CN103422772A - Wood-plastic composite section and preparation method thereof - Google Patents
Wood-plastic composite section and preparation method thereof Download PDFInfo
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- CN103422772A CN103422772A CN2012101650385A CN201210165038A CN103422772A CN 103422772 A CN103422772 A CN 103422772A CN 2012101650385 A CN2012101650385 A CN 2012101650385A CN 201210165038 A CN201210165038 A CN 201210165038A CN 103422772 A CN103422772 A CN 103422772A
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- 229920001587 Wood-plastic composite Polymers 0.000 title claims abstract description 38
- 239000011155 wood-plastic composite Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 79
- 239000003063 flame retardant Substances 0.000 claims abstract description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229920003023 plastic Polymers 0.000 claims abstract description 24
- 239000004033 plastic Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 19
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 229920005610 lignin Polymers 0.000 claims description 51
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 28
- 229920002635 polyurethane Polymers 0.000 claims description 27
- 239000004814 polyurethane Substances 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000012948 isocyanate Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- -1 polypropylene Polymers 0.000 claims description 19
- 239000010902 straw Substances 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 235000011187 glycerol Nutrition 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 17
- 150000005846 sugar alcohols Polymers 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000012978 lignocellulosic material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 239000011496 polyurethane foam Substances 0.000 claims description 13
- 239000002028 Biomass Substances 0.000 claims description 11
- 239000004604 Blowing Agent Substances 0.000 claims description 11
- 229920002472 Starch Polymers 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- GNDMWRNTJIARLO-UHFFFAOYSA-N ClC(C)Cl.[F] Chemical group ClC(C)Cl.[F] GNDMWRNTJIARLO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 claims description 2
- 229940099364 dichlorofluoromethane Drugs 0.000 claims description 2
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 claims description 2
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Chemical compound CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-MDZDMXLPSA-N propan-2-yl (ne)-n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)\N=N\C(=O)OC(C)C VVWRJUBEIPHGQF-MDZDMXLPSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract description 12
- 229920001276 ammonium polyphosphate Polymers 0.000 abstract description 4
- 229920005862 polyol Polymers 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 abstract 1
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 229920002522 Wood fibre Polymers 0.000 abstract 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 abstract 1
- 229920000570 polyether Polymers 0.000 abstract 1
- 239000002025 wood fiber Substances 0.000 abstract 1
- 229920001451 polypropylene glycol Polymers 0.000 description 35
- 238000003756 stirring Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 5
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 235000009973 maize Nutrition 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000002990 reinforced plastic Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 2
- 241000153282 Theope Species 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a wood-plastic composite section and a preparation method thereof. The wood-plastic composite section is characterized by comprising a shell and a light material filled in the shell, the shell is made of a wood-plastic composite, and the density of the light material is lower than that of the wood-plastic composite. A shell preparation method includes uniformly mixing raw materials prior to extrusion molding, and the raw materials include plastic, a wood fiber material and a flame retardant. A flame retardant preparation method includes subjecting phosphoric acid and pentaerythritol to first contact reaction for 0.5-5 hours at the temperature of 100-180 DEG C, adding polyether polyol, ammonium polyphosphate and melamine and/or urea into a product obtained by the first contact reaction, and performing second contact reaction for 0.5-4 hours at the temperature of 100-180 DEG C. The section has excellent flame retardance. In addition, the light material is filled in the shell, so that strength of the section is improved on the premise of not increasing the weight of the section greatly.
Description
Technical field
The present invention relates to a kind of wood plastic composite material sections and preparation method thereof, particularly be filled with flame-retardant wood-plastic composite material section bar of light material and preparation method thereof.
Background technology
Section bar is the transition zone of body of wall and window, can play and fix and prevent the window effect that body of wall caves on every side.For conservation and alleviate the weight of section bar, section bar generally is made into hollow, but this can affect the intensity of section bar to a certain extent.
Wood plastic composite is the class advanced composite material (ACM) in recent years be surging forward both at home and abroad, refer to and utilize polyethylene, polypropylene and polyvinyl chloride etc. and the useless strings such as wood powder, rice husk, stalk to be mixed into new wood materials, again through the plastic processings such as extruding, mold pressing, injection moulding, the new material of producing.Wood plastic composite has modulus of elasticity preferably and the resistance to compression suitable with hardwood, the physical and mechanical properties such as counter-bending, case hardness be general timber 2-5 doubly, durability obviously is better than the normal wood material.Therefore wood plastic composite is widely used in preparing in the finishing materials such as section bar, decorative panel, floor.
But the hydrocarbons such as plastics are all than being easier to burning, make wood plastic composite also be easy to burning, in order to overcome the inflammability of wood plastic composite, giving the wood plastic composite surface flame-retardant is a kind of effective mode, as CN101486267A discloses a kind of surface flame-retardant wood-plastic composite material plate and preparation method thereof, this surface flame-retardant wood-plastic composite material is by two-layer crystal whisker modified plastic layer, the string reinforced plastic layer forms, between two-layer crystal whisker modified plastic layer, mold pressing has the string reinforced plastic layer, the crystal whisker modified plastic layer is by the modification alkali magnesium sulfate crystal whisker, the mixing such as plastic pellet calendering forms, the string reinforced plastic layer is by plastic pellet, the string thing mixes calendering and forms.CN101486267A has certain fire resistance by pressure sintering or at the surperficial wood plastic composite that uses flame-retarding adhesive to make of wood plastic composite, but operation is comparatively loaded down with trivial details.
Also by add fire retardant in wood plastic composite, give its anti-flammability at present, for example, halogen-containing fire retardant and phosphorous fire retardant, described halogen-containing fire retardant has penta-BDE and dibromo phenyl glycidol ether, described phosphorous fire retardant mainly contains take APP as base (as Exolit AP), the phosphonium flame retardant that the organic phosphorus compound of take is base (as Exolit RP) etc. as base (as Exolit OP) or the red phosphorus of take, but, halogen-containing fire retardant performance is lower, smoke-producing amount and addition are large, toxicity is high, phosphorous fire retardant performance is lower.And above-mentioned fire retardant is difficult to even mixing while directly mixing to prepare wood plastic composite with plastics and lignocellulosic material.
Summary of the invention
The purpose of this invention is to provide the flame-retardant wood-plastic composite material section bar that a kind of light weight and intensity are high.
To achieve these goals, the invention provides a kind of wood plastic composite material sections, it is characterized in that, described section bar comprises housing and is filled in the light material in described housing, the material of described housing is wood plastic composite, the density of described light material is lower than the density of described wood plastic composite, the preparation method of described housing comprises the evenly rear extrusion molding of mixing of raw material, described raw material comprises plastics, lignocellulosic material and fire retardant, the preparation method of described fire retardant is included under 100-180 ℃, make phosphoric acid and pentaerythrite carry out the first haptoreaction 0.5-5 hour, add PPG in the product obtained to this first haptoreaction, APP, and melamine and/or urea, and carry out the second haptoreaction 0.5-4 hour under 100-180 ℃.
The present invention also provides the preparation method of above-mentioned wood plastic composite material sections, and the method comprises and prepare housing, then filling with light material in described housing.
Pass through technique scheme, what adopt due to the housing of section bar of the present invention is the halogen-free flame-retardant wood plastic composite, therefore section bar of the present invention has good fire-retardant and smoke suppressing, with the Halogen flame-retardant wood-plastic composite material, compare, average ignitor firing time, heat release amount, smoke-producing amount and oxygen index (OI) all make moderate progress, and molten drop does not occur, have good anti-flammability.In addition, the present invention is filled to light material in housing, in assurance, increases not significantly under the prerequisite of described section bar weight, has increased the intensity of described section bar.
Other features and advantages of the present invention will partly be described in detail in the specific embodiment subsequently.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
In the present invention, " wood plastic composite material sections " refers to the object with certain geometrical shape that the raw material for preparing wood plastic composite is made through splicing through the techniques such as extrusion molding or in type wood plastic composite.
Wood plastic composite material sections provided by the invention comprises housing and is filled in the light material in described housing, the material of described housing is wood plastic composite, the density of described light material is lower than the density of described wood plastic composite, the preparation method of described housing comprises the evenly rear extrusion molding of mixing of raw material, described raw material comprises plastics, lignocellulosic material and fire retardant, the preparation method of described fire retardant is included under 100-180 ℃, make phosphoric acid and pentaerythrite carry out the first haptoreaction 0.5-5 hour, add PPG in the product obtained to this first haptoreaction, APP, and melamine and/or urea, and carry out the second haptoreaction 0.5-4 hour under 100-180 ℃.
According to the present invention, with respect to the plastics of 100 weight portions, the addition of described lignocellulosic material can be the 100-200 weight portion, is preferably the 100-150 weight portion, and the addition of described fire retardant can be the 40-100 weight portion, is preferably the 40-80 weight portion.
According to the present invention, described plastics and described lignocellulosic material can be usually used in preparing for this area the material of wood plastic composite.
Preferably, described plastics are one or more in polypropylene, polyethylene and polyvinyl chloride.
Preferably, described lignocellulosic material is one or more in wood, bamboo, rice husk, agricultural crop straw.To the particle size of described lignocellulosic material, there is no particular limitation in the present invention, and under preferable case, the particle size of described lignocellulosic material is the 10-200 order.
According to the present invention, make pentaerythrite and phosphoric acid generation condensation by described the first haptoreaction, afterwards by described the second haptoreaction, to improve the reactivity of fire retardant, make the fire retardant of final acquisition there is stable fire resistance.If phosphoric acid, pentaerythrite, PPG, APP and melamine and/or urea are directly mixed and are reacted, pentaerythrite and phosphoric acid condensation are insufficient, affect the reactivity of fire retardant, thereby make the fire-retardant less stable of the fire retardant of final acquisition.
The described first catalytic condition comprises: reaction temperature is 100-180 ℃, and the reaction time is 0.5-5 hour.When reaction temperature is less than 0.5 hour lower than 100 ℃ or reaction time, pentaerythrite can not fully react with phosphoric acid, thereby can produce adverse influence to the fire resistance of the fire retardant of final preparation; And, when reaction temperature should be greater than 5 hours with 180 ℃ or reaction time, the side reaction occurred may occur between pentaerythrite and phosphoric acid not wish.Under preferable case, the described first catalytic condition comprises: reaction temperature is 120-160 ℃, and the reaction time is 1-2 hour.
The described second catalytic condition comprises: reaction temperature is 100-180 ℃, and the reaction time is 0.5-4 hour.This reaction temperature higher than 180 ℃ easily generation do not wish the side reaction occurred, this reaction temperature lower than 100 ℃ reaction can not fully occur.Under preferable case, the described second catalytic condition comprises: reaction temperature is 120-160 ℃, and the reaction time is 0.5-2 hour.
The described first catalytic condition and the described second catalytic condition can be identical or different, and preferably the two is identical.
According to the present invention, with respect to the pentaerythrite of 100 weight portions, the addition of described phosphoric acid can be the 75-125 weight portion, is preferably the 80-110 weight portion; The addition of described PPG can be the 125-225 weight portion, is preferably the 150-210 weight portion; The addition of described APP can be the 125-200 weight portion, is preferably the 140-185 weight portion; The addition of described melamine and/or urea can be the 100-200 weight portion, is preferably the 120-180 weight portion.
In the present invention, described PPG can be the PPG of commercially available various routines, and its weight average molecular weight is preferably 200-5000, and more preferably 400-1000, can be for example PPG 4110 and/or PPG 403.
In the present invention, the degree of polymerization of described APP can be 50-2000, is preferably 100-1500.
According to the present invention, described raw material can also comprise one or more in fluidizer, antioxidant and sliding agent, and those skilled in the art can carry out to determine the addition of described plasticizing agent, antioxidant and sliding agent as required, under preferable case, plastics with respect to 100 weight portions, the addition of described plasticizing agent is the 2-6 weight portion, and the addition of described antioxidant is the 1-3 weight portion, and the addition of described sliding agent is the 2-5 weight portion.
Described plasticizing agent, antioxidant and sliding agent can adopt this area material commonly used, and for example, described plasticizing agent can be one or more in epoxidized soybean oil, D-sorbite, glycerine, pentaerythrite; Described antioxidant can be one or more in four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (antioxidant 1010), thio-2 acid distearate (antioxidant DSTP), phosphite ester kind antioxidant, composite antioxidant PKY, bisphenol-A; Described sliding agent can be one or more in stearic acid, stearate, low molecular weight polyethylene wax, low-molecular-weight polypropylene wax, OPE, brown paulownia wax, paraffin and montan wax.
In the present invention, described housing can be processed and make according to conventional processing technology, as long as described raw material is that above-mentioned raw materials can be realized purpose of the present invention, for example, can be by the plastics of 100 weight portions, the lignocellulosic material of 100-200 weight portion (particle size is the 10-200 order), the fire retardant of 40-100 weight portion, the selective plasticizing agent that uses the 2-6 weight portion, the antioxidant of the selective 1-3 of use weight portion and the selective sliding agent that uses the 2-5 weight portion, in homogenizer with 90-125 ℃ of mixed at high speed 3-15 minute, obtain uniform material, the gained material is proceeded in tapered double screw extruder and plastified, in double screw extruder, the heating-up temperature of each section is 140-200, pressure is the 8-18 MPa, screw speed is 10-20 rev/min, material, in the screw rod and cylindrical shell of above-mentioned extruder, passes through shearing, dispersion, compression, exhaust, plasticizing, extrudes through die head, makes housing.
In the present invention, fire retardant can mix by Direct Uniform with plastics and lignocellulosic material, the mechanical performance excellence of the housing made.Housing preparation process of the present invention is simple in addition, and raw materials used safety is easy to get.
According to the present invention, can realize purpose of the present invention as long as be filled with the light material with some strength in described housing, under preferable case, described light material is polyurethane foam, described polyurethane foam can make by the method for this area routine, also can be by commercially available.
More preferably, described light material is living beings based polyurethanes foam, and the preparation method of described biomass-based polyurethane foam comprises the following steps:
(1) under 100-135 ℃, make straw lignin material, polyalcohol and acidic catalyst carry out the first haptoreaction 1-4 hour, then add starch to carry out the second haptoreaction, obtain modified lignin;
(2) described modified lignin, PPG, amines catalyst and blowing agent evenly being mixed, by isocyanate index, be then that 1-1.4 adds isocyanates to carry out the 3rd haptoreaction, and the product that the 3rd haptoreaction is obtained is cured.
In the present invention, term " isocyanate index " refers to the ratio of isocyanate equivalent number and polyalcohol equivalents, mean the excessive degree of isocyanates in polyurethane formulations, described isocyanate equivalent number refers to the molal quantity of the isocyano in isocyanates, and described polyalcohol equivalents refers to the molal quantity of the alcoholic extract hydroxyl group of polyalcohol.
Along with people are constantly deep to the understanding of environmental crisis and crisis of resource, the exploitation of the natural polymer new materials such as lignin, starch comes into one's own day by day.Lignin and starch belong to natural polymer, are the huge and reproducible organic resources of reserves, extensively are present in plant.Polyurethane, because it is cheap, superior performance, has become one of modern Polymeric Industry kind with fastest developing speed.Because lignin, starch have the multiple functional groups such as hydroxyl, can petroleum replacing base chemicals (as the petroleum base polyalcohol) after exploitation, become the important sources of organic compound, for the synthesis of macromolecular materials such as polyurethane.Particularly biomass-based polyurethane foam has light weight to the polyurethane high molecule material, compressive property is strong and environment amenable characteristic, is widely used.Yet in the existing method of utilizing lignin to prepare polyurethane, most lignin composition can only be present in the form of filler in the polyurethane of final preparation, therefore, can't realize on the one hand the purpose with lignin composition petroleum replacing polylol, the lignin composition can not play the effect of the crosslinked core of large molecule polyfunctionality in polyurethane on the other hand, causes the binding ability of lignin composition and polyurethane poor.
And in above-mentioned steps (1), the modified lignin of preparation has higher reactivity, make lignin can replace the petroleum base polyalcohol to participate in the polymerisation of polyurethane, realize that components of biomass is to the substituting of petroleum base reactant, modification temperature is lower simultaneously; In addition, prepare in the process of described biomass-based polyurethane foam and do not need to use volatile solvent, thus can be to environment.
According to the present invention, in step (1), described the first haptoreaction is for described straw lignin is carried out to modification, to improve its reactivity.The described first catalytic reaction condition preferably includes: reaction temperature is 120-135 ℃, and the reaction time is 1-2 hour.
According to the present invention, in step (1), described the second haptoreaction is in order to control the condensation side reaction of straw lignin, makes the modified lignin of final acquisition have higher reactivity.The described second catalytic condition can comprise: reaction temperature is 60-100 ℃, is preferably 80-90 ℃; Reaction time is 0.5-1 hour, is preferably 0.5-0.8 hour.
According to the present invention, in step (1), if straw lignin material, polyalcohol, acidic catalyst and starch are directly mixed and carry out the first haptoreaction, starch can consume modifier and catalyzer, thereby greatly reduce the modified effect of lignin, thereby be difficult to reach the purpose of the reactivity that improves modified lignin.
According to the present invention, in step (1), with respect to the straw lignin material of 100 weight portions, the addition of described polyalcohol can be the 90-200 weight portion, is preferably the 120-160 weight portion; The addition of described acidic catalyst can be the 0.1-3 weight portion, is preferably the 0.5-2 weight portion; The addition of starch can be the 60-200 weight portion, is preferably the 100-150 weight portion.
According to the present invention, in step (1), described straw lignin material can be the stalk of various conventional plants, can be for example the stalk of grass, is preferably wheat stalk and/or maize straw.There is no particular limitation for the particle size of described straw lignin material, and under preferable case, the particle size of described straw lignin material is the 10-200 order.
According to the present invention, in step (1), described polyalcohol can be the polyalcohol of various routines, can be macromolecular polyol, can be also little molecular polylol, as long as contain at least 2 hydroxyls in a molecule simultaneously.Under preferable case, described polyalcohol is one or more in ethylene glycol, polyethylene glycol and glycerine, and the weight average molecular weight of described polyethylene glycol can be 200-5000, is preferably 400-1000; In preferred situation, the mixture that described polyalcohol is polyethylene glycol and glycerine, under this preferable case, glycerine and polyethylene glycol acting in conjunction can suppress the condensation reaction of lignin, thereby can further improve the reactivity of the modified lignin of final acquisition.
According to the present invention, in step (1), when mixture that described polyalcohol is polyethylene glycol and glycerine, the mixed weight ratio of polyethylene glycol and glycerine is preferably 1-15:1, more preferably 1.5-10:1.Further, under preferable case, with respect to the straw lignin material of 100 weight portions, the addition of described polyethylene glycol is preferably the 80-150 weight portion, and the addition of described glycerine is preferably the 10-50 weight portion.
According to the present invention, in step (1), described acidic catalyst can be one or more in phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid, ethanedioic acid, malonic acid, succinic acid, benzene sulfonic acid and benzoic acid, most preferably is sulfuric acid.
According to the present invention, in step (1), described starch can be one or more in farina, cornstarch, tapioca and sweet potato starch.The particle size of described starch is preferably the 10-200 order.
According to the present invention, in step (2), described the 3rd catalytic reaction condition can comprise: reaction temperature is 15-30 ℃, is preferably 15-20 ℃; Reaction time is 0.5-5min, is preferably 1-2min.
According to the present invention, in step (2), the condition that the product that described the 3rd haptoreaction is obtained is cured can comprise: curing temperature is 60-120 ℃, is preferably 60-80 ℃; The curing time is 2-24 hour, is preferably 2-10 hour.Described solidifying can adopt conventional curing to implement, for example baking oven for drying solidification.
According to the present invention, in step (2), the addition of described modified lignin, PPG, amines catalyst and blowing agent can change separately in the larger context.Under preferable case, with respect to the described modified lignin of 100 weight portions, the addition of described PPG is the 50-300 weight portion, and the addition of described amines catalyst is the 1-10 weight portion, and the addition of described blowing agent is the 10-100 weight portion.When described lignin, PPG, amines catalyst and blowing agent all add fashionablely in above-mentioned number range, the biomass-based polyurethane foam of final preparation has mechanical performance preferably.Further, under preferable case, with respect to the described modified lignin of 100 weight portions, the addition of described PPG is the 100-200 weight portion, and the addition of described amines catalyst is the 1.5-8 weight portion, and the addition of described blowing agent is the 20-50 weight portion.Described PPG can be the PPG of commercially available various routines, and its weight average molecular weight is preferably 200-5000, and more preferably 400-1000, can be for example PPG 4110 and/or PPG 403.
Described amines catalyst can be one or more in triethylene diamine, triethylamine, triethanolamine and dimethyl cyclohexyl amine, most preferably is triethylene diamine.
Described blowing agent can be the blowing agent of various routines, it can be for example a fluorine dichloroethanes, 1, 1, 1, 3, the 3-pentafluoropropane, 1, 1, 1, 3, the 3-3-pentafluorobutane, N, the N-dinitrosopentamethlyene tetramine, Celogen Az, azodiisobutyronitrile, diisopropyl azodiformate, diethyl azodiformate, Barium azodicarboxylate, 4, the 4-disulfonyl hydrazide diphenyl ether, unifor, 1, the 3-benzene disulfohydrazide, 1, the 4-benzene disulfohydrazide, normal butane, pentane, n-hexane, normal heptane, benzinum, Arcton 11, dichlorofluoromethane, one or more in dicholorodifluoromethane and dichlorotetra-fluoroethane.Under preferable case, described blowing agent is the unreactive hydrocarbons compounds that boiling point is lower, and as a fluorine dichloroethanes, 1,1,1,3, one or more in 3-pentafluoropropane and 1,1,1,3,3-3-pentafluorobutane, most preferably be a fluorine dichloroethanes.
Described isocyanates is preferably the isocyanates (being also vulcabond or polyisocyanates) with two above isocyanos, and the described isocyanates with two above isocyanos can be for example one or more in toluene di-isocyanate(TDI), hexamethylene diisocyanate, IPDI, poly methylene poly phenyl poly isocyanate and methyl diphenylene diisocyanate.
According to the present invention, for the mechanical performance of the biomass-based polyurethane foam that improves final preparation, the preparation method of described biomass-based polyurethane foam can also be included in step (2) and add foam stabiliser.With respect to the described modified lignin of 100 weight portions, the addition of described foam stabiliser can be the 1-10 weight portion, is preferably the 1.5-8 weight portion.In the present invention, described foam stabiliser is preferably dimethyl siloxane and/or silicone oil.
The preparation method of section bar provided by the invention comprises and prepares housing, then filling with light material in described housing.
Wherein, the described method for preparing housing is above-described method.
Preferably, described in housing the mode of filling with light material comprise after the raw material that will prepare light material mixes and recharging to housing, then will be filled with the described housing for preparing the raw material of light material and be placed under the condition that makes the described raw material reaction for preparing light material generate light material and reacted.Described raw material and the condition for preparing light material can be all above-described raw material and condition.Therefore, method of the present invention can directly prepare light material in type housing, and technique is more simply controlled.
Below will describe the present invention by embodiment.In following examples, the experimental technique of unreceipted actual conditions, according to normal condition, carry out.
Embodiment 1
(1) preparation of housing
The phosphoric acid of the pentaerythrite of 100 weight portions and 85 weight portions is mixed, and 140 ℃ of lower stirring reactions 1 hour, afterwards to the APP of the PPG that adds 185 weight portions in product (purchased from the PPG 4110 of the clear month polyurethane factory of Beijing lark), 160 weight portions (purchased from Beijing Linkage chemical industry Co., Ltd, the degree of polymerization is 1500) and the melamine of 150 weight portions, and 140 ℃ of lower stirring reactions 0.5 hour, thereby make fire retardant.
Plastics (polypropylene by 100 weight portions, weight average molecular weight is 250000), lignocellulosic material (the wood powder of 100 weight portions, particle size is 100 orders), the above-mentioned fire retardant of 80 weight portions, the plasticizing agent of 5 weight portions (epoxidized soybean oil), sliding agent (the OPE of the antioxidant of 3 weight portions (antioxidant 1010) and 5 weight portions, Weng Kaier Co., Ltd, SH1), in homogenizer (Zhangjiagang compressor mechanical company, SRL200/500) in 115 ℃ of mixed at high speed 15 minutes, obtain uniform material, the gained material is proceeded to tapered double screw extruder (Zhe-jiang Jiang Hua industry plastics machinery Co., Ltd, HX φ 62/132) in, plastified, in double screw extruder, the heating-up temperature of each section is respectively 155 ℃, 165 ℃, 175 ℃, 180 ℃, 175 ℃, pressure is the 9-15 MPa, screw speed is l5 rev/min, material, in the screw rod and cylindrical shell of above-mentioned extruder, passes through shearing, dispersion, compression, exhaust, plasticizing, extrudes through die head, makes housing.
(2) preparation of modified lignin
The sulfuric acid (98% the concentrated sulfuric acid) of the glycerine of the polyethylene glycol (PEG400) of the maize straw of 100 weight portions (particle size is the 80-120 order), 110 weight portions, 30 weight portions and 1.5 weight portions is mixed, and react 2 hours under 120 ℃.Then, to the farina (particle size is the 80-120 order) that adds 100 weight portions in reaction gained mixture, and, 80 ℃ of lower stirring reactions 0.8 hour, obtain modified lignin.
(3) filling of biomass-based polyurethane foam
Under agitation, modified lignin by preparation in (1) of 100 weight portions, the PPG of 150 weight portions (purchased from the PPG 4110 of the clear month polyurethane factory of Beijing lark), the triethylene diamine solution of 5 weight portions is (purchased from the clear month polyurethane factory of Beijing lark, the trade mark is A33), 7.5 a fluorine dichloroethanes (purchased from the clear month polyurethane factory of Beijing lark) of the dimethyl siloxane of weight portion (purchased from the clear month polyurethane factory of Beijing lark) and 50 weight portions evenly mixes, then, the methyl diphenylene diisocyanate (purchased from Hangzhou Green's Chemical trade Co., Ltd) that adds wherein 322 weight portions, so that isocyanate index is adjusted to 1.2, after stirring, be filled in the housing that step (1) makes, the mixture obtained is reacted 1.5 minutes under 20 ℃, then, in the baking oven of 85 ℃, solidify 12 hours, obtain section bar A1.
Comparative Examples 1
Method according to embodiment 1 prepares section bar C1, different is, by the APP of the phosphoric acid of the pentaerythrite of 100 weight portions, 85 weight portions, the PPG of 185 weight portions (purchased from the PPG 4110 of the clear month polyurethane factory of Beijing lark), 160 weight portions (purchased from Beijing Linkage chemical industry Co., Ltd, the degree of polymerization is 1500) and the melamine of 150 weight portions directly mix, and 140 ℃ of lower stirring reactions 1.5 hours, thereby make fire retardant.
Comparative Examples 2
Method according to embodiment 1 prepares section bar C2, different, and the reaction between the two of pentaerythrite and phosphoric acid is carried out under 90 ℃, thereby makes fire retardant.
Comparative Examples 3
Method according to embodiment 1 prepares section bar C3, different, and pentaerythrite and phosphoric acid react between the two and carries out under 200 ℃, thereby make fire retardant.
Comparative Examples 4
Method according to embodiment 1 prepares section bar C4, different, adds the reaction afterwards of PPG, APP and melamine to carry out under 90 ℃, thereby makes fire retardant.
Comparative Examples 5
Method according to embodiment 1 prepares section bar C5, different, adds the reaction afterwards of PPG, APP and melamine to carry out under 200 ℃, thereby makes fire retardant.
Comparative Examples 6
Method according to embodiment 1 prepares section bar C6, different, with halogen containing flame-retardant (Polybrominated biphenyl, auspicious bio tech ltd of Shenzhen iris, the fire retardant that B-030N) replaces embodiment 1 to make.
Comparative Examples 7
Method according to embodiment 1 prepares section bar C7, different, and the housing directly step (1) made is as section bar C7.
Embodiment 2
Prepare section bar A2 according to the method for embodiment 1, different is, in step (2), the sulfuric acid (98% the concentrated sulfuric acid) of the glycerine of the polyethylene glycol of the maize straw of 110 weight portions (particle size is the 80-120 order), 100 weight portions, 30 weight portions and 1.5 weight portions is mixed, and react 2.5 hours under 120 ℃, to prepare modified lignin.
Embodiment 3
Prepare section bar A3 according to the method for embodiment 1, different is, in step (2), the sulfuric acid (98% the concentrated sulfuric acid) of the glycerine of the polyethylene glycol (PEG400) of the maize straw of 100 weight portions (particle size is the 80-120 order), 110 weight portions, 30 weight portions, 1.5 weight portions and 100 weight portion farinas (particle size is the 80-120 order) are directly mixed, and react 3.3 hours under 120 ℃, to prepare modified lignin.
Embodiment 4
Prepare section bar A4 according to the method for embodiment 1, different, in step (2), the ethylene glycol of the weight such as use replaces glycerine, to prepare modified lignin.
Embodiment 5
Prepare section bar A5 according to the method for embodiment 1, different, in step (2), the polyethylene glycol of use and the weight ratio of glycerine are 0.5:1, and both gross weights are 140 weight portions, to prepare modified lignin.
Embodiment 6
Prepare section bar A6 according to the method for embodiment 1, different, in step (2), the polyethylene glycol of use and the weight ratio of glycerine are 20:1, and both gross weights are 140 weight portions, to prepare modified lignin.
Embodiment 7
(1) preparation of housing
The phosphoric acid of the pentaerythrite of 100 weight portions and 80 weight portions is mixed, and 130 ℃ of lower stirring reactions 1.5 hours, afterwards to the APP of the PPG that adds 210 weight portions in product (purchased from the PPG 403 of the clear month polyurethane factory of Beijing lark), 185 weight portions (purchased from Beijing Linkage chemical industry Co., Ltd, the degree of polymerization is 100) and the melamine of 120 weight portions, and 130 ℃ of lower stirring reactions 0.5 hour, thereby make fire retardant.
Plastics (polypropylene by 100 weight portions, weight average molecular weight is 250000), lignocellulosic material (the rice husk of 150 weight portions, particle size is 100 orders), the above-mentioned fire retardant of 40 weight portions, the plasticizing agent of 6 weight portions (pentaerythrite), sliding agent (the OPE of the antioxidant of 2 weight portions (bisphenol-A) and 3 weight portions, Weng Kaier Co., Ltd, SH1), in homogenizer (Zhangjiagang compressor mechanical company, SRL200/500) in 115 ℃ of mixed at high speed 15 minutes, obtain uniform material, the gained material is proceeded to tapered double screw extruder (Zhe-jiang Jiang Hua industry plastics machinery Co., Ltd, HX φ 62/132) in, plastified, in double screw extruder, the heating-up temperature of each section is respectively 155 ℃, 165 ℃, 175 ℃, 180 ℃, 175 ℃, pressure is the 9-15 MPa, screw speed is l5 rev/min, material, in the screw rod and cylindrical shell of above-mentioned extruder, passes through shearing, dispersion, compression, exhaust, plasticizing, extrudes through die head, makes housing,
(2) preparation of modified lignin
The sulfuric acid (98% the concentrated sulfuric acid) of the glycerine of the polyethylene glycol of the wheat stalk of 100 weight portions (particle size is the 10-50 order), 80 weight portions, 50 weight portions and 0.5 weight portion is mixed, and react 1.5 hours under 135 ℃.Then, to the tapioca (particle size is the 10-50 order) that adds 120 weight portions in reaction gained mixture, and, 90 ℃ of lower stirring reactions 0.5 hour, obtain modified lignin.
(3) filling of biomass-based polyurethane foam
Under agitation, modified lignin by preparation in (1) of 100 weight portions, the PPG of 100 weight portions (purchased from the PPG 403 of the clear month polyurethane factory of Beijing lark), 1.5 the triethanolamine of weight portion (purchased from Beijing China imperial chemical industry Co., Ltd), 1 of the dimethyl siloxane of 5 weight portions (purchased from the clear month polyurethane factory of Beijing lark) and 40 weight portions, 1, 1, 3, 3-pentafluoropropane (purchased from the clear month polyurethane factory of Beijing lark) evenly mixes, then, the hexamethylene diisocyanate (purchased from Hangzhou Green's Chemical trade Co., Ltd) that adds wherein 302 weight portions, so that isocyanate index is adjusted to 1.0, after stirring, be filled in the housing that step (1) makes, the mixture obtained is reacted 30 seconds under 20 ℃, then, in the baking oven of 85 ℃, solidify 12 hours, obtain section bar A7.
Embodiment 8
(1) preparation of housing
The phosphoric acid of the pentaerythrite of 100 weight portions and 110 weight portions is mixed, and 150 ℃ of lower stirring reactions 1 hour, afterwards to the APP of the PPG that adds 150 weight portions in product (purchased from the PPG 4110 of the clear month polyurethane factory of Beijing lark), 140 weight portions (purchased from Beijing Linkage chemical industry Co., Ltd, the degree of polymerization is 1500) and the melamine of 180 weight portions, and 150 ℃ of lower stirring reactions 0.5 hour, thereby make fire retardant.
Plastics (polypropylene by 100 weight portions, weight average molecular weight is 250000), lignocellulosic material (the stalk of 200 weight portions, particle size is 100 orders), the above-mentioned fire retardant of 100 weight portions, the plasticizing agent of 3 weight portions (glycerine), sliding agent (the paraffin of the antioxidant of 3 weight portions (antioxidant 1010) and 4 weight portions, CNPC's Fushun Petrochemical Company, No. 64 paraffin wax fully refineds), in homogenizer (Zhangjiagang compressor mechanical company, SRL200/500) in 115 ℃ of mixed at high speed 15 minutes, obtain uniform material, the gained material is proceeded to tapered double screw extruder (Zhe-jiang Jiang Hua industry plastics machinery Co., Ltd, HX φ 62/132) in, plastified, in double screw extruder, the heating-up temperature of each section is respectively 155 ℃, 165 ℃, 175 ℃, 180 ℃, 175 ℃, pressure is the 9-15 MPa, screw speed is l5 rev/min, material, in the screw rod and cylindrical shell of above-mentioned extruder, passes through shearing, dispersion, compression, exhaust, plasticizing, extrudes through die head, makes housing.
(2) preparation of modified lignin
The sulfuric acid (98% the concentrated sulfuric acid) of the glycerine of the polyethylene glycol of the maize straw of 100 weight portions (particle size is the 100-150 order), 145 weight portions, 15 weight portions and 2 weight portions is mixed, and react 1 hour under 130 ℃.Then, to the sweet potato starch (particle size is the 100-150 order) that adds 150 weight portions in reaction gained mixture, and, 85 ℃ of lower stirring reactions 0.5 hour, obtain modified lignin.
(3) filling of biomass-based polyurethane foam
Under agitation, modified lignin by preparation in (1) of 100 weight portions, the PPG (purchased from the PPG 403 of the clear month polyurethane factory of Beijing lark) of the PPG of 80 weight portions (purchased from the PPG 4110 of the clear month polyurethane factory of Beijing lark) and 120 weight portions, the triethylene diamine solution of 8 weight portions (purchased from the clear month polyurethane factory of Beijing lark), 1.5 a fluorine dichloroethanes (purchased from the clear month polyurethane factory of Beijing lark) of the silicone oil of weight portion (purchased from the clear month polyurethane factory of Beijing lark) and 20 weight portions evenly mixes, then, the toluene di-isocyanate(TDI) (purchased from Hangzhou Green's Chemical trade Co., Ltd) that adds wherein 597 weight portions, so that isocyanate index is adjusted to 1.4, after stirring, be filled in the housing that step (1) makes, the mixture obtained is reacted 3 minutes under 20 ℃, then, in the baking oven of 85 ℃, solidify 12 hours, obtain section bar A8.
Test case 1
The section bar that above-described embodiment 1-8 and Comparative Examples 7 are made adopts respectively following method to carry out measuring mechanical property, and bending property (bending strength and bending modulus) is according to ASTM D 790 standard testings; Hold screw power according to GB 11718.9-1989 standard testing; Notched Izod impact strength is according to ASTM D 6110 standard testings.Test result is as shown in table 1 below.
Table 1
From the result of table 1 can find out, every physical and mechanical properties excellence of the section bar that the present invention adopts conventional machining equipment to make; Embodiment 1 relatively can be found out with Comparative Examples 7, and the weight of section bar A1 is only 105.8% of section bar C7 weight, illustrates that the present invention has increased the intensity of described section bar under the prerequisite that guarantees section bar weight.
Test case 2
Use the taper calorimeter to detect the fire resistance of the section bar that embodiment 1,7,8 and Comparative Examples 1-6 make according to the method for ISO 5660-1:2002, its test result is as shown in table 2 below:
Table 2
From can find out in table 2, the flame-retardant wood-plastic composite material that adopts the prepared according to the methods of the invention fire retardant to make has good fire resistance.And, by embodiment 1 and Comparative Examples 1-6 are compared and can find out, the fire resistance of the section bar A1 that embodiment 1 makes obviously is better than not using the method according to this invention to prepare the section bar C1-C6 of fire retardant, therefore, section bar of the present invention is the halogen-free flame-retardant section bar, and fire resistance is high, preparation technology is simple.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in the above-mentioned specific embodiment, in reconcilable situation, can be combined by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can carry out any combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a wood plastic composite material sections, it is characterized in that, described section bar comprises housing and is filled in the light material in described housing, the material of described housing is wood plastic composite, the density of described light material is lower than the density of described wood plastic composite, the preparation method of described housing comprises the evenly rear extrusion molding of mixing of raw material, described raw material comprises plastics, lignocellulosic material and fire retardant, the preparation method of described fire retardant is included under 100-180 ℃, make phosphoric acid and pentaerythrite carry out the first haptoreaction 0.5-5 hour, add PPG in the product obtained to this first haptoreaction, APP, and melamine and/or urea, and carry out the second haptoreaction 0.5-4 hour under 100-180 ℃.
2. section bar according to claim 1, wherein, with respect to the plastics of 100 weight portions, the addition of described lignocellulosic material is the 100-200 weight portion, the addition of described fire retardant is the 40-100 weight portion; Described plastics are one or more in polypropylene, polyethylene and polyvinyl chloride; Described lignocellulosic material is one or more in wood, bamboo, rice husk, agricultural crop straw.
3. section bar according to claim 1, wherein, pentaerythrite with respect to 100 weight portions, the addition of described phosphoric acid is the 75-125 weight portion, the addition of described PPG is the 125-225 weight portion, the addition of described APP is the 125-200 weight portion, and the addition of described melamine and/or urea is the 100-200 weight portion.
4. according to the described section bar of claim 1 or 3, wherein, the weight average molecular weight of described PPG is 200-5000; The degree of polymerization of described APP is 50-2000.
5. section bar according to claim 1, wherein, described raw material also comprises one or more in fluidizer, antioxidant and sliding agent.
6. section bar according to claim 1, wherein, described light material is polyurethane foam.
7. according to the described section bar of claim 1 or 6, wherein, described light material is living beings based polyurethanes foam, and the preparation method of described biomass-based polyurethane foam comprises the following steps:
(1) under 100-135 ℃, make straw lignin material, polyalcohol and acidic catalyst carry out the first haptoreaction 1-4 hour, then add starch to carry out the second haptoreaction, obtain modified lignin;
(2) described modified lignin, PPG, amines catalyst and blowing agent evenly being mixed, by isocyanate index, be then that 1-1.4 adds isocyanates to carry out the 3rd haptoreaction, and the product that the 3rd haptoreaction is obtained is cured.
8. section bar according to claim 7, wherein, in step (1), straw lignin material with respect to 100 weight portions, the addition of described polyalcohol is the 90-200 weight portion, and the addition of described acidic catalyst is the 0.1-3 weight portion, and the addition of starch is the 60-200 weight portion; Described polyalcohol is at least one in ethylene glycol, polyethylene glycol and glycerine; Described acidic catalyst is at least one in phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid, ethanedioic acid, malonic acid, succinic acid, benzene sulfonic acid and benzoic acid; The particle size of described straw lignin material is the 10-200 order; The described second catalytic condition comprises: reaction temperature is 60-100 ℃, and the reaction time is 0.5-1 hour.
9. according to the described section bar of claim 7 or 8, wherein, the mixture that described polyalcohol is polyethylene glycol and glycerine.
10. section bar according to claim 7, wherein, in step (2), described modified lignin with respect to 100 weight portions, the addition of described PPG is the 50-300 weight portion, the addition of described amines catalyst is the 1-10 weight portion, and the addition of described blowing agent is the 10-100 weight portion; Described amines catalyst is one or more of triethylene diamine, triethylamine, triethanolamine and dimethyl cyclohexyl amine; Described blowing agent is a fluorine dichloroethanes, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-3-pentafluorobutane, N, N-dinitrosopentamethlyene tetramine, Celogen Az, azodiisobutyronitrile, diisopropyl azodiformate, diethyl azodiformate, Barium azodicarboxylate, 4,4-disulfonyl hydrazide diphenyl ether, unifor, 1, one or more in 3-benzene disulfohydrazide, Isosorbide-5-Nitrae-benzene disulfohydrazide, normal butane, pentane, n-hexane, normal heptane, benzinum, Arcton 11, dichlorofluoromethane, dicholorodifluoromethane and dichlorotetra-fluoroethane; Described isocyanates is one or more in toluene di-isocyanate(TDI), hexamethylene diisocyanate, IPDI, polymethylene multi-phenenyl isocyanate and methyl diphenylene diisocyanate; Described the 3rd catalytic reaction condition comprises: reaction temperature is 15-30 ℃, and the reaction time is 0.5-5 minute; Described curing condition comprises: curing temperature is 60-120 ℃, and the curing time is 2-24 hour.
11. in claim 1-10, the preparation method of the described section bar of any one, is characterized in that, the method comprises and prepares housing, then filling with light material in described housing.
12. method according to claim 11, wherein, described in housing the mode of filling with light material comprise after the raw material that will prepare light material mixes and recharging to housing, then will be filled with the described housing for preparing the raw material of light material and be placed under the condition that makes the described raw material reaction for preparing light material generate light material and reacted.
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| CN103848870A (en) * | 2014-03-18 | 2014-06-11 | 王鹏 | Preparation method of N-P intumescent oily fiberglass reinforced plastic flame retardant |
| CN104405075A (en) * | 2014-11-11 | 2015-03-11 | 南京工业职业技术学院 | Composite wall sheet material and preparation method thereof |
| CN104479531A (en) * | 2014-12-09 | 2015-04-01 | 泰兴市和庆机械配件厂 | Isophorone diisocyanate fireproof coating used for solid wood particle board and preparation method of coating |
| CN105542500A (en) * | 2016-01-21 | 2016-05-04 | 苏州法斯特信息科技有限公司 | Environment-friendly foamed buffer material and preparation method thereof |
| CN109575622A (en) * | 2017-09-29 | 2019-04-05 | 中科众创（重庆）秸秆产业研究院有限公司 | A kind of fire-retardant stalk compound material and preparation method thereof |
| CN110105780A (en) * | 2019-04-11 | 2019-08-09 | 贵州力宏建筑工程有限公司 | A kind of flame-retardant wood floor manufacturing method in building decoration engineering |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848870A (en) * | 2014-03-18 | 2014-06-11 | 王鹏 | Preparation method of N-P intumescent oily fiberglass reinforced plastic flame retardant |
| CN104405075A (en) * | 2014-11-11 | 2015-03-11 | 南京工业职业技术学院 | Composite wall sheet material and preparation method thereof |
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| CN104479531A (en) * | 2014-12-09 | 2015-04-01 | 泰兴市和庆机械配件厂 | Isophorone diisocyanate fireproof coating used for solid wood particle board and preparation method of coating |
| CN105542500A (en) * | 2016-01-21 | 2016-05-04 | 苏州法斯特信息科技有限公司 | Environment-friendly foamed buffer material and preparation method thereof |
| CN109575622A (en) * | 2017-09-29 | 2019-04-05 | 中科众创（重庆）秸秆产业研究院有限公司 | A kind of fire-retardant stalk compound material and preparation method thereof |
| CN110105780A (en) * | 2019-04-11 | 2019-08-09 | 贵州力宏建筑工程有限公司 | A kind of flame-retardant wood floor manufacturing method in building decoration engineering |
| CN110423483A (en) * | 2019-08-14 | 2019-11-08 | 淮北市菲美得环保科技有限公司 | A kind of biology base degradable foam materials and preparation method thereof |
| CN112126215A (en) * | 2020-09-23 | 2020-12-25 | 湖南大学 | Elastic wood-plastic composite material for 3D printing and preparation method and application thereof |
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| CN103422772B (en) | 2015-04-08 |
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