CN107988811B - 一种阻燃性聚氨酯合成革 - Google Patents
一种阻燃性聚氨酯合成革 Download PDFInfo
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- CN107988811B CN107988811B CN201711262033.3A CN201711262033A CN107988811B CN 107988811 B CN107988811 B CN 107988811B CN 201711262033 A CN201711262033 A CN 201711262033A CN 107988811 B CN107988811 B CN 107988811B
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- Prior art keywords
- flame
- synthetic leather
- retardant
- polyurethane
- prepared
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 106
- 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 100
- 239000002649 leather substitute Substances 0.000 title claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 31
- 239000004814 polyurethane Substances 0.000 title claims abstract description 31
- 239000004744 fabric Substances 0.000 claims abstract description 41
- 229920006264 polyurethane film Polymers 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000004381 surface treatment Methods 0.000 claims abstract description 15
- -1 styrene-ethylene-butylene-styrene Chemical class 0.000 claims abstract description 11
- 239000004952 Polyamide Substances 0.000 claims abstract description 10
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 10
- 229920002647 polyamide Polymers 0.000 claims abstract description 10
- 229920002545 silicone oil Polymers 0.000 claims abstract description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 10
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 10
- 229920006132 styrene block copolymer Polymers 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 8
- 239000003086 colorant Substances 0.000 claims abstract description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 39
- 239000000347 magnesium hydroxide Substances 0.000 claims description 32
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- UVTXHAOLTBFLDL-UHFFFAOYSA-N 4-[(4-carboxyphenyl)-phenylphosphoryl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1P(=O)(C=1C=CC(=CC=1)C(O)=O)C1=CC=CC=C1 UVTXHAOLTBFLDL-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- YBTVSGCNBZPRBD-UHFFFAOYSA-N 4-acetamidosalicylic acid Chemical compound CC(=O)NC1=CC=C(C(O)=O)C(O)=C1 YBTVSGCNBZPRBD-UHFFFAOYSA-N 0.000 claims description 9
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 9
- OLSDAJRAVOVKLG-UHFFFAOYSA-N 3-hydroxymandelic acid Chemical compound OC(=O)C(O)C1=CC=CC(O)=C1 OLSDAJRAVOVKLG-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 8
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 8
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 229920001410 Microfiber Polymers 0.000 claims description 7
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004049 embossing Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 claims description 7
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- QZAYGJVTTNCVMB-UHFFFAOYSA-N serotonin Chemical compound C1=C(O)C=C2C(CCN)=CNC2=C1 QZAYGJVTTNCVMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000004595 color masterbatch Substances 0.000 claims description 5
- ZHQLTKAVLJKSKR-UHFFFAOYSA-N homophthalic acid Chemical compound OC(=O)CC1=CC=CC=C1C(O)=O ZHQLTKAVLJKSKR-UHFFFAOYSA-N 0.000 claims description 5
- LOQLDQJTSMKBJU-UHFFFAOYSA-N 4-(chloromethyl)benzonitrile Chemical compound ClCC1=CC=C(C#N)C=C1 LOQLDQJTSMKBJU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 4
- NILQLFBWTXNUOE-UHFFFAOYSA-N 1-aminocyclopentanecarboxylic acid Chemical compound OC(=O)C1(N)CCCC1 NILQLFBWTXNUOE-UHFFFAOYSA-N 0.000 claims description 3
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 3
- 229950004394 ditiocarb Drugs 0.000 claims description 3
- XVAIDCNLVLTVFM-UHFFFAOYSA-N methacetin Chemical compound COC1=CC=C(NC(C)=O)C=C1 XVAIDCNLVLTVFM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000002759 woven fabric Substances 0.000 description 5
- WQRQPAHIQRQBNP-UHFFFAOYSA-N 2-[carboxy(phenyl)methyl]benzoic acid Chemical compound C=1C=CC=C(C(O)=O)C=1C(C(=O)O)C1=CC=CC=C1 WQRQPAHIQRQBNP-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- ZJVMUAMBOGFWRS-UHFFFAOYSA-M potassium;2-carboxy-5-nitrobenzenesulfonate Chemical compound [K+].OS(=O)(=O)C1=CC([N+]([O-])=O)=CC=C1C([O-])=O ZJVMUAMBOGFWRS-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZGTNBBQKHJMUBI-UHFFFAOYSA-N bis[tetrakis(hydroxymethyl)-lambda5-phosphanyl] sulfate Chemical group OCP(CO)(CO)(CO)OS(=O)(=O)OP(CO)(CO)(CO)CO ZGTNBBQKHJMUBI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GINSPFZBRUHFCY-UHFFFAOYSA-L dipotassium;4-nitro-2-sulfonatobenzoate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C([N+]([O-])=O)C=C1S([O-])(=O)=O GINSPFZBRUHFCY-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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- 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
- D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/1845—Aromatic mono- or polycarboxylic acids
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
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- 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
- D06M13/402—Amides imides, sulfamic acids
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- 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
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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- 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
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- 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
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- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/0004—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 ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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- 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
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Abstract
阻燃性聚氨酯合成革,采用下述步骤制备得到,其特征在于,将12g热塑性聚氨酯与3g苯乙烯‑丁二烯‑苯乙烯嵌段共聚物、苯乙烯‑乙烯‑丁烯‑苯乙烯嵌段共聚物3g、聚酰胺型热塑性弹性体7g、着色剂2g和物质A2g于90~370℃通过挤压机挤出制得厚度0.8mm的聚氨酯膜;在改性聚氨酯膜膜冷却前将其与阻燃基布在1.0Mpa的压力下通过挤压辊复合压制,然后在0.2Mpa压力下由带有纹络的辊筒压纹,冷却后,制得初级合成革;在制得的初级合成革通过90℃水溶性硅油溶液进行表面处理,在110℃的烘箱中烘干,制得阻燃性聚氨酯合成革,所制的阻燃性聚氨酯合成革阻燃性达到良好以上级别。
Description
本申请是申请号为201610611485.7发明名称为一种阻燃性聚氨酯合成革的制备方法的专利申请的分案申请。
技术领域
本发明涉及一种聚氨酯合成革的制备方法,尤其涉及到一种阻燃性聚氨酯合成革及其制备方法。
背景技术
聚氨酯合成革经过多年的发展以其良好的外观手感和透气透湿性、耐磨耐溶剂、高强度、应用广泛等诸多优点,在工业、民用、军用等领域得到了广泛应用,与人们的生产、生活息息相关。
聚氨酯合成革主要采用聚氨酯树脂溶液与无纺布、机织布、针织布等布基进行干、湿法 加工而成,此类传统聚氨酯合成革不具有阻燃特性,存在普通高分子材料易于燃烧的缺点, 作为一种高分子材料在给人们的生产、生活带来舒适和方便的同时,也潜伏了很大的安全 隐患,尤其是汽车坐垫、高速列车、航空、特殊用途的鞋类、建筑装饰对阻燃有特殊用途。
由于聚氨酯材料是一种有机高分子材料,未经阻燃处理的聚氨酯不抗燃,遇火会燃烧并分解,产生大量有毒烟雾和气体,危害人身财产安全。特别在家具汽车行业中,阻燃性能更为重要。如何开发出安全可靠的阻燃合成革产品,是整个合成革行业亟需解决的一个问题。添加阻燃剂是最常用的方法,阻燃剂可以被用来提高皮革的抗燃性,以达到具有阻燃性能的目的。
常规阻燃剂有卤系阻燃剂、磷系阻燃剂和无机类阻燃剂3大类。卤系阻燃剂具有优异的稳定性、分解温度高(300℃以上)、使用量少、阻燃效率高等优点,其主要缺点是分解产物毒性大、燃烧生烟多、有腐蚀性、毒性气体放出,因而近年来正逐步被其他无卤阻燃剂所替代。磷系阻燃剂包括有机磷系和无机磷系两大类。磷系阻燃剂稳定性好、不易挥发、不产生腐蚀性气体、阻燃效果持久、毒性低。磷系阻燃剂具有良好的阻燃性,又不会对环境造成污染,被认为是当今阻燃剂。
发明内容
本发明利用膨胀型阻燃剂与环保型氢氧化镁阻燃剂络和对聚氨酯合成革进行阻燃处理,利用邻羧基苯乙酸、双(4-羧基苯基)苯基氧化膦、4-乙酰氨基水杨酸和次氮基三乙酸与氢氧化镁和膨胀型阻燃剂络合,得到氢氧化镁和膨胀型阻燃剂的复合体系,弥补传统氢氧化镁与有机材料相容性差的缺陷,提高环保型氢氧化镁阻燃剂与基布的相容性。
一种阻燃性聚氨酯合成革的制备方法,其特征在于:
(1)氢氧化镁与氮磷膨胀型阻燃剂络合体系:将15.4g三羟甲基丙烷、27.8g四羟甲基硫 酸磷、34.5g磷酸,依次加入250ml的三口烧瓶中,放入恒温油浴锅80℃并保持恒温,再加入 三聚氯氰4.2g、四羟丙基乙二胺2.2g、四乙酰乙二胺0.3g和四乙基溴化铵0.5g,反应时间为 2h,得到膨胀型阻燃剂,再加入氢氧化镁2.7g、邻羧基苯乙酸0.7g、双(4-羧基苯基)苯基氧 化膦0.2g、4-乙酰氨基水杨酸0.3g、次氮基三乙酸0.5g和3-羟基扁桃酸0.6g,60℃并保持恒 温2h,最终得到红棕色粘稠状液体,即氢氧化镁与氮磷膨胀型阻燃剂络合体系;
(2)相容剂的制备:取丙烯酰胺13g置于三口烧瓶中,并加入0.12g催化剂,取月桂酰氯 2ml置于烘干的恒压滴液漏斗中并加入溶剂正己烷2ml;将月桂酰氯溶液滴加到三口烧瓶 中,控制滴加速度为5 秒/滴,滴加过程在冰水浴中进行,并用质量分数为10%的氢氧化钠调 节反应的pH值为8,冰水浴中滴加反应时间0.6 h,然后升高温度至20℃,反应时间3h,反应 结束后减压蒸出溶剂,进行喷雾干燥,得相容剂;
(3)基布的处理:将基布20g浸入到100g的步骤(1)的改性氢氧化镁阻燃剂、步骤(2)的 相容剂1.8g和氨基脲0.4g,然后在 100℃的烘道中将其烘干,制得阻燃基布待用;
(4) 改性聚氨酯膜
将12g热塑性聚氨酯与 3g苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁烯-苯 乙烯嵌段共聚物3g、聚酰胺型热塑性弹性体7g、着色剂2g和物质A2g于90℃-370℃通过挤压 机挤出制得厚度 0.8mm 的聚氨酯膜;
(5) 初级合成革
在步骤 (4)制得的改性聚氨酯膜膜冷却前将其与步骤 (3) 制得的阻燃基布在1.0Mpa 的压力下通过挤压辊复合压制,然后在 0.2Mpa 压力下由带有纹络的辊筒压纹,冷却后,制得初级合成革。
(6) 表面处理及修饰 :
将步骤 (5) 制得的初级合成革通过90℃水溶性硅油溶液进行表面处理,在110℃的烘 箱中烘干,制得阻燃性聚氨酯合成革。
基布为机织布或超纤布;催化剂为二硫代二苯甲酸、甲醇钠、过硫酸铵、二乙基二硫代氨基甲酸钠、苄基三乙基氯化中的任意一种;着色剂为色母料或色粉; 物质A为三羟甲基乙烷、双(4-羧基苯基)苯基氧化膦、2-羧基-5-硝基苯磺酸钾、5-羟基色胺、环亮氨酸、对甲氧基乙酰苯胺、对氰基氯苄、羟乙基纤维素。
本发明与传统技术具有的优点
(1)水溶性硅油选择TS-19水溶性硅油,购买于青岛中宝硅材料科技有限公司;热塑性 聚氨酯购买于得创热塑性聚氨酯(东莞)有限公司;聚酰胺型热塑性弹性体购买于美国杜邦 公司的聚酰胺型热塑性弹性体TPAE,其它化料常规购买,当然所有材料可以购买于主要成 分含有此类的厂家;
(2)利用邻羧基苯乙酸、双(4-羧基苯基)苯基氧化膦、4-乙酰氨基水杨酸和次氮基三乙 酸与氢氧化镁和膨胀型阻燃剂络合,得到氢氧化镁和膨胀型阻燃剂的复合体系,弥补传统 氢氧化镁与有机材料相容性差的缺陷;
(3)物质A为三羟甲基乙烷、双(4-羧基苯基)苯基氧化膦、2-羧基-5-硝基苯磺酸钾、5- 羟基色胺、环亮氨酸、对甲氧基乙酰苯胺、对氰基氯苄、羟乙基纤维素降低聚氨酯燃烧所形 成熔滴,避免聚氨酯燃烧进行;
(4)相容剂增加了氢氧化镁与机织布或超纤布的相容性,氨基脲增强相容剂、氢氧化镁 与基布结合,相当于相容剂、氢氧化镁之间的催化剂;
(5)苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物也就是SEBS,苯乙烯-丁二烯-苯乙烯嵌段共 聚物可常规方法合成,也可从市场购买;
(6)本发明所用化工材料只要主要成分为其均可适用本发明。
(7)根据膨胀型阻燃剂构成的碳源为三羟甲基丙烷、酸源为四羟甲基硫酸磷和磷酸,三聚氯氰为气源,四羟丙基乙二胺、四乙酰乙二胺、四乙基溴化铵和3-羟基扁桃酸增加了膨胀型阻燃剂的立体型,使所制备的阻燃性成炭性提高。
具体实施方式
实施例1
(1)氢氧化镁与氮磷膨胀型阻燃剂络合体系:将15.4g三羟甲基丙烷、27.8g四羟甲基硫 酸磷、34.5g磷酸,依次加入250ml的三口烧瓶中,放入恒温油浴锅80℃并保持恒温,再加入 三聚氯氰4.2g、四羟丙基乙二胺2.2g、四乙酰乙二胺0.3g和四乙基溴化铵0.5g,反应时间为 2h,得到膨胀型阻燃剂,再加入氢氧化镁2.7g、邻羧基苯乙酸0.7g、双(4-羧基苯基)苯基氧 化膦0.2g、4-乙酰氨基水杨酸0.3g、次氮基三乙酸0.5g和3-羟基扁桃酸0.6g,60℃恒温2h, 最终得到红棕色粘稠状液体,即氢氧化镁与氮磷膨胀型阻燃剂络合体系;
(2)相容剂的制备:取丙烯酰胺13g置于三口烧瓶中,并加入0.12g二硫代二苯甲酸,取 月桂酰氯2ml置于烘干的恒压滴液漏斗中并加入溶剂正己烷2ml;将月桂酰氯溶液滴加到三 口烧瓶中,控制滴加速度为5 秒/滴,滴加过程在冰水浴中进行,并用质量分数为10%的氢氧 化钠调节反应的pH值为8,冰水浴中滴加反应时间0.6 h,然后升高温度至20℃,反应时间 3h,反应结束后减压蒸出溶剂,进行喷雾干燥,得相容剂;
(3)基布的处理:将机织布20g浸入到100g的步骤(1)的改性氢氧化镁阻燃剂、步骤(2) 的相容剂1.8g和氨基脲0.4g,然后在 100℃的烘道将其烘干,制得阻燃基布待用;
(4) 改性聚氨酯膜
将12g热塑性聚氨酯与 3g苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁烯-苯 乙烯嵌段共聚物3g、聚酰胺型热塑性弹性体7g、色母料2g和三羟甲基乙烷2g于90℃通过挤 压机挤出制得厚度 0.8mm 的聚氨酯膜;
(5) 初级合成革
在步骤 (4)制得的改性聚氨酯膜膜冷却前将其与步骤 (3) 制得的阻燃基布在1.0Mpa 的压力下通过挤压辊复合压制,然后在 0.2Mpa 压力下由带有纹络的辊筒压纹,冷却后,制得初级合成革。
(6) 表面处理及修饰 :
将步骤 (5) 制得的初级合成革通过90℃水溶性硅油溶液进行表面处理,在110℃的烘 箱中烘干,制得阻燃性聚氨酯合成革。
实施例2
(1)氢氧化镁与氮磷膨胀型阻燃剂络合体系:将15.4g三羟甲基丙烷、27.8g四羟甲基硫 酸磷、34.5g磷酸,依次加入250ml的三口烧瓶中,放入恒温油浴锅80℃并保持恒温,再加入 三聚氯氰4.2g、四羟丙基乙二胺2.2g、四乙酰乙二胺0.3g和四乙基溴化铵0.5g,反应时间为 2h,得到膨胀型阻燃剂,再加入氢氧化镁2.7g、邻羧基苯乙酸0.7g、双(4-羧基苯基)苯基氧 化膦0.2g、4-乙酰氨基水杨酸0.3g、次氮基三乙酸0.5g和3-羟基扁桃酸0.6g,60℃并保持恒 温2h,最终得到红棕色粘稠状液体,即氢氧化镁与氮磷膨胀型阻燃剂络合体系;
(2)相容剂的制备:取丙烯酰胺13g置于三口烧瓶中,并加入0.12g甲醇钠,取月桂酰氯 2ml置于烘干的恒压滴液漏斗中并加入溶剂正己烷2ml;将月桂酰氯溶液滴加到三口烧瓶 中,控制滴加速度为5 秒/滴,滴加过程在冰水浴中进行,并用质量分数为10%的氢氧化钠调 节反应的pH值为8,冰水浴中滴加反应时间0.6 h,然后升高温度至20℃,反应时间3h,反应 结束后减压蒸出溶剂,进行喷雾干燥,得相容剂;
(3)基布的处理:将超纤布20g浸入到100g的步骤(1)的改性氢氧化镁阻燃剂、步骤(2) 的相容剂1.8g和氨基脲0.4g,然后在 100℃的烘道中将其烘干,制得阻燃基布待用;
(4) 改性聚氨酯膜
将12g热塑性聚氨酯与 3g苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁烯-苯 乙烯嵌段共聚物3g、聚酰胺型热塑性弹性体7g、色粉2g和双(4-羧基苯基)苯基氧化膦2g于 370℃通过挤压机挤出制得厚度 0.8mm 的聚氨酯膜;
(5) 初级合成革
在步骤 (4)制得的改性聚氨酯膜膜冷却前将其与步骤 (3) 制得的阻燃基布在1.0Mpa 的压力下通过挤压辊复合压制,然后在 0.2Mpa 压力下由带有纹络的辊筒压纹,冷却后,制得初级合成革。
(6) 表面处理及修饰 :
将步骤 (5) 制得的初级合成革通过90℃水溶性硅油溶液进行表面处理,在110℃的烘 箱中烘干,制得阻燃性聚氨酯合成革。
实施例3
(1)氢氧化镁与氮磷膨胀型阻燃剂络合体系:将15.4g三羟甲基丙烷、27.8g四羟甲基硫 酸磷、34.5g磷酸,依次加入250ml的三口烧瓶中,放入恒温油浴锅80℃并保持恒温,再加入 三聚氯氰4.2g、四羟丙基乙二胺2.2g、四乙酰乙二胺0.3g和四乙基溴化铵0.5g,反应时间为 2h,得到膨胀型阻燃剂,再加入氢氧化镁2.7g、邻羧基苯乙酸0.7g、双(4-羧基苯基)苯基氧 化膦0.2g、4-乙酰氨基水杨酸0.3g、次氮基三乙酸0.5g和3-羟基扁桃酸0.6g,60℃并保持恒 温2h,最终得到红棕色粘稠状液体,即氢氧化镁与氮磷膨胀型阻燃剂络合体系;
(2)相容剂的制备:取丙烯酰胺13g置于三口烧瓶中,并加入0.12g过硫酸铵,取月桂酰 氯2ml置于烘干的恒压滴液漏斗中并加入溶剂正己烷2ml;将月桂酰氯溶液滴加到三口烧瓶 中,控制滴加速度为5 秒/滴,滴加过程在冰水浴中进行,并用质量分数为10%的氢氧化钠调 节反应的pH值为8,冰水浴中滴加反应时间0.6 h,然后升高温度至20℃,反应时间3h,反应 结束后减压蒸出溶剂,进行喷雾干燥,得相容剂;
(3)基布的处理:将机织布20g浸入到100g的步骤(1)的改性氢氧化镁阻燃剂、步骤(2) 的相容剂1.8g和氨基脲0.4g,然后在 100℃的烘道中将其烘干,制得阻燃基布待用;
(4) 改性聚氨酯膜
将12g热塑性聚氨酯与 3g苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁烯-苯 乙烯嵌段共聚物3g、聚酰胺型热塑性弹性体7g、色母料2g和2-羧基-5-硝基苯磺酸钾2g于 230℃通过挤压机挤出制得厚度 0.8mm 的聚氨酯膜;
(5) 初级合成革
在步骤 (4)制得的改性聚氨酯膜膜冷却前将其与步骤 (3) 制得的阻燃基布在1.0Mpa 的压力下通过挤压辊复合压制,然后在 0.2Mpa 压力下由带有纹络的辊筒压纹,冷却后,制得初级合成革。
(6) 表面处理及修饰 :
将步骤 (5) 制得的初级合成革通过90℃水溶性硅油溶液进行表面处理,在110℃的烘 箱中烘干,制得阻燃性聚氨酯合成革。
实施例4
(1)氢氧化镁与氮磷膨胀型阻燃剂络合体系:将15.4g三羟甲基丙烷、27.8g四羟甲基硫 酸磷、34.5g磷酸,依次加入250ml的三口烧瓶中,放入恒温油浴锅80℃并保持恒温,再加入 三聚氯氰4.2g、四羟丙基乙二胺2.2g、四乙酰乙二胺0.3g和四乙基溴化铵0.5g,反应时间为 2h,得到膨胀型阻燃剂,再加入氢氧化镁2.7g、邻羧基苯乙酸0.7g、双(4-羧基苯基)苯基氧 化膦0.2g、4-乙酰氨基水杨酸0.3g、次氮基三乙酸0.5g和3-羟基扁桃酸0.6g,60℃恒温2h, 最终得到红棕色粘稠状液体,即氢氧化镁与氮磷膨胀型阻燃剂络合体系;
(2)相容剂的制备:取丙烯酰胺13g置于三口烧瓶中,并加入0.12g二乙基二硫代氨基甲 酸钠,取月桂酰氯2ml置于烘干的恒压滴液漏斗中并加入溶剂正己烷2ml;将月桂酰氯溶液 滴加到三口烧瓶中,控制滴加速度为5 秒/滴,滴加过程在冰水浴中进行,并用质量分数为 10%的氢氧化钠调节反应的pH值为8,冰水浴中滴加反应时间0.6 h,然后升高温度至20℃, 反应时间3h,反应结束后减压蒸出溶剂,进行喷雾干燥,得相容剂;
(3)基布的处理:将机织布20g浸入到100g的步骤(1)的改性氢氧化镁阻燃剂、步骤(2) 的相容剂1.8g和氨基脲0.4g,然后在 100℃的烘道将其烘干,制得阻燃基布待用;
(4) 改性聚氨酯膜
将12g热塑性聚氨酯与 3g苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁烯-苯 乙烯嵌段共聚物3g、聚酰胺型热塑性弹性体7g、色母料2g和对氰基氯苄2g于90℃通过挤压 机挤出制得厚度 0.8mm 的聚氨酯膜;
(5) 初级合成革
在步骤 (4)制得的改性聚氨酯膜膜冷却前将其与步骤 (3) 制得的阻燃基布在1.0Mpa 的压力下通过挤压辊复合压制,然后在 0.2Mpa 压力下由带有纹络的辊筒压纹,冷却后,制得初级合成革。
(6) 表面处理及修饰 :
将步骤 (5) 制得的初级合成革通过90℃水溶性硅油溶液进行表面处理,在110℃的烘 箱中烘干,制得阻燃性聚氨酯合成革。
实施例5
(1)氢氧化镁与氮磷膨胀型阻燃剂络合体系:将15.4g三羟甲基丙烷、27.8g四羟甲基硫 酸磷、34.5g磷酸,依次加入250ml的三口烧瓶中,放入恒温油浴锅80℃并保持恒温,再加入 三聚氯氰4.2g、四羟丙基乙二胺2.2g、四乙酰乙二胺0.3g和四乙基溴化铵0.5g,反应时间为 2h,得到膨胀型阻燃剂,再加入氢氧化镁2.7g、邻羧基苯乙酸0.7g、双(4-羧基苯基)苯基氧 化膦0.2g、4-乙酰氨基水杨酸0.3g、次氮基三乙酸0.5g和3-羟基扁桃酸0.6g,60℃并保持恒 温2h,最终得到红棕色粘稠状液体,即氢氧化镁与氮磷膨胀型阻燃剂络合体系;
(2)相容剂的制备:取丙烯酰胺13g置于三口烧瓶中,并加入0.12g苄基三乙基氯化铵, 取月桂酰氯2ml置于烘干的恒压滴液漏斗中并加入溶剂正己烷2ml;将月桂酰氯溶液滴加到 三口烧瓶中,控制滴加速度为5 秒/滴,滴加过程在冰水浴中进行,并用质量分数为10%的氢 氧化钠调节反应的pH值为8,冰水浴中滴加反应时间0.6 h,然后升高温度至20℃,反应时间 3h,反应结束后减压蒸出溶剂,进行喷雾干燥,得相容剂;
(3)基布的处理:将超纤布20g浸入到100g的步骤(1)的改性氢氧化镁阻燃剂、步骤(2) 的相容剂1.8g和氨基脲0.4g,然后在 100℃的烘道中将其烘干,制得阻燃基布待用;
(4) 改性聚氨酯膜
将12g热塑性聚氨酯与 3g苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁烯-苯 乙烯嵌段共聚物3g、聚酰胺型热塑性弹性体7g、色粉2g和羟乙基纤维素2g于370℃通过挤压 机挤出制得厚度 0.8mm 的聚氨酯膜;
(5) 初级合成革
在步骤 (4)制得的改性聚氨酯膜膜冷却前将其与步骤 (3) 制得的阻燃基布在1.0Mpa 的压力下通过挤压辊复合压制,然后在 0.2Mpa 压力下由带有纹络的辊筒压纹,冷却后,制得初级合成革。
(6) 表面处理及修饰 :
将步骤 (5) 制得的初级合成革通过90℃水溶性硅油溶液进行表面处理,在110℃的烘 箱中烘干,制得阻燃性聚氨酯合成革。
表1 阻燃性聚氨酯合成革性能
从表1可以发现,加入阻燃剂的合成革性能优于未加合成革的性能(拉伸负荷、断裂伸 长率等方面)。
表2 阻燃性聚氨酯合成革阻燃性能
项目 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 未加阻燃剂 |
燃烧速度mm/min | 0 | 11 | 14 | 15 | 9 | 132 |
依据FMVSS-302判断标准,可知燃烧速度为0,为优级;燃烧速度小于50 ,满足燃烧速度 要求,良;燃烧速度50~100,满足燃烧速度要求,一般;燃烧速度大于100mm/min,不合格;由 此可知,本发明的阻燃性能达到优或者良级,同时在燃烧过程中可以发现本发明的阻燃性 合成革无熔滴出现。
Claims (4)
1.一种阻燃性聚氨酯合成革,采用下述步骤制备得到,其特征在于:
(1)氢氧化镁与氮磷膨胀型阻燃剂络合体系:将15.4g三羟甲基丙烷、27.8g四羟甲基硫酸磷、34.5g磷酸,依次加入250ml的三口烧瓶中,放入恒温油浴锅80℃并保持恒温,再加入三聚氯氰4.2g、四羟丙基乙二胺2.2g、四乙酰乙二胺0.3g和四乙基溴化铵0.5g,反应时间为2h,得到膨胀型阻燃剂,再加入氢氧化镁2.7g、邻羧基苯乙酸0.7g、双(4-羧基苯基)苯基氧化膦0.2g、4-乙酰氨基水杨酸0.3g、次氮基三乙酸0.5g和3-羟基扁桃酸0.6g,60℃并保持恒温2h,最终得到红棕色粘稠状液体,即氢氧化镁与氮磷膨胀型阻燃剂络合体系;
(2)相容剂的制备:取丙烯酰胺13g置于三口烧瓶中,并加入0.12g催化剂,取月桂酰氯2ml置于烘干的恒压滴液漏斗中并加入溶剂正己烷2ml;将月桂酰氯溶液滴加到三口烧瓶中,控制滴加速度为5 秒/滴,滴加过程在冰水浴中进行,并用质量分数为10%的氢氧化钠调节反应的pH值为8,冰水浴中滴加反应时间0.6 h,然后升高温度至20℃,反应时间3h,反应结束后减压蒸出溶剂,进行喷雾干燥,得相容剂;
(3)基布的处理:将基布20g浸入到100g的步骤(1)的改性氢氧化镁阻燃剂、步骤(2)的相容剂1.8g和氨基脲0.4g,然后在 100℃的烘道中将其烘干,制得阻燃基布待用;
(4) 改性聚氨酯膜
将12g热塑性聚氨酯与 3g苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物3g、聚酰胺型热塑性弹性体7g、着色剂2g和2g的物质A于90℃-370℃通过挤压机挤出制得厚度 0.8mm 的聚氨酯膜,所述的物质A为三羟甲基 乙烷、双(4-羧基苯基)苯基氧化膦、2-羧基-5-硝基苯磺酸钾、5-羟基色胺、环亮氨酸、对甲 氧基乙酰苯胺、对氰基氯苄、羟乙基纤维素的任意一种;
(5) 初级合成革
在步骤 (4)制得的改性聚氨酯膜冷却前将其与步骤 (3) 制得的阻燃基布在 1.0Mpa的压力下通过挤压辊复合压制,然后在 0.2Mpa 压力下由带有纹络的辊筒压纹,冷 却后,制得初级合成革;
(6) 表面处理及修饰 :
将步骤 (5) 制得的初级合成革通过90℃水溶性硅油溶液进行表面处理,在110℃的烘箱中烘干,制得阻燃性聚氨酯合成革。
2.根据权利1所述的阻燃性聚氨酯合成革, 其特征在于:所述的基布为机织布或超纤布。
3.根据权利1所述的阻燃性聚氨酯合成革,其特征在于:所述的催化剂为二硫代二苯甲酸、甲醇钠、过硫酸铵、二乙基二硫代氨基甲酸钠、苄基三乙基氯化铵中的任意一种。
4.根据权利1所述的阻燃性聚氨酯合成革,其特征在于:所述的着色剂为色母料或色粉。
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