for 5 hours, keeping the stirring speed at 180r/min, adding N, N-dimethyl-1, 3-propanediamine after the reaction, keeping the temperature of 90 ℃ and the stirring speed at 180r/min for continuous reaction for 5 hours, filtering after the reaction, washing filter residues with deionized water, and drying at 65 ℃ for 7.5 hours to obtain tertiary amino acrylic fiber;
wherein the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5:52;
(3) Uniformly mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, heating to 80 ℃ under stirring, keeping the temperature of 80 ℃ for stirring reaction for 6 hours, wherein the stirring speed is 180r/min, filtering after the reaction, washing filter residues with ethanol, and drying at 75 ℃ for 5 hours to obtain quaternary amino acrylic fiber;
Wherein the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5:18:35;
(4) Uniformly stirring tetraethoxysilane, vinyl triethoxysilane and ethanol aqueous solution at a stirring speed of 150r/min, adding 1mol/L hydrochloric acid aqueous solution to adjust the pH value to 4, heating to 38 ℃, stirring and hydrolyzing for 9 hours, adding N, N-dimethylformamide, uniformly mixing, adding 1mol/L ammonia aqueous solution to adjust the pH value to 8, continuously stirring for 5 minutes, stopping stirring, standing for 1.5 hours to form gel, adding ethanol to immerse the gel, aging for 15 hours, replacing ethanol every 5 hours, adding N-hexane, immersing the gel, exchanging solvents for two times, exchanging 7 hours each time, adding trimethylchlorosilane, carrying out modification reaction on the mixture, reacting for 23 hours at normal temperature, drying for 4 hours at 50 ℃, drying for 3 hours at 80 ℃, drying for 2 hours at 120 ℃, crushing and sieving through a 600-mesh sieve to obtain hydrophobic modified vinyl silica aerogel;
wherein the mass ratio of the tetraethoxysilane to the vinyl triethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is 210:15:380:19:27, and the mass ratio of the ethanol to the water in the ethanol aqueous solution is 335:45;
(5) Blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 75:25 to obtain warp yarns; blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 70:30 to obtain weft yarn, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
the warp density of the modified acrylic fiber blended fabric is 320 roots/10 cm, and the weft density is 380 roots/10 cm;
(6) Mixing ethanol, methyl methacrylate, butyl acrylate and styreneEvenly adding diphenyl ketone, and irradiating for 25 seconds under ultraviolet light with lambda=365 nm at a stirring speed of 150r/min to obtain an acrylic ester prepolymer; uniformly mixing the hydrophobic modified vinyl silicon dioxide aerogel and ethanol according to the mass ratio of 4:11, and performing ultrasonic dispersion for 90min at the frequency of 30kHz to obtain silicon dioxide aerogel dispersion liquid; dipping the modified acrylic fiber blended fabric in 3wt% of benzophenone ethanol solution for 3 hours, and taking out to obtain the dipped modified acrylic fiber blended fabric; uniformly mixing acrylate prepolymer, silica aerogel dispersion liquid and tripropylene glycol diacrylate, and coating the mixture on the surface of the dipped modified acrylic fiber blended fabric, wherein the coating amount is 10g/m 2 After being irradiated for 20min under ultraviolet light with lambda=365 nm, the fabric is soaked and washed for 1 time by acetone, soaked and washed twice by water, and dried for 7.5h at 65 ℃ to obtain the cold-proof thermal fabric with self-heating effect;
Wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is 35:23:10:7:0.7, and the mass ratio of the acrylate prepolymer to the silica aerogel dispersion to the tripropylene glycol diacrylate is 75:15:10.
Example 3
The embodiment discloses a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
(1) Uniformly mixing an aminopropyl triethoxy silane coupling agent and a 90wt% ethanol water solution according to the mass ratio of 1.5:50, stirring for 4.5 hours at room temperature to obtain a silane hydrolysate, uniformly mixing nano zirconium carbide and the 50wt% ethanol water solution according to the mass ratio of 2.5:50, adding acetic acid to adjust pH=5, performing ultrasonic dispersion for 60 minutes at the frequency of 30kHz to obtain a nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion according to the mass ratio of 1:1, heating to 75 ℃ under stirring, maintaining the temperature of 75 ℃ for stirring and reacting for 2.5 hours, wherein the stirring speed is 150r/min, filtering, washing filter residues by water and ethanol in sequence, and drying for 5 hours at the temperature of 75 ℃ to obtain amino modified nano zirconium carbide;
(2) Adding acrylic fiber into deionized water, boiling off the acrylic fiber for 30 minutes at 85 ℃ according to the mass ratio of the acrylic fiber to the deionized water of 5:50, filtering, and drying the acrylic fiber for 5 hours at 65 ℃ to obtain pretreated acrylic fiber; mixing amino modified nano zirconium carbide and deionized water, and performing ultrasonic dispersion for 30min at the frequency of 30kHz to obtain amino modified nano zirconium carbide dispersion; adding the pretreated acrylic fiber into amino modified nano zirconium carbide dispersion liquid, heating to 90 ℃ under stirring, keeping the temperature of 90 ℃ for stirring reaction for 5 hours, keeping the stirring speed at 180r/min, adding N, N-dimethyl-1, 3-propanediamine after the reaction, keeping the temperature of 90 ℃ and the stirring speed at 180r/min for continuous reaction for 5 hours, filtering after the reaction, washing filter residues with deionized water, and drying at 70 ℃ for 7 hours to obtain tertiary acrylic fiber;
Wherein the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5:55;
(3) Uniformly mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, heating to 80 ℃ under stirring, keeping the temperature of 80 ℃ for stirring reaction for 6 hours, wherein the stirring speed is 180r/min, filtering after the reaction, washing filter residues with ethanol, and drying at 75 ℃ for 5 hours to obtain quaternary amino acrylic fiber;
wherein the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5:20:40;
(4) Uniformly stirring tetraethoxysilane, vinyl triethoxysilane and ethanol aqueous solution at a stirring speed of 150r/min, adding 1mol/L hydrochloric acid aqueous solution to adjust the pH value to 4, heating to 38 ℃, stirring and hydrolyzing for 9 hours, adding N, N-dimethylformamide, uniformly mixing, adding 1mol/L ammonia aqueous solution to adjust the pH value to 8, continuously stirring for 5 minutes, stopping stirring, standing for 1.5 hours to form gel, adding ethanol to immerse the gel, aging for 15 hours, replacing ethanol every 5 hours, adding N-hexane, immersing the gel, exchanging solvents for two times, exchanging 7 hours each time, adding trimethylchlorosilane, carrying out modification reaction on the mixture, reacting for 23 hours at normal temperature, drying for 4 hours at 50 ℃, drying for 3 hours at 80 ℃, drying for 2 hours at 120 ℃, crushing and sieving through a 600-mesh sieve to obtain hydrophobic modified vinyl silica aerogel;
Wherein the mass ratio of the tetraethoxysilane to the vinyl triethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is 210:15:400:20:27, and the mass ratio of the ethanol to the water in the ethanol aqueous solution is 345:55;
(5) Blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 75:25 to obtain warp yarns; blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 70:30 to obtain weft yarn, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
the warp density of the modified acrylic fiber blended fabric is 350 roots/10 cm, and the weft density is 400 roots/10 cm;
(6) Mixing ethanol, methyl methacrylate, butyl acrylate and styrene uniformly, adding benzophenone, and irradiating for 25s under ultraviolet light with lambda=365 nm at a stirring speed of 150r/min to obtain an acrylate prepolymer; uniformly mixing the hydrophobic modified vinyl silicon dioxide aerogel and ethanol according to the mass ratio of 5:10, and performing ultrasonic dispersion for 90min at the frequency of 30kHz to obtain silicon dioxide aerogel dispersion liquid; dipping the modified acrylic fiber blended fabric in 3wt% of benzophenone ethanol solution for 3 hours, and taking out to obtain the dipped modified acrylic fiber blended fabric; uniformly mixing acrylate prepolymer, silica aerogel dispersion liquid and tripropylene glycol diacrylate, and coating the mixture on the surface of the dipped modified acrylic fiber blended fabric, wherein the coating amount is 10g/m 2 After being irradiated for 20min under ultraviolet light with lambda=365 nm, the fabric is soaked and washed for 1 time by acetone, soaked and washed for two times by water, and dried for 7 hours at 70 ℃ to obtain the cold-proof thermal fabric with self-heating effect;
wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is 35:22:12:6:0.7, and the mass ratio of the acrylate prepolymer to the silica aerogel dispersion to the tripropylene glycol diacrylate is 75:15:10.
Example 4
The embodiment discloses a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
(1) Uniformly mixing an aminopropyl triethoxy silane coupling agent and a 90wt% ethanol water solution according to the mass ratio of 2:50, stirring for 4.5 hours at room temperature to obtain a silane hydrolysate, uniformly mixing nano zirconium carbide and the 50wt% ethanol water solution according to the mass ratio of 3:50, adding acetic acid to adjust pH to be less than 5, performing ultrasonic dispersion at the frequency of 30kHz for 60 minutes to obtain a nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion according to the mass ratio of 1:1, heating to 75 ℃ under stirring, keeping the temperature of 75 ℃ for stirring and reacting for 2.5 hours, wherein the stirring speed is 150r/min, filtering, washing filter residues by using water and ethanol in sequence, and drying for 5 hours at the temperature of 75 ℃ to obtain amino modified nano zirconium carbide;
(2) Adding acrylic fiber into deionized water, boiling off at 85 ℃ for 30min, filtering, and drying at 65 ℃ for 5h to obtain pretreated acrylic fiber, wherein the mass ratio of acrylic fiber to deionized water is 5:50; mixing amino modified nano zirconium carbide and deionized water, and performing ultrasonic dispersion for 30min at the frequency of 30kHz to obtain amino modified nano zirconium carbide dispersion; adding the pretreated acrylic fiber into amino modified nano zirconium carbide dispersion liquid, heating to 90 ℃ under stirring, keeping the temperature of 90 ℃ for stirring reaction for 5 hours, keeping the stirring speed at 180r/min, adding N, N-dimethyl-1, 3-propanediamine after the reaction, keeping the temperature of 90 ℃ and the stirring speed at 180r/min for continuous reaction for 5 hours, filtering after the reaction, washing filter residues with deionized water, and drying at 75 ℃ for 6.5 hours to obtain tertiary amino acrylic fiber;
wherein the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5:58;
(3) Uniformly mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, heating to 80 ℃ under stirring, keeping the temperature of 80 ℃ for stirring reaction for 6 hours, wherein the stirring speed is 180r/min, filtering after the reaction, washing filter residues with ethanol, and drying at 75 ℃ for 5 hours to obtain quaternary amino acrylic fiber;
Wherein the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5:22:45;
(4) Uniformly stirring tetraethoxysilane, vinyl triethoxysilane and ethanol aqueous solution at a stirring speed of 150r/min, adding 1mol/L hydrochloric acid aqueous solution to adjust the pH value to 4, heating to 38 ℃, stirring and hydrolyzing for 9 hours, adding N, N-dimethylformamide, uniformly mixing, adding 1mol/L ammonia aqueous solution to adjust the pH value to 8, continuously stirring for 5 minutes, stopping stirring, standing for 1.5 hours to form gel, adding ethanol to immerse the gel, aging for 15 hours, replacing ethanol every 5 hours, adding N-hexane, immersing the gel, exchanging solvents for two times, exchanging 7 hours each time, adding trimethylchlorosilane, carrying out modification reaction on the mixture, reacting for 23 hours at normal temperature, drying for 4 hours at 50 ℃, drying for 3 hours at 80 ℃, drying for 2 hours at 120 ℃, crushing and sieving through a 600-mesh sieve to obtain hydrophobic modified vinyl silica aerogel;
wherein the mass ratio of the tetraethoxysilane to the vinyltriethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is 210:15:420:21:27, and the mass ratio of the ethanol to the water in the ethanol aqueous solution is 355:65;
(5) Blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 75:25 to obtain warp yarns; blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 70:30 to obtain weft yarn, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
the warp density of the modified acrylic fiber blended fabric is 380 roots/10 cm, and the weft density is 420 roots/10 cm;
(6) Mixing ethanol, methyl methacrylate, butyl acrylate and styrene uniformly, adding benzophenone, and irradiating for 25s under ultraviolet light with lambda=365 nm at a stirring speed of 150r/min to obtain an acrylate prepolymer; uniformly mixing the hydrophobic modified vinyl silicon dioxide aerogel and ethanol according to the mass ratio of 6:9, and performing ultrasonic dispersion for 90min at the frequency of 30kHz to obtain silicon dioxide aerogel dispersion liquid; dipping the modified acrylic fiber blended fabric in 3wt% of benzophenone ethanol solution for 3 hours, and taking out to obtain the dipped modified acrylic fiber blended fabric; uniformly mixing acrylate prepolymer, silica aerogel dispersion liquid and tripropylene glycol diacrylate, and coating the mixture on the surface of the dipped modified acrylic fiber blended fabric, wherein the coating amount is 10g/m 2 After irradiation with ultraviolet light of λ=365 nm for 20min, washing with acetone 1 time, washing with water twice Drying at 75 ℃ for 6.5 hours to obtain the cold-proof thermal fabric with self-heating effect;
wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is 35:21:14:5:0.7, and the mass ratio of acrylate prepolymer to silica aerogel dispersion to tripropylene glycol diacrylate is 75:15:10.
Example 5
The embodiment discloses a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
(1) Uniformly mixing an aminopropyl triethoxy silane coupling agent with a 90wt% ethanol water solution according to the mass ratio of 2.5:50, stirring for 5 hours at room temperature to obtain a silane hydrolysate, uniformly mixing nano zirconium carbide with the 50wt% ethanol water solution according to the mass ratio of 3.5:50, adding acetic acid to adjust pH to be 5, ultrasonically dispersing for 45 minutes at the frequency of 40kHz to obtain a nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion according to the mass ratio of 1:1, heating to 80 ℃ under stirring, keeping the temperature of 80 ℃ for stirring and reacting for 2 hours, wherein the stirring speed is 150r/min, filtering, washing filter residues by using water and ethanol in sequence, and drying for 4 hours at 80 ℃ to obtain amino modified nano zirconium carbide;
(2) Adding acrylic fiber into deionized water, boiling off the acrylic fiber for 20 minutes at 90 ℃ according to the mass ratio of the acrylic fiber to the deionized water of 5:50, filtering, and drying the acrylic fiber for 4 hours at 70 ℃ to obtain pretreated acrylic fiber; mixing the amino modified nano zirconium carbide and deionized water, and performing ultrasonic dispersion for 20min at the frequency of 40kHz to obtain an amino modified nano zirconium carbide dispersion; adding the pretreated acrylic fiber into amino modified nano zirconium carbide dispersion liquid, heating to 95 ℃ under stirring, keeping the temperature of 95 ℃ for stirring reaction for 4 hours, keeping the stirring speed at 180r/min, adding N, N-dimethyl-1, 3-propanediamine after the reaction, keeping the temperature of 95 ℃ and the stirring speed at 180r/min for continuous reaction for 4.5 hours, filtering after the reaction, washing filter residues with deionized water, and drying at 80 ℃ for 6 hours to obtain tertiary amino acrylic fiber;
wherein the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5:60;
(3) Uniformly mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, heating to 85 ℃ under stirring, maintaining the temperature of 85 ℃ for stirring reaction for 5 hours, wherein the stirring speed is 180r/min, filtering after the reaction, washing filter residues with ethanol, and drying at 80 ℃ for 4 hours to obtain quaternary amino acrylic fiber;
Wherein the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5:25:50;
(4) Uniformly stirring tetraethoxysilane, vinyl triethoxysilane and ethanol aqueous solution at a stirring speed of 150r/min, adding 1mol/L hydrochloric acid aqueous solution to adjust the pH value to 4, heating to 40 ℃, stirring and hydrolyzing for 8 hours, adding N, N-dimethylformamide, uniformly mixing, adding 1mol/L ammonia aqueous solution to adjust the pH value to 8, continuously stirring for 5 minutes, stopping stirring, standing for 2 hours to form gel, adding ethanol immersed gel, aging for 18 hours, replacing ethanol every 6 hours, adding N-hexane, immersing gel, exchanging solvents twice, exchanging 8 hours each time, adding trimethylchlorosilane, carrying out modification reaction on the mixture, reacting for 24 hours at normal temperature, drying for 4 hours at 50 ℃ after the reaction, drying for 3 hours at 80 ℃, drying for 2 hours at 120 ℃, crushing and sieving with a 600 mesh sieve to obtain hydrophobic modified vinyl silica aerogel;
wherein the mass ratio of the tetraethoxysilane to the vinyl triethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is 210:15:440:22:32, and the mass ratio of the ethanol to the water in the ethanol aqueous solution is 365:75;
(5) Blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 75:25 to obtain warp yarns; blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 70:30 to obtain weft yarn, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
the warp density of the modified acrylic fiber blended fabric is 400 roots/10 cm, and the weft density is 450 roots/10 cm;
(6) Mixing ethanol, methyl methacrylate, butyl acrylate and styrene, adding benzophenone, stirring at 150r/min at λ =Irradiating for 30s under 365nm ultraviolet light to obtain an acrylic ester prepolymer; uniformly mixing the hydrophobic modified vinyl silicon dioxide aerogel and ethanol according to the mass ratio of 7:13, and performing ultrasonic dispersion for 60min at the frequency of 40kHz to obtain silicon dioxide aerogel dispersion liquid; dipping the modified acrylic fiber blended fabric in 4wt% of benzophenone ethanol solution for 3 hours, and taking out to obtain the dipped modified acrylic fiber blended fabric; uniformly mixing acrylate prepolymer, silica aerogel dispersion liquid and tripropylene glycol diacrylate, and coating the mixture on the surface of the dipped modified acrylic fiber blended fabric, wherein the coating amount is 10g/m 2 After being irradiated for 25min under ultraviolet light with lambda=365 nm, the fabric is soaked and washed for 1 time by acetone, soaked and washed for two times by water, and dried for 6 hours at 80 ℃ to obtain the cold-proof thermal fabric with self-heating effect;
Wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is 30:20:16:4:1, and the mass ratio of the acrylate prepolymer to the silica aerogel dispersion to the tripropylene glycol diacrylate is 75:15:10.
Comparative example 1
The comparative example discloses a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
(1) Adding acrylic fiber into deionized water, boiling off the acrylic fiber for 30 minutes at 85 ℃ according to the mass ratio of the acrylic fiber to the deionized water of 5:50, filtering, and drying the acrylic fiber for 5 hours at 65 ℃ to obtain pretreated acrylic fiber; uniformly mixing N, N-dimethyl-1, 3-propylene diamine and deionized water; adding the pretreated acrylic fiber into amino modified nano zirconium carbide dispersion liquid, heating to 90 ℃ under stirring, keeping the temperature of 90 ℃ for stirring reaction for 5 hours, wherein the stirring speed is 180r/min, filtering after the reaction, washing filter residues with deionized water, and drying at 65 ℃ for 7.5 hours to obtain tertiary acrylic fiber;
wherein the mass ratio of deionized water to acrylic fiber to N, N-dimethyl-1, 3-propanediamine is 50:5:57;
(3) Uniformly mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, heating to 80 ℃ under stirring, keeping the temperature of 80 ℃ for stirring reaction for 6 hours, wherein the stirring speed is 180r/min, filtering after the reaction, washing filter residues with ethanol, and drying at 75 ℃ for 5 hours to obtain quaternary amino acrylic fiber;
Wherein the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5:18:35;
(4) Uniformly stirring tetraethoxysilane, vinyl triethoxysilane and ethanol aqueous solution at a stirring speed of 150r/min, adding 1mol/L hydrochloric acid aqueous solution to adjust the pH value to 4, heating to 38 ℃, stirring and hydrolyzing for 9 hours, adding N, N-dimethylformamide, uniformly mixing, adding 1mol/L ammonia aqueous solution to adjust the pH value to 8, continuously stirring for 5 minutes, stopping stirring, standing for 1.5 hours to form gel, adding ethanol to immerse the gel, aging for 15 hours, replacing ethanol every 5 hours, adding N-hexane, immersing the gel, exchanging solvents for two times, exchanging 7 hours each time, adding trimethylchlorosilane, carrying out modification reaction on the mixture, reacting for 23 hours at normal temperature, drying for 4 hours at 50 ℃, drying for 3 hours at 80 ℃, drying for 2 hours at 120 ℃, crushing and sieving through a 600-mesh sieve to obtain hydrophobic modified vinyl silica aerogel;
wherein the mass ratio of the tetraethoxysilane to the vinyl triethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is 210:15:380:19:27, and the mass ratio of the ethanol to the water in the ethanol aqueous solution is 335:45;
(5) Blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 75:25 to obtain warp yarns; blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 70:30 to obtain weft yarn, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
the warp density of the modified acrylic fiber blended fabric is 320 roots/10 cm, and the weft density is 380 roots/10 cm;
(6) Mixing ethanol, methyl methacrylate, butyl acrylate and styrene uniformly, adding benzophenone, and irradiating for 25s under ultraviolet light with lambda=365 nm at a stirring speed of 150r/min to obtain an acrylate prepolymer; uniformly mixing the hydrophobic modified vinyl silicon dioxide aerogel and ethanol according to the mass ratio of 4:11, and performing ultrasonic dispersion for 90min at the frequency of 30kHz to obtain silicon dioxide aerogel dispersionA liquid; dipping the modified acrylic fiber blended fabric in 3wt% of benzophenone ethanol solution for 3 hours, and taking out to obtain the dipped modified acrylic fiber blended fabric; uniformly mixing acrylate prepolymer, silica aerogel dispersion liquid and tripropylene glycol diacrylate, and coating the mixture on the surface of the dipped modified acrylic fiber blended fabric, wherein the coating amount is 10g/m 2 After being irradiated for 20min under ultraviolet light with lambda=365 nm, the fabric is soaked and washed for 1 time by acetone, soaked and washed twice by water, and dried for 7.5h at 65 ℃ to obtain the cold-proof thermal fabric with self-heating effect;
Wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is 35:23:10:7:0.7, and the mass ratio of the acrylate prepolymer to the silica aerogel dispersion to the tripropylene glycol diacrylate is 75:15:10.
Comparative example 2
The embodiment discloses a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
(1) Uniformly mixing an aminopropyl triethoxy silane coupling agent and a 90wt% ethanol water solution according to a mass ratio of 1:50, stirring for 4.5 hours at room temperature to obtain a silane hydrolysate, uniformly mixing nano zirconium carbide and the 50wt% ethanol water solution according to a mass ratio of 2:50, adding acetic acid to adjust pH to be less than 5, performing ultrasonic dispersion at a frequency of 30kHz for 60 minutes to obtain a nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion according to a mass ratio of 1:1, heating to 75 ℃ under stirring, keeping the temperature of 75 ℃ for stirring and reacting for 2.5 hours, wherein the stirring speed is 150r/min, filtering, washing filter residues by using water and ethanol in sequence, and drying for 5 hours at 75 ℃ to obtain amino modified nano zirconium carbide;
(2) Adding acrylic fiber into deionized water, boiling off the acrylic fiber for 30 minutes at 85 ℃ according to the mass ratio of the acrylic fiber to the deionized water of 5:50, filtering, and drying the acrylic fiber for 5 hours at 65 ℃ to obtain pretreated acrylic fiber; mixing amino modified nano zirconium carbide and deionized water, and performing ultrasonic dispersion for 30min at the frequency of 30kHz to obtain amino modified nano zirconium carbide dispersion; adding the pretreated acrylic fiber into amino modified nano zirconium carbide dispersion liquid, heating to 90 ℃ under stirring, keeping the temperature of 90 ℃ for stirring reaction for 5 hours, keeping the stirring speed at 180r/min, adding N, N-dimethyl-1, 3-propanediamine after the reaction, keeping the temperature of 90 ℃ and the stirring speed at 180r/min for continuous reaction for 5 hours, filtering after the reaction, washing filter residues with deionized water, and drying at 65 ℃ for 7.5 hours to obtain tertiary amino acrylic fiber;
Wherein the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5:52;
(3) Uniformly mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, heating to 80 ℃ under stirring, keeping the temperature of 80 ℃ for stirring reaction for 6 hours, wherein the stirring speed is 180r/min, filtering after the reaction, washing filter residues with ethanol, and drying at 75 ℃ for 5 hours to obtain quaternary amino acrylic fiber;
wherein the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5:18:35;
(4) Blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 75:25 to obtain warp yarns; blending quaternized acrylic fiber and polypropylene fiber according to a mass ratio of 70:30 to obtain weft yarn, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
the warp density of the modified acrylic fiber blended fabric is 320 roots/10 cm, and the weft density is 380 roots/10 cm; comparative example 3
The embodiment discloses a preparation method of cold-proof thermal fabric with self-heating effect, which comprises the following steps:
(1) Uniformly mixing an aminopropyl triethoxy silane coupling agent and a 90wt% ethanol water solution according to a mass ratio of 1:50, stirring for 4.5 hours at room temperature to obtain a silane hydrolysate, uniformly mixing nano zirconium carbide and the 50wt% ethanol water solution according to a mass ratio of 2:50, adding acetic acid to adjust pH to be less than 5, performing ultrasonic dispersion at a frequency of 30kHz for 60 minutes to obtain a nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion according to a mass ratio of 1:1, heating to 75 ℃ under stirring, keeping the temperature of 75 ℃ for stirring and reacting for 2.5 hours, wherein the stirring speed is 150r/min, filtering, washing filter residues by using water and ethanol in sequence, and drying for 5 hours at 75 ℃ to obtain amino modified nano zirconium carbide;
(2) Adding acrylic fiber into deionized water, boiling off the acrylic fiber for 30 minutes at 85 ℃ according to the mass ratio of the acrylic fiber to the deionized water of 5:50, filtering, and drying the acrylic fiber for 5 hours at 65 ℃ to obtain pretreated acrylic fiber; mixing amino modified nano zirconium carbide and deionized water, and performing ultrasonic dispersion for 30min at the frequency of 30kHz to obtain amino modified nano zirconium carbide dispersion; adding the pretreated acrylic fiber into amino modified nano zirconium carbide dispersion liquid, heating to 90 ℃ under stirring, keeping the temperature of 90 ℃ for stirring reaction for 5 hours, keeping the stirring speed at 180r/min, adding N, N-dimethyl-1, 3-propanediamine after the reaction, keeping the temperature of 90 ℃ and the stirring speed at 180r/min for continuous reaction for 5 hours, filtering after the reaction, washing filter residues with deionized water, and drying at 65 ℃ for 7.5 hours to obtain tertiary amino acrylic fiber;
wherein the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5:52;
(3) Uniformly stirring tetraethoxysilane, vinyl triethoxysilane and ethanol aqueous solution at a stirring speed of 150r/min, adding 1mol/L hydrochloric acid aqueous solution to adjust the pH value to 4, heating to 38 ℃, stirring and hydrolyzing for 9 hours, adding N, N-dimethylformamide, uniformly mixing, adding 1mol/L ammonia aqueous solution to adjust the pH value to 8, continuously stirring for 5 minutes, stopping stirring, standing for 1.5 hours to form gel, adding ethanol to immerse the gel, aging for 15 hours, replacing ethanol every 5 hours, adding N-hexane, immersing the gel, exchanging solvents for two times, exchanging 7 hours each time, adding trimethylchlorosilane, carrying out modification reaction on the mixture, reacting for 23 hours at normal temperature, drying for 4 hours at 50 ℃, drying for 3 hours at 80 ℃, drying for 2 hours at 120 ℃, crushing and sieving through a 600-mesh sieve to obtain hydrophobic modified vinyl silica aerogel;
Wherein the mass ratio of the tetraethoxysilane to the vinyl triethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is 210:15:380:19:27, and the mass ratio of the ethanol to the water in the ethanol aqueous solution is 335:45;
(4) Blending tertiary acrylic fiber and polypropylene fiber according to the mass ratio of 75:25 to obtain warp yarn; blending the tertiary acrylic fiber and the polypropylene fiber according to the mass ratio of 70:30 to obtain weft yarns, and weaving the warp yarns and the weft yarns into the modified acrylic blended fabric through a tatting process;
the warp density of the modified acrylic fiber blended fabric is 320 roots/10 cm, and the weft density is 380 roots/10 cm;
(5) Mixing ethanol, methyl methacrylate, butyl acrylate and styrene uniformly, adding benzophenone, and irradiating for 25s under ultraviolet light with lambda=365 nm at a stirring speed of 150r/min to obtain an acrylate prepolymer; uniformly mixing the hydrophobic modified vinyl silicon dioxide aerogel and ethanol according to the mass ratio of 4:11, and performing ultrasonic dispersion for 90min at the frequency of 30kHz to obtain silicon dioxide aerogel dispersion liquid; dipping the modified acrylic fiber blended fabric in 3wt% of benzophenone ethanol solution for 3 hours, and taking out to obtain the dipped modified acrylic fiber blended fabric; uniformly mixing acrylate prepolymer, silica aerogel dispersion liquid and tripropylene glycol diacrylate, and coating the mixture on the surface of the dipped modified acrylic fiber blended fabric, wherein the coating amount is 10g/m 2 After being irradiated for 20min under ultraviolet light with lambda=365 nm, the fabric is soaked and washed for 1 time by acetone, soaked and washed twice by water, and dried for 7.5h at 65 ℃ to obtain the cold-proof thermal fabric with self-heating effect;
wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is 35:23:10:7:0.7, and the mass ratio of the acrylate prepolymer to the silica aerogel dispersion to the tripropylene glycol diacrylate is 75:15:10.
The aminopropyl triethoxysilane of examples 1-5 and comparative examples 1-3 was from Shanghai Ala Ding Shenghua reagent technologies Co., ltd., CAS No. 919-30-2, nano zirconium carbide was from Shanghai ultra micro nano technologies Co., ltd., model CW-ZrC-001, acrylic fiber was from Huzhou Wu Xingjiang wet textile mill, fineness was 4D, length was 60mm, N-dimethyl-1, 3-propanediamine was from Beijing Baolin Wired technology Co., ltd., CAS No. 111-33-1, bromo n-butane was from Nanj chemical Co., ltd., CAS No. 109-65-9, ethyl orthosilicate was from Nanj chemical Co., CAS No. 78-10-4, vinyl triethoxysilane was from Beijing Baolin Wig technology Co., ltd., the CAS number is 78-08-0, the trimethylchlorosilane is from Jinan century chemical industry Co., ltd, the CAS number is 75-77-4, the polypropylene fiber is from Shanghai mountain area chemical industry Co., ltd, the fineness is 1.5D, the length is 50mm, the methyl methacrylate is from Shanghai Altin Biotechnology Co., ltd, the CAS number is 80-62-6, the butyl acrylate is from Nanjing chemical reagent Co., ltd, the CAS number is 141-32-2, the styrene is from Shanghai Altin Biotechnology Co., ltd, the CAS number is 100-42-5, the benzophenone is from Shanghai Altin deep technology Co., ltd, the CAS number is 119-61-9, the tripropylene glycol diacrylate is from Guangzhou Ten technology Co., ltd, and the CAS number is 42978-66-5.
Performance test:
test one: spontaneous thermal performance test: the spontaneous thermal performance of the fabric was tested according to GB/T29866-2013 textile moisture absorption and heating performance test method, and simultaneously, sunlight irradiation was applied to the fabric, and the fabric was characterized by an average temperature rise value (delta T) within 30min, and the test results are shown in Table 1:
TABLE 1
| Examples | Examples | Examples | Examples | Examples | Comparative example | Comparative example | Comparative example | |
| ΔT/℃ | 3.7 | 4.2 | 4.8 | 5.6 | 6.5 | 2.7 | 3.9 | 4.0 |
As can be seen from the test results in Table 1, the cold-proof thermal fabric with the self-heating effect has better self-heating performance, and as can be seen from examples 1 to 5, the self-heating performance of the fabric is continuously improved along with the increase of the hydrophilicity of the acrylic fiber and the increase of the textile density of the fabric; as can be seen from comparative examples 1 and 2, when no nano zirconium carbide is added to the fabric, the spontaneous heating effect of the fabric is obviously reduced, because the nano zirconium carbide can convert solar energy into heat energy under the irradiation of sunlight, so that the temperature of the fabric can be raised more, and therefore the Δt value is larger; as can be seen from comparative example 2 and example 2, when the fabric is not coated with the acrylate silica aerogel coating, the heat insulation performance is poor, so the Δt value of the fabric is slightly reduced; as can be seen from comparative example 3 and example 2, when the acrylic fiber is not quaternized, the hydrophilicity of the acrylic fiber is reduced, and the heat and moisture absorption performance is also reduced, so that the delta T value of the fabric is also reduced.
And II, testing: antistatic test: evaluation of textile static Properties according to GB/T12703.3-2009, section 3: charge amount "the antistatic property of the fabric was tested, and the test results are shown in table 2:
TABLE 2
| Examples | Examples | Examples | Examples | Examples | Comparative example | Comparative example | Comparative example | |
| Charge density | 1.8 | 1.6 | 1.5 | 1.4 | 1.2 | 1.6 | 1.6 | 2.2 |
As can be seen from the test results of Table 2, the cold-proof thermal fabric with self-heating effect of the invention has certain antistatic performance, and examples 1 to 5 show that the better the antistatic performance of the fabric is along with the increase of the quaternary ammonium salt content in the acrylic fiber, and comparative examples 3 and 2 show that the higher the charge surface density of the fabric is and the worse the antistatic performance is when the fabric is not subjected to quaternization modification.
And (3) testing: moisture absorption quick-drying performance test: determination of moisture absorption and quick drying Properties of textiles according to GB/T21655.1-2008 part 1: the moisture absorption and quick drying performance test of the fabric is carried out by a single combined test method, and the test results are shown in Table 3:
TABLE 3 Table 3
| Examples | Examples | Examples | Examples | Examples | Comparative example | Comparative example | Comparative example | |
| The moisture permeability value of the water vapor, | 7976 | 7495 | 6980 | 6439 | 5879 | 7503 | 7025 | 7531 |
as can be seen from the test results of Table 3, the cold-proof thermal fabric with self-heating effect of the present invention has a certain moisture absorption and quick-drying performance, examples 1 to 5 show that the moisture absorption and quick-drying performance of the fabric decreases with the increase of the textile density of the fabric, and comparative examples 2 and example 2 show that when the fabric is not coated with the acrylate silica aerogel coating, the moisture permeability value is relatively large, because the acrylate coating can obstruct the passage of water vapor molecules, the air permeability and moisture permeability of the fabric are limited to a certain extent, and thus the moisture absorption and quick-drying performance of the fabric decreases.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the cold-proof thermal fabric with the self-heating effect is characterized by comprising the following steps of:
step (1) placing acrylic fiber in deionized water, boiling off, drying to obtain pretreated acrylic fiber, mixing amino modified nano zirconium carbide with deionized water, performing ultrasonic dispersion to obtain amino modified nano zirconium carbide dispersion, adding the pretreated acrylic fiber into the amino modified nano zirconium carbide dispersion, reacting, adding N, N-dimethyl-1, 3-propylene diamine, continuing the reaction, separating, purifying and drying after the reaction to obtain tertiary acrylic fiber;
step (2) mixing tertiary amino acrylic fiber, bromo-n-butane and ethanol, reacting, separating, purifying and drying to obtain quaternary amino acrylic fiber;
step (3) blending the quaternized acrylic fiber and the polypropylene fiber to obtain warp yarn and weft yarn respectively, and weaving the warp yarn and the weft yarn into modified acrylic blended fabric through a tatting process;
Step (4) dipping the modified acrylic fiber blended fabric in benzophenone ethanol solution to obtain the dipped modified acrylic fiber blended fabric;
mixing the acrylic ester prepolymer, the silicon dioxide aerogel dispersion liquid and the tripropylene glycol diacrylate, coating the mixture on the surface of the modified acrylic fiber blended fabric subjected to the dipping treatment, irradiating with ultraviolet light, washing and drying to obtain the cold-proof thermal fabric with the self-heating effect.
2. The method for preparing cold-proof thermal fabric with self-heating effect according to claim 1, wherein in the step (1): the mass ratio of the acrylic fiber to the deionized water is 5:50, the boiling-off temperature is 80-90 ℃, and the boiling-off time is 20-40min; the mass ratio of the amino modified nano zirconium carbide to deionized water to the pretreated acrylic fiber to the N, N-dimethyl-1, 3-propanediamine is 5:50:5 (50-60), and the reaction conditions are as follows: reacting for 4-6h at 85-95 ℃, and continuing the reaction under the following conditions: reacting at 85-95 deg.c for 4.5-5.5 hr.
3. The method for preparing the cold-proof thermal fabric with the self-heating effect according to claim 1, wherein the amino modified nano zirconium carbide in the step (1) comprises the following steps: mixing 50 parts by mass of an aminopropyl triethoxy silane coupling agent and 50 parts by mass of an ethanol water solution, stirring and hydrolyzing at room temperature to obtain silane hydrolysate, mixing 50 parts by mass of nano zirconium carbide and ethanol water solution, adjusting pH to be less than 5, performing ultrasonic dispersion to obtain nano zirconium carbide dispersion, mixing the silane hydrolysate and the nano zirconium carbide dispersion, reacting, separating and purifying, and drying to obtain amino modified nano zirconium carbide;
Wherein, the mass ratio of the silane hydrolysate to the nano zirconium carbide dispersion liquid is 1:1, and the reaction conditions are as follows: reacting at 70-80 deg.c for 2-3 hr.
4. The method for preparing cold-proof thermal fabric with self-heating effect according to claim 1, wherein in the step (2): the mass ratio of the tertiary amine acrylic fiber to the bromon-butane to the ethanol is 5 (15-25): (30-50), and the reaction conditions are as follows: reacting at 75-85 deg.c for 5-7 hr.
5. The method for preparing cold-proof thermal fabric with self-heating effect according to claim 1, wherein in the step (3): the mass ratio of the quaternized acrylic fiber to the polypropylene fiber in the warp yarn is 75:25, the mass ratio of the quaternized acrylic fiber to the polypropylene fiber in the weft yarn is 70:30, the warp density of the modified acrylic blended fabric is 300-400 yarns/10 cm, and the weft density is 360-450 yarns/10 cm.
6. The method for preparing cold-proof thermal fabric with self-heating effect according to claim 1, wherein in the step (4): the content of benzophenone in the benzophenone ethanol solution is 2 to 4 weight percent, the mass ratio of the acrylate prepolymer to the silicon dioxide aerogel dispersion liquid to the tripropylene glycol diacrylate is (70 to 80): 10 to 20): 10, and the ultraviolet irradiation condition is: and irradiating with ultraviolet light of lambda=365 nm for 15-25min.
7. The method for preparing the cold-proof thermal fabric with the self-heating effect according to claim 1, wherein the acrylate prepolymer in the step (4) is prepared by the following steps: mixing ethanol, methyl methacrylate, butyl acrylate and styrene, adding benzophenone, stirring, and irradiating with ultraviolet light to obtain an acrylate prepolymer;
wherein the mass ratio of ethanol to methyl methacrylate to butyl acrylate to styrene to benzophenone is (30-40), the mass ratio of 20-24 to 8-16 to 4-8 to 0.5-1, and the ultraviolet irradiation conditions are as follows: and irradiating with ultraviolet light of lambda=365 nm for 20-30s.
8. The method for preparing the cold-proof thermal fabric with the self-heating effect according to claim 1, wherein the silica aerogel dispersion liquid in the step (4) is prepared by the following steps: mixing the hydrophobic modified vinyl silica aerogel and ethanol, and performing ultrasonic dispersion to obtain a silica aerogel dispersion liquid;
the mass ratio of the hydrophobic modified vinyl silicon dioxide aerogel to the ethanol is (3-7) (7-13), and the ultrasonic conditions are as follows: ultrasonic treatment is carried out at 20-40kHz for 60-120min.
9. The method for preparing the cold-proof thermal fabric with the self-heating effect according to claim 8, wherein the hydrophobically modified vinyl silica aerogel comprises the following steps: mixing ethyl orthosilicate, vinyl triethoxysilane and ethanol water solution, adjusting the pH value to 4, heating for hydrolysis, adding N, N-dimethylformamide, adjusting the pH value to 8 by adding ammonia water solution after mixing, continuously stirring for 5min, standing, adding ethanol for aging, adding N-hexane solvent for solvent exchange after aging, adding trimethylchlorosilane for modification reaction, drying, crushing and sieving to obtain hydrophobic modified vinyl silicon dioxide aerogel;
The mass ratio of the tetraethoxysilane to the vinyl triethoxysilane to the ethanol aqueous solution to the N, N-dimethylformamide to the trimethylchlorosilane is as follows: 210 (10-20), 360-440, 18-22, 22-32, the mass ratio of ethanol and water in the ethanol aqueous solution is 325-365, 35-75, the standing time is 1-2h, the aging time is 12-18h, the ethanol is replaced every 4-6h, and the solvent exchange conditions are as follows: adding n-hexane immersed gel, and performing solvent exchange twice, wherein the time length of each time is 6-8h, and the modification reaction conditions are as follows: reacting for 22-26h at normal temperature.
10. A cold-proof thermal fabric with self-heating effect prepared by the preparation method of the cold-proof thermal fabric with self-heating effect as claimed in any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0571012A (en) * | 1991-09-05 | 1993-03-23 | Mitsubishi Rayon Co Ltd | Acrylic synthetic fiber |
| CN1651617A (en) * | 2005-01-13 | 2005-08-10 | 东华大学 | Nano-antibacterial material, its preparation method and use |
| CN201709408U (en) * | 2009-07-23 | 2011-01-19 | 中山市康益保健用品有限公司 | Novel far infrared fabric |
| CN110735194A (en) * | 2019-11-29 | 2020-01-31 | 福建六树网络科技有限公司 | silicon dioxide composite aerogel, PET polyester fiber and polyester fabric |
| CN114197071A (en) * | 2021-12-22 | 2022-03-18 | 上海帼帆化工新材料有限公司 | Heat-storage warm-keeping antistatic acrylic fiber blending spinning solution |
-
2023
- 2023-06-21 CN CN202310740764.3A patent/CN116905241B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0571012A (en) * | 1991-09-05 | 1993-03-23 | Mitsubishi Rayon Co Ltd | Acrylic synthetic fiber |
| CN1651617A (en) * | 2005-01-13 | 2005-08-10 | 东华大学 | Nano-antibacterial material, its preparation method and use |
| CN201709408U (en) * | 2009-07-23 | 2011-01-19 | 中山市康益保健用品有限公司 | Novel far infrared fabric |
| CN110735194A (en) * | 2019-11-29 | 2020-01-31 | 福建六树网络科技有限公司 | silicon dioxide composite aerogel, PET polyester fiber and polyester fabric |
| CN114197071A (en) * | 2021-12-22 | 2022-03-18 | 上海帼帆化工新材料有限公司 | Heat-storage warm-keeping antistatic acrylic fiber blending spinning solution |
Non-Patent Citations (2)
| Title |
|---|
| Qingshuai Yan,et al.High-Efficiency Electro/Solar-Driven Wearable Heater Tailored bySuperelastic Hollow-Porous Polypyrrole/Polyurethane/ZirconiumCarbide Fibers for Personal Cold Protection.ACS Applied Materials & Interfaces.2022,第14卷第24073-24992页. * |
| 涤纶织物纳米碳化锆复合镀Ni-P镀层;张辉等;电镀与环保;20110331;第31卷(第2期);第22-25页 * |
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| CN116905241A (en) | 2023-10-20 |
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