CN113279143B - Degradable flame-retardant plant fiber non-woven fabric - Google Patents
Degradable flame-retardant plant fiber non-woven fabric Download PDFInfo
- Publication number
- CN113279143B CN113279143B CN202110567885.3A CN202110567885A CN113279143B CN 113279143 B CN113279143 B CN 113279143B CN 202110567885 A CN202110567885 A CN 202110567885A CN 113279143 B CN113279143 B CN 113279143B
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- Prior art keywords
- woven fabric
- flame retardant
- base cloth
- fiber
- fabric base
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 137
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000000835 fiber Substances 0.000 title claims abstract description 124
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 123
- 239000004744 fabric Substances 0.000 claims abstract description 81
- 239000013115 Zn-MOF-74 Substances 0.000 claims abstract description 48
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 43
- 239000004626 polylactic acid Substances 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 38
- 229920001661 Chitosan Polymers 0.000 claims abstract description 31
- 241000196324 Embryophyta Species 0.000 claims abstract description 30
- 229920000742 Cotton Polymers 0.000 claims abstract description 23
- 241000208202 Linaceae Species 0.000 claims abstract description 22
- 235000004431 Linum usitatissimum Nutrition 0.000 claims abstract description 22
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 21
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001630 malic acid Substances 0.000 claims abstract description 21
- 235000011090 malic acid Nutrition 0.000 claims abstract description 21
- 239000004952 Polyamide Substances 0.000 claims abstract description 20
- 229920002647 polyamide Polymers 0.000 claims abstract description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 44
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000012153 distilled water Substances 0.000 claims description 37
- 238000002360 preparation method Methods 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 21
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 235000013311 vegetables Nutrition 0.000 claims description 13
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007900 aqueous suspension Substances 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000004156 Azodicarbonamide Substances 0.000 claims description 5
- 239000013118 MOF-74-type framework Substances 0.000 claims description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 5
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 230000003014 reinforcing effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000003068 static effect Effects 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 239000012757 flame retardant agent Substances 0.000 abstract 3
- 230000000295 complement effect Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 5
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000004049 embossing Methods 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013309 porous organic framework Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/732—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by fluid current, e.g. air-lay
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B13/00—Treatment of textile materials with liquids, gases or vapours with aid of vibration
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
- D06B3/18—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics combined with squeezing, e.g. in padding machines
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- 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
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Abstract
The invention discloses a degradable flame-retardant plant fiber non-woven fabric, and belongs to the technical field of non-woven fabrics. The flame retardant agent comprises a plant fiber non-woven fabric taking polylactic acid as a main body and a flame retardant agent slurry padded on the surface of a base fabric, wherein Zn-MOF-74/PVA flame retardant agent is anchored on the surface of the plant fiber non-woven fabric base fabric by taking an ionic state generated by dissolving chitosan in malic acid as a medium, so that a flame retardant effect is generated; the hydrophilicity generated by the cooperation of the hydroxyl structure with rich surfaces of the flame retardant, the hydroxyl and amino polar groups contained in the chitosan and the cotton stalk fibers doped in the non-woven fabric is utilized to optimize and complement the hydrophobicity of the polylactic acid, so that the hydrolysis degradation rate of the polylactic acid is effectively increased; meanwhile, the polyamide fiber and the flax fiber are doped to improve the performances of wear resistance, bacteriostasis, static resistance and the like of the non-woven fabric, and the application range of the non-woven fabric is widened.
Description
Technical Field
The invention relates to the technical field of non-woven fabrics, in particular to a degradable flame-retardant plant fiber non-woven fabric.
Background
Flame retardants are functional adjuvants that impart flame retardancy to flammable polymers, mainly organic and inorganic flame retardants, halogen-based flame retardants (organic chlorides and organic bromides) and non-halogen. The organic flame retardants are some flame retardants represented by bromine system, phosphorus-nitrogen system, red phosphorus and compounds, and the inorganic flame retardants are mainly flame retardant systems such as antimony trioxide, magnesium hydroxide, aluminum hydroxide, silicon system and the like. Among them, the most commonly used halogen-based flame retardant has an incomparable high efficiency with other flame retardants, but is not negligible to the environment and human. Therefore, the product structure of the flame retardant is always regulated at home and abroad, and the development of the efficient environment-friendly flame retardant is enlarged. The metal organic frame material has the characteristics of porous nano structure, rich gaps, excellent compatibility with polymers, metal nodes, multifunctional ligands and the like, and provides various possibilities for flame retardants for polymeric materials.
Nonwoven fabrics are constructed of oriented or random fibers. The biodegradable environment-friendly polylactic acid polymer material is mostly adopted as a raw material, and because the material has inflammability, the material is easy to burn and generate molten drops to cause fire, so how to increase the flame retardance of the non-woven fabric and improve the use safety are the problems to be solved. The flame retardant used in the current market generally has only flame retardant effect and cannot help the non-woven fabric to degrade rapidly. Meanwhile, the common non-woven fabric has the defects of weak strength, poor durability, weak hydrophilicity and the like.
Aiming at the problems, a degradable flame-retardant plant fiber non-woven fabric and a preparation method thereof are designed.
Disclosure of Invention
The invention aims to provide a degradable flame-retardant plant fiber non-woven fabric and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a degradable flame-retardant plant fiber non-woven fabric comprises plant fiber non-woven fabric base fabric and flame retardant slurry padded on the surface of the base fabric.
The invention discloses a degradable flame-retardant plant fiber non-woven fabric, wherein a plant fiber non-woven fabric base fabric has the characteristics of easy decomposition, ventilation, moisture resistance, recycling and the like, and polylactic acid is used as a main raw material; because polylactic acid is a polymer material with inflammability, the padding process is used for padding the flame retardant slurry on the surface of the base cloth, so that the fire disaster caused by molten dripping generated by burning of the non-woven base cloth is effectively prevented.
More optimally, the plant fiber non-woven fabric base fabric takes polylactic acid as a main body, and the raw material components are as follows: 85-90 parts of polylactic acid, 15-20 parts of cotton stalk fiber, 3-8 parts of flax fiber and 8-12 parts of polyamide fiber.
The plant fiber non-woven fabric base fabric in the technical scheme comprises polylactic acid, cotton stalk fiber, flax fiber and polyamide fiber, wherein the polylactic acid is a biodegradable substance and has the defects of weak strength, poor durability and the like. Therefore, the cotton stalk fiber with good doping strength and toughness is used for increasing the toughness and strength of the non-woven fabric, and the polyamide fiber doping is used for effectively improving the wear resistance of the non-woven fabric; however, since polyamide fibers are hydrophobic fibers, static electricity is easily generated and heat resistance is poor. Therefore, flax fibers with the performances of moisture absorption, heat dissipation, bacteriostasis, static resistance and the like are added to optimize complementation, and meanwhile, the flax fibers have a certain flame retardant effect in the textile fibers due to the moisture absorption and heat dissipation of the flax fibers.
The degradation of the non-woven fabric is the degradation of polylactic acid which is a main material, most of the material is hydrolysis, and generally, an aqueous medium permeates into a polymer, so that a polymer molecular chain is loosened, lipid bonds begin to hydrolyze and gradually degrade into an oligomer, more carboxyl groups are generated, and the degradation speed is increased. However, polylactic acid has strong hydrophobicity, and the added cotton stalk fiber has natural hygroscopicity, so that the hydrolysis and degradation speed of the polylactic acid can be improved.
More optimally, the components of the raw materials of the flame retardant slurry are as follows: 5-10 parts of flame retardant, 8-15 parts of chitosan, 0.1-3 parts of malic acid and 200-220 parts of distilled water.
In the technical scheme, the raw materials of the slurry of the flame retardant comprise the flame retardant, chitosan, acetic acid and distilled water; the flame retardant is the core of the flame retardant slurry, and on one hand, the flame retardant can be directly adsorbed on the surface of the non-woven fabric base cloth by utilizing Van der Waals force through an impregnation method; on the other hand, the chitosan can be anchored on the surface of the non-woven fabric base cloth, and the specific principle is as follows: the surface of the flame retardant contains rich hydroxyl structures, and the flame retardant is hydrolyzed in distilled water to generate the flame retardant with free hydroxyl structures and has negative charges; the chitosan is dissolved in the malic acid to generate protonated chitosan, and the protonated chitosan has positive charge; so that a large amount of hydroxyl groups on the surface of the flame retardant and cationic chitosan are subjected to deprotonation reaction to generate stable hydrogen bonds. Simultaneously, amino on chitosan and the carboxyl on polylactic acid link with the mode of ionic bond, therefore, the fire retardant is anchored on the non-woven fabrics base cloth surface through the ionic state of chitosan, and intermolecular force is strong, bond energy is higher for the fire retardant is difficult to drop. Meanwhile, the hydroxyl groups on the surface of the flame retardant, the hydroxyl groups, amino groups and other polar groups contained in the chitosan have stronger hydrophilicity, can generate synergistic effect with cotton stalk fibers in non-woven fabric base cloth, and improve the hydrolysis degradation speed of polylactic acid.
More preferably, the flame retardant is Zn-MOF-74/PVA.
In the technical scheme, zn-MOF-74 is a porous organic framework taking Zn as a metal center and having carbon dioxide gas adsorption capacity, and Zn-MOF-74/PVA is prepared by uniformly wrapping Zn-MOF-74 with PVA by utilizing an electronic effect generated by divalent zinc ions in Zn-MOF-74 and hydrogen bonds in PVA.
Flame retardant principle: when the surface burns, one of the Zn-MOF-74 is oxidized to generate zinc oxide, and a compact zinc oxide protective layer is formed to prevent flame generation; secondly, carbon dioxide adsorbed in the Zn-MOF-74 pore canal and carbon dioxide generated by PVA combustion pyrolysis can effectively prevent flame from being generated; thirdly, the solid carbon layer formed by carbonization effectively prevents oxygen from diffusing and heat and mass transfer in the process of volatilizing and burning combustible substances; fourth, the flax fiber contained in the non-woven fabric has moisture absorption and heat dissipation properties, so that heat transfer is effectively prevented; in conclusion, the four flame retardant mechanisms cooperate to produce a strong flame retardant effect.
More preferably, the malic acid concentration is 10%.
In the technical scheme, the concentration of malic acid is not more than 20%, and the malic acid is more than that which is easy to cause corrosion of the surface of the flame retardant structure, so that the flame retardant is not beneficial to maintaining the porous structure of the flame retardant.
More preferably, the chitosan is prepared by deacetylation of chitin.
More preferably, the cotton stalk fiber has a flexible diameter of 25-85 μm and a length of 2-8cm.
More optimally, the preparation method of the degradable flame-retardant plant fiber non-woven fabric comprises the following steps:
1) Preparing a flame retardant;
2) Preparing plant fiber non-woven fabric base cloth;
3) Padding non-woven fabric base cloth with flame retardant slurry;
more optimally, the preparation method of the degradable flame-retardant plant fiber non-woven fabric comprises the following steps:
1) Preparation of flame retardant:
a) Raw material preparation: preparing zinc nitrate hexahydrate, 2, 5-dihydroxyterephthalic acid, DMF (azodicarbonamide), isopropanol, distilled water and PVA (polyvinyl alcohol) for later use;
b) Zn-MOF-74 preparation:
A. accurately weighing 0.604 g zinc nitrate hexahydrate and 0.19 g 2, 5-dihydroxyterephthalic acid, accurately weighing 20 mL DMF, 1 mL isopropanol and 1 mL distilled water, uniformly mixing under stirring to obtain a mixed material, and amplifying according to the required amount in equal proportion;
B. placing the mixed material in the step A into a polytetrafluoroethylene reaction kettle, sleeving an iron sheet, placing into a muffle furnace, raising the temperature to 110 ℃ at a heating rate of 3-5 ℃/min for reacting for 72 hours, and then lowering the temperature to room temperature at a heating rate of 3-5 ℃/min to obtain a reacted material;
C. b, carrying out solid-liquid separation on the reacted materials in the step B at the rotating speed of 10000r/min by using a centrifugal machine, washing 3 times by using methanol, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a Zn-MOF-74 product for later use;
c) Preparation of Zn-MOF-74/PVA flame retardant:
A. mixing the Zn-MOF-74 prepared in the step b) with distilled water, and performing ultrasonic dispersion for 30 minutes to prepare 10wt% Zn-MOF-74 aqueous suspension A for later use;
B. mixing PVA with distilled water, and stirring and dissolving at 80 ℃ to prepare 10wt% PVA aqueous suspension B for later use;
C. mixing and stirring the suspension A in the step A and the suspension B in the step B for 30 minutes, and putting the mixture into a refrigerator to be frozen at the temperature of minus 80 ℃ for 12 hours to obtain a material C;
D. c, putting the material C in the step C into a freeze dryer to be dried for 48 hours to prepare Zn-MOF-74/PVA serving as a flame retardant;
2) Preparing a vegetable fiber non-woven fabric base fabric:
a) Raw material preparation: weighing polylactic acid, cotton stalk fiber, flax fiber and polyamide fiber for standby;
b) Preparing a vegetable fiber non-woven fabric base fabric:
A. fully drying polylactic acid in a vacuum drying oven at 60 ℃, and mixing the polylactic acid with cotton stalk fibers, flax fibers and polyamide fibers by a high-speed mixer to obtain a mixture;
B. the mixture in the step A is extruded and melted by a screw, the working temperature is controlled to be 80-100 ℃, and the rotating speed is controlled to be 50-60 r/min; spraying the polylactic acid fibers through the spinneret holes, controlling the spinneret hole diameter to be 0.16-0.19 and mm, and controlling the working speed to be 6000-8000 m/min; then cooling the fiber by blowing, stretching the fiber into a net by using air flow, and controlling the air flow stretching speed to be 6000-7000 m/min; finally, rolling and reinforcing by a rolling mill embossing roller to form a non-woven fabric base fabric, controlling the roller speed to be 8-10 m/min, controlling the working pressure to be 20-25 MPa, and controlling the working temperature to be 120-140 ℃;
3) Padding non-woven fabric base cloth with flame retardant slurry:
a) Raw material preparation: weighing a flame retardant, chitosan, malic acid and distilled water for standby;
b) Padding non-woven fabric base cloth with flame retardant slurry:
A. adding the flame retardant, chitosan, malic acid and distilled water into a stirring barrel, and mixing to obtain flame retardant slurry for later use;
B. b, completely dipping the non-woven fabric base cloth in the flame retardant slurry in the step A for 12-24 hours, and taking out the non-woven fabric base cloth to squeeze in a padding machine after the dipping is finished, wherein the first padding is performed;
C. immersing the non-woven fabric base cloth padded in the step B into the flame retardant slurry again, adding an ultrasonic oscillator to carry out ultrasonic treatment for 30 minutes, and putting the non-woven fabric base cloth into a padding machine again to carry out extrusion, wherein the padding is the second padding;
D. c, padding the non-woven fabric base cloth twice in the step C, and drying the non-woven fabric base cloth in a dryer at 60 ℃ to obtain the degradable flame-retardant plant fiber non-woven fabric.
More optimally, a preparation method of the degradable flame-retardant plant fiber non-woven fabric comprises the following steps of: mass fraction ratio (1:1) - (3:1).
Compared with the prior art, the invention has the beneficial effects that:
in the preparation process, the Zn-MOF-74/PVA flame retardant is anchored on the surface of the degradable plant fiber non-woven fabric base fabric by taking the ionic state generated by dissolving chitosan in malic acid as a medium, so that the flame retardant effect is generated; the hydrophobicity of polylactic acid is optimized and complemented by utilizing the rich hydroxyl structure on the surface of the flame retardant, the hydroxyl and amino polar groups contained in chitosan and the hydrophilicity generated by cotton stalk fibers doped in non-woven fabrics, and the rate of hydrolytic degradation of the polylactic acid is effectively increased; meanwhile, the wear resistance of the non-woven fabric is effectively improved by doping the polyamide fiber, the performances of moisture absorption, heat dissipation, bacteriostasis, static resistance and the like of the non-woven fabric are improved by doping the fibrilia, and the application range of the non-woven fabric is widened.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
step S1: preparation of flame retardant:
step S11: raw material preparation: preparing zinc nitrate hexahydrate, 2, 5-dihydroxyterephthalic acid, azodicarbonamide (DMF), isopropanol, distilled water and polyvinyl alcohol (PVA) for later use;
step S12: zn-MOF-74 preparation: accurately weighing zinc nitrate hexahydrate and 2, 5-dihydroxyterephthalic acid, accurately weighing DMF, isopropanol and distilled water, and uniformly mixing under the stirring condition; putting the mixed material into a polytetrafluoroethylene reaction kettle, sleeving an iron sheet, putting into a muffle furnace, raising the temperature to 110 ℃ at a heating rate of 3 ℃/min, reacting for 72 hours, and then lowering the temperature to room temperature at the heating rate of 3 ℃/min to obtain a reacted material; solid-liquid separation is carried out by using a centrifugal machine at the rotating speed of 10000r/min, methanol is washed for 3 times, and vacuum drying is carried out at 60 ℃ for 24 hours to obtain a product Zn-MOF-74 for standby;
step S13: preparation of Zn-MOF-74/PVA flame retardant: mixing the prepared Zn-MOF-74 with distilled water, and performing ultrasonic dispersion for 30 minutes to prepare 10wt% Zn-MOF-74 aqueous suspension A; mixing PVA with distilled water, and stirring and dissolving at 80 ℃ to prepare 10wt% PVA aqueous suspension B; mixing and stirring the suspension A and the suspension B for 30 minutes, and putting the mixture into a refrigerator to be frozen for 12 hours at the temperature of minus 80 ℃; c, putting the material C in the step C into a freeze dryer to be dried for 48 hours to prepare Zn-MOF-74/PVA serving as a flame retardant;
step S2: preparing a vegetable fiber non-woven fabric base fabric:
step S21: weighing polylactic acid, cotton stalk fiber, flax fiber and polyamide fiber for standby;
step S22: preparing a vegetable fiber non-woven fabric base fabric: fully drying polylactic acid in a vacuum drying oven at 60 ℃, and mixing the polylactic acid with cotton stalk fibers, flax fibers and polyamide fibers by a high-speed mixer to obtain a mixture; extruding and melting the mixture by a screw, controlling the working temperature at 80 ℃ and the rotating speed at 50 r/min; then spraying the polylactic acid fibers through the spinneret holes, controlling the spinneret hole diameter to be 0.16 mm and the working speed to be 6000 m/min; then the fiber is cooled by blowing, and is stretched into a net by air flow, and the air flow drafting speed is controlled at 6000 m/min; finally, rolling and reinforcing by a roller mill embossing roller to form a non-woven fabric base fabric, controlling the roller speed to be 8 m/min, controlling the working pressure to be 20 MPa and controlling the working temperature to be 120 ℃;
step S3: padding non-woven fabric base cloth with flame retardant slurry:
step S31: raw material preparation: weighing a flame retardant, chitosan, malic acid and distilled water for standby;
step S32: padding non-woven fabric base cloth with flame retardant slurry: adding the flame retardant, chitosan, malic acid and distilled water into a stirring barrel, and mixing to obtain flame retardant slurry; completely dipping the non-woven fabric base cloth in the flame retardant slurry for 12 hours, taking out the non-woven fabric base cloth after the dipping is finished, and extruding in a padding machine, wherein the first padding is performed; immersing the non-woven fabric base cloth which is padded once again into the flame retardant slurry, adding an ultrasonic oscillator to carry out ultrasonic treatment for 30 minutes, and putting the non-woven fabric base cloth into a padding machine again for extrusion, wherein the second padding is carried out; and (3) padding the non-woven fabric base cloth twice, and drying the non-woven fabric base cloth at the temperature of 60 ℃ in a dryer to obtain the degradable flame-retardant plant fiber non-woven fabric.
In this embodiment, the raw material group of the degradable non-woven fabric base fabric includes 85 parts of polylactic acid, 15 parts of cotton stalk fiber, 3 parts of flax fiber and 8 parts of polyamide fiber. The components of the flame retardant slurry comprise 5 parts of flame retardant, 8 parts of chitosan, 0.1 part of malic acid and 200 parts of distilled water.
Wherein, the mixing proportion of the suspension A and the suspension B in the preparation of the Zn-MOF-74/PVA flame retardant is as follows: the mass fraction ratio is 1:1.
Wherein the first padding time of the non-woven fabric base cloth is 12 hours.
Example 2:
step S1: preparation of flame retardant:
step S11: raw material preparation: preparing zinc nitrate hexahydrate, 2, 5-dihydroxyterephthalic acid, azodicarbonamide (DMF), isopropanol, distilled water and polyvinyl alcohol (PVA) for later use;
step S12: zn-MOF-74 preparation: accurately weighing zinc nitrate hexahydrate and 2, 5-dihydroxyterephthalic acid, accurately weighing DMF, isopropanol and distilled water, and uniformly mixing under stirring; putting the mixed material into a polytetrafluoroethylene reaction kettle, sleeving an iron sheet, putting into a muffle furnace, raising the temperature to 110 ℃ at a heating rate of 4 ℃/min, reacting for 72 hours, and then lowering the temperature to room temperature at the heating rate of 4 ℃/min to obtain a reacted material; solid-liquid separation is carried out by using a centrifugal machine at the rotating speed of 10000r/min, methanol is washed for 3 times, and vacuum drying is carried out at 60 ℃ for 24 hours to obtain a product Zn-MOF-74 for standby;
step S13: preparation of Zn-MOF-74/PVA flame retardant: mixing the prepared Zn-MOF-74 with distilled water, and performing ultrasonic dispersion for 30 minutes to prepare 10wt% Zn-MOF-74 aqueous suspension A; mixing PVA with distilled water, and stirring and dissolving at 80 ℃ to prepare 10wt% PVA aqueous suspension B; mixing and stirring the suspension A and the suspension B for 30 minutes, and putting the mixture into a refrigerator to be frozen for 12 hours at the temperature of minus 80 ℃; c, putting the material C in the step C into a freeze dryer to be dried for 48 hours to prepare Zn-MOF-74/PVA serving as a flame retardant;
step S2: preparing a vegetable fiber non-woven fabric base fabric:
step S21: weighing polylactic acid, cotton stalk fiber, flax fiber and polyamide fiber for standby;
step S22: preparing a vegetable fiber non-woven fabric base fabric: fully drying polylactic acid in a vacuum drying oven at 60 ℃, and mixing the polylactic acid with cotton stalk fibers, flax fibers and polyamide fibers by a high-speed mixer to obtain a mixture; extruding and melting the mixture by a screw, controlling the working temperature at 90 ℃ and the rotating speed at 55r/min; then spraying the polylactic acid fibers through the spinneret holes, controlling the spinneret hole diameter to be 0.18mm and the working speed to be 7000m/min; then the fiber is cooled by blowing, and is stretched into a net by air flow, and the air flow drafting speed is controlled to be 6500m/min; finally, rolling and reinforcing by a rolling mill embossing roller to form a non-woven fabric base fabric, controlling the roller speed at 9m/min, controlling the working pressure at 23MPa and controlling the working temperature at 130 ℃;
step S3: padding non-woven fabric base cloth with flame retardant slurry:
step S31: raw material preparation: weighing a flame retardant, chitosan, malic acid and distilled water for standby;
step S32: padding non-woven fabric base cloth with flame retardant slurry: adding the flame retardant, chitosan, malic acid and distilled water into a stirring barrel, and mixing to obtain flame retardant slurry; completely dipping the non-woven fabric base cloth in the flame retardant slurry for 18 hours, and taking out the non-woven fabric base cloth to be extruded in a padding machine after the dipping is finished, wherein the first padding is performed; immersing the non-woven fabric base cloth which is padded once again into the flame retardant slurry, adding an ultrasonic oscillator to carry out ultrasonic treatment for 30 minutes, and putting the non-woven fabric base cloth into a padding machine again for extrusion, wherein the second padding is carried out; and (3) padding the non-woven fabric base cloth twice, and drying the non-woven fabric base cloth at the temperature of 60 ℃ in a dryer to obtain the degradable flame-retardant plant fiber non-woven fabric.
In this embodiment, the raw material group of the degradable non-woven fabric base fabric includes 88 parts of polylactic acid, 18 parts of cotton stalk fiber, 5 parts of flax fiber and 10 parts of polyamide fiber. The components of the flame retardant slurry comprise 8 parts of flame retardant, 12 parts of chitosan, 1.5 parts of malic acid and 210 parts of distilled water.
Wherein, the mixing proportion of the suspension A and the suspension B in the preparation of the Zn-MOF-74/PVA flame retardant is as follows: the mass fraction ratio is 2:1.
Wherein the first padding time of the non-woven fabric base cloth is 18 hours.
Example 3:
step S1: preparation of flame retardant:
step S11: raw material preparation: preparing zinc nitrate hexahydrate, 2, 5-dihydroxyterephthalic acid, azodicarbonamide (DMF), isopropanol, distilled water and polyvinyl alcohol (PVA) for later use;
step S12: zn-MOF-74 preparation: accurately weighing zinc nitrate hexahydrate and 2, 5-dihydroxyterephthalic acid, accurately weighing DMF, isopropanol and distilled water, and uniformly mixing under stirring; putting the mixed material into a polytetrafluoroethylene reaction kettle, sleeving an iron sheet, putting into a muffle furnace, raising the temperature to 110 ℃ at a heating rate of 5 ℃/min, reacting for 72 hours, and then lowering the temperature to room temperature at the heating rate of 5 ℃/min to obtain a reacted material; solid-liquid separation is carried out by using a centrifugal machine at the rotating speed of 10000r/min, methanol is washed for 3 times, and vacuum drying is carried out at 60 ℃ for 24 hours to obtain a product Zn-MOF-74 for standby;
step S13: preparation of Zn-MOF-74/PVA flame retardant: mixing the prepared Zn-MOF-74 with distilled water, and performing ultrasonic dispersion for 30 minutes to prepare 10wt% Zn-MOF-74 aqueous suspension A; mixing PVA with distilled water, and stirring and dissolving at 80 ℃ to prepare 10wt% PVA aqueous suspension B; mixing and stirring the suspension A and the suspension B for 30 minutes, and putting the mixture into a refrigerator to be frozen for 12 hours at the temperature of minus 80 ℃; c, putting the material C in the step C into a freeze dryer to be dried for 48 hours to prepare Zn-MOF-74/PVA serving as a flame retardant;
step S2: preparing a vegetable fiber non-woven fabric base fabric:
step S21: weighing polylactic acid, cotton stalk fiber, flax fiber and polyamide fiber for standby;
step S22: preparing a vegetable fiber non-woven fabric base fabric: fully drying polylactic acid in a vacuum drying oven at 60 ℃, and mixing the polylactic acid with cotton stalk fibers, flax fibers and polyamide fibers by a high-speed mixer to obtain a mixture; extruding and melting the mixture by a screw, controlling the working temperature at 100 ℃ and the rotating speed at 60 r/min; then spraying the polylactic acid fibers through spinneret holes, controlling the spinneret hole diameter to be 0.19 and mm, and controlling the working speed to be 8000 m/min; then the fiber is cooled by blowing, and is stretched into a net by air flow, and the air flow drafting speed is controlled at 7000m/min; finally, rolling and reinforcing by a rolling mill embossing roller to form a non-woven fabric base fabric, controlling the roller speed to be 10 m/min, controlling the working pressure to be 25 MPa and controlling the working temperature to be 140 ℃;
step S3: padding non-woven fabric base cloth with flame retardant slurry:
step S31: raw material preparation: weighing a flame retardant, chitosan, malic acid and distilled water for standby;
step S32: padding non-woven fabric base cloth with flame retardant slurry: adding the flame retardant, chitosan, malic acid and distilled water into a stirring barrel, and mixing to obtain flame retardant slurry; completely dipping the non-woven fabric base cloth in the flame retardant slurry for 18 hours, and taking out the non-woven fabric base cloth to be extruded in a padding machine after the dipping is finished, wherein the first padding is performed; immersing the non-woven fabric base cloth which is padded once again into the flame retardant slurry, adding an ultrasonic oscillator to carry out ultrasonic treatment for 30 minutes, and putting the non-woven fabric base cloth into a padding machine again for extrusion, wherein the second padding is carried out; and (3) padding the non-woven fabric base cloth twice, and drying the non-woven fabric base cloth at the temperature of 60 ℃ in a dryer to obtain the degradable flame-retardant plant fiber non-woven fabric.
In this embodiment, the raw material group of the degradable non-woven fabric base fabric includes 90 parts of polylactic acid, 20 parts of cotton stalk fiber, 8 parts of flax fiber and 12 parts of polyamide fiber; the components of the flame retardant slurry comprise 10 parts of flame retardant, 15 parts of chitosan, 3 parts of malic acid and 220 parts of distilled water.
Wherein, the mixing proportion of the suspension A and the suspension B in the preparation of the Zn-MOF-74/PVA flame retardant is as follows: the mass fraction ratio is 3:1.
Wherein the first padding time of the non-woven fabric base cloth is 24 hours.
Example 4:
the procedure was the same as in example 3, except that Zn-MOF-74 was used as a flame retardant.
Example 5:
the procedure is as in example 3, with ZIF-8 as flame retardant.
Example 6:
the procedure was as in example 3, without adding flame retardant.
Experiment 1:
a sample of the degradable flame retardant plant fiber nonwoven fabric prepared in examples 1-6 was taken, and the polar oxygen index (LOI) of the sample was measured according to the GB/T2406-1993 standard test method, and the results were as follows:
LOI values after detection of the samples of examples 1-6 were 32.3%, 39.1%, 35.0%,26.0%, 24.0%, 21.0%, respectively
Conclusion: it can be seen from the data of examples 1 to 6 that the flame retardance of the vegetable fiber nonwoven fabric can be improved indeed by adding a flame retardant; from examples 1-5, it can be stated that: the Zn-MOF-74 or ZIF-8 is used as a flame retardant alone, but the flame retardance of the Zn-MOF-74/PVA is far higher than that of the Zn-MOF-74 or ZIF-8, because when the surface burns, not only Zn-MOF-74 is oxidized to generate zinc oxide to form a compact zinc oxide protective layer, but also carbon dioxide generated by burning and pyrolyzing PVA effectively blocks the generation of flame, and a synergistic effect is generated between the Zn-MOF-74 and the ZIF-8, so that the flame retardant has strong flame retardance.
Experiment 2: the sample of the degradable flame-retardant plant fiber nonwoven fabric prepared in examples 1-4 was taken for testing the flame retardant loading, the nonwoven fabrics before and after loading the flame retardant were weighed according to the method described in CN201911067737.4, and were respectively recorded as M nonwoven fabric and M composite material, the loading was a (unit g/g), and the formula was calculated:
a= (M composite-M nonwoven)/M nonwoven,
wherein, M composite material is the mass after the load, and M non-woven fabrics is the mass before the load, and the calculation result is as follows:
the loading of the samples in examples 1-4 was 69.2%, 90.6%, 79.1%, 42.6%, respectively.
It was concluded that from examples 1-3, the Zn-MOF-74/PVA flame retardant slurry was the most loaded when it was first pad-rolled, preferably with an immersion time of 18 hours. Comparing example 4 with example 3, the loading amount of Zn-MOF-74 alone is not high, because Zn-MOF-74 is only adsorbed on the surface of the plant fiber nonwoven fabric substrate by virtue of Van der Waals force, and Zn-MOF-74/PVA is not only adsorbed by Van der Waals force, but also anchored on the surface of the plant fiber nonwoven fabric substrate by virtue of chitosan.
Experiment 3: taking a degradable flame-retardant plant fiber non-woven fabric sample prepared in examples 1-6, carrying out hydrophilicity test by taking a common non-woven fabric in the market as a control sample, adhering the sample on a glass slide by using glue according to the method described in CN202010214691.2, placing the sample on a JY-82 video contact angle measuring instrument for testing, adopting static contact angle measurement, dripping water drops with the volume of 3 on the surface of the sample, repeatedly measuring three times by measuring the included angle from the solid-liquid interface to the gas-liquid interface at the three-phase junction, and taking the average value, wherein the result is as follows:
the average contact angles of the samples in examples 1-6 were 36.28 °, 33.33 °, 35.67 °, 70.51 °, 70.92 °, 120.36, respectively, whereas the contact angles of the commercially available conventional nonwoven fabrics were 110.25 °.
Conclusion that the contact angle is smaller than 80 degrees indicates that the samples in examples 1-5 are hydrophilic, and the hydrophilic property is generated by the cooperation of the hydroscopic property of the doped flax fiber, the natural hydroscopicity of the cotton stalk fiber, the hydroxyl and amino contained in chitosan and other polar groups; whereas examples 1-3 are more hydrophilic than examples 4 and 5 because of the abundant hydroxyl structure on the surface of the flame retardant. The hydrophilicity is responsible for accelerating the hydrolysis self-degradation rate of polylactic acid. Example 6 has hydrophobicity because ZIF-8 has strong hydrophobicity.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A degradable flame retardant vegetable fiber nonwoven fabric, characterized in that: the degradable flame-retardant plant fiber non-woven fabric comprises: the flame retardant comprises a vegetable fiber non-woven fabric base cloth and flame retardant slurry padded on the surface of the base cloth; the flame retardant slurry comprises the following raw materials in parts by weight: 8 parts of flame retardant, 12 parts of chitosan, 1.5 parts of malic acid and 210 parts of distilled water by weight; the plant fiber non-woven fabric base cloth takes polylactic acid as a main body, and comprises the following raw material components: 88 parts of polylactic acid, 18 parts of cotton stalk fiber, 5 parts of flax fiber and 10 parts of polyamide fiber by weight;
the preparation method comprises the following steps:
step S1: preparation of flame retardant:
step S11: raw material preparation: preparing zinc nitrate hexahydrate, 2, 5-dihydroxyterephthalic acid, azodicarbonamide (DMF), isopropanol, distilled water and polyvinyl alcohol (PVA) for later use;
step S12: zn-MOF-74 preparation: accurately weighing zinc nitrate hexahydrate and 2, 5-dihydroxyterephthalic acid, accurately weighing DMF, isopropanol and distilled water, and uniformly mixing under stirring; putting the mixed material into a polytetrafluoroethylene reaction kettle, sleeving an iron sheet, putting into a muffle furnace, raising the temperature to 110 ℃ at a heating rate of 4 ℃/min, reacting for 72 hours, and then lowering the temperature to room temperature at the heating rate of 4 ℃/min to obtain a reacted material; solid-liquid separation is carried out by using a centrifugal machine at the rotating speed of 10000r/min, methanol is washed for 3 times, and vacuum drying is carried out at 60 ℃ for 24 hours to obtain a product Zn-MOF-74 for standby;
step S13: preparation of Zn-MOF-74/PVA flame retardant: mixing the prepared Zn-MOF-74 with distilled water, and performing ultrasonic dispersion for 30 minutes to prepare 10wt% Zn-MOF-74 aqueous suspension A; mixing PVA with distilled water, and stirring and dissolving at 80 ℃ to prepare 10wt% PVA aqueous suspension B; mixing and stirring the suspension A and the suspension B for 30 minutes, and putting the mixture into a refrigerator to be frozen for 12 hours at the temperature of minus 80 ℃; c, putting the material C in the step C into a freeze dryer to be dried for 48 hours to prepare Zn-MOF-74/PVA serving as a flame retardant;
step S2: preparing a vegetable fiber non-woven fabric base fabric:
step S21: weighing polylactic acid, cotton stalk fiber, flax fiber and polyamide fiber for standby;
step S22: preparing a vegetable fiber non-woven fabric base fabric: fully drying polylactic acid in a vacuum drying oven at 60 ℃, and mixing the polylactic acid with cotton stalk fibers, flax fibers and polyamide fibers by a high-speed mixer to obtain a mixture; extruding and melting the mixture by a screw, controlling the working temperature at 90 ℃ and the rotating speed at 55r/min; then spraying the polylactic acid fibers through spinneret holes, controlling the spinneret hole diameter to be 0.18mm, and controlling the working speed to be 7000m/min; then cooling the fiber by blowing, stretching the fiber into a net by using air flow, and controlling the air flow stretching speed to 6500m/min; finally, rolling and reinforcing by a roller of a rolling mill to form non-woven fabric base cloth, controlling the roller speed at 9m/min, controlling the working pressure at 23MPa and controlling the working temperature at 130 ℃;
step S3: padding non-woven fabric base cloth with flame retardant slurry:
step S31: raw material preparation: weighing a flame retardant, chitosan, malic acid and distilled water for standby;
step S32: padding non-woven fabric base cloth with flame retardant slurry: adding the flame retardant, chitosan, malic acid and distilled water into a stirring barrel, and mixing to obtain flame retardant slurry; completely dipping the non-woven fabric base cloth in the flame retardant slurry for 18 hours, and taking out the non-woven fabric base cloth to be extruded in a padding machine after the dipping is finished, wherein the first padding is performed; immersing the non-woven fabric base cloth which is padded once again into the flame retardant slurry, adding an ultrasonic oscillator to carry out ultrasonic treatment for 30 minutes, and putting the non-woven fabric base cloth into a padding machine again for extrusion, wherein the second padding is carried out; padding the non-woven fabric base cloth twice, and drying the non-woven fabric base cloth at the temperature of 60 ℃ in a dryer to obtain the degradable flame-retardant plant fiber non-woven fabric;
wherein, the mixing proportion of the suspension A and the suspension B in the preparation of the Zn-MOF-74/PVA flame retardant is as follows: the mass fraction ratio is 2:1;
wherein the first padding time of the non-woven fabric base cloth is 18 hours.
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