CN115746277B - Bio-based flame-retardant unsaturated polyester for wood enhancement modification and preparation and application thereof - Google Patents
Bio-based flame-retardant unsaturated polyester for wood enhancement modification and preparation and application thereof Download PDFInfo
- Publication number
- CN115746277B CN115746277B CN202211368353.8A CN202211368353A CN115746277B CN 115746277 B CN115746277 B CN 115746277B CN 202211368353 A CN202211368353 A CN 202211368353A CN 115746277 B CN115746277 B CN 115746277B
- Authority
- CN
- China
- Prior art keywords
- wood
- unsaturated polyester
- bio
- based flame
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002023 wood Substances 0.000 title claims abstract description 121
- 239000003063 flame retardant Substances 0.000 title claims abstract description 107
- 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 102
- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 65
- 238000012986 modification Methods 0.000 title claims abstract description 40
- 230000004048 modification Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 32
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 30
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005470 impregnation Methods 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000000155 melt Substances 0.000 claims abstract description 4
- 230000002787 reinforcement Effects 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 241000219000 Populus Species 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 4
- 235000011613 Pinus brutia Nutrition 0.000 claims description 4
- 241000018646 Pinus brutia Species 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- 229920002531 Rubberwood Polymers 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- FFIUNPRXUCRYFU-UHFFFAOYSA-N tert-butyl pentaneperoxoate Chemical compound CCCCC(=O)OOC(C)(C)C FFIUNPRXUCRYFU-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000000703 high-speed centrifugation Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 description 5
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000010875 treated wood Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- -1 formaldehyde, compound Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000003171 wood protecting agent Substances 0.000 description 1
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention belongs to the field of wood modification, and discloses bio-based flame-retardant unsaturated polyester for wood enhancement modification, and preparation and application thereof. The invention synthesizes the bio-based flame-retardant unsaturated polyester by itaconic acid and flame retardant FRC-6 through one step by a melt polycondensation method, and adopts a vacuum-pressurizing impregnation method and in-situ polymerization to modify wood, thereby realizing the high-value utilization of the wood. The bio-based flame-retardant unsaturated polyester prepared by the invention has the advantages of high efficiency, environmental protection, excellent water dispersibility, stability after high-speed centrifugation and indoor storage (1-6 months), good permeability in wood, high drug loading rate and remarkable modification effect. The bio-based flame-retardant unsaturated polyester is adopted to modify the wood through vacuum-pressurization impregnation and in-situ polymerization, so that the flame retardance and the physical and mechanical properties of the wood are obviously improved, the loss of a flame retardant is reduced, multiple effects of one agent are realized, a good thought is provided for the flame-retardant enhancement modification of the wood, and the method has a wide application prospect.
Description
Technical Field
The invention belongs to the field of wood modification, and in particular relates to bio-based flame-retardant unsaturated polyester for wood enhancement modification, and preparation and application thereof.
Background
The wood is used as a porous natural polymer material which is light, high in strength, excellent in processing performance, attractive in pattern, environment-friendly, nontoxic, renewable, and widely applied to various fields of building, home furnishing, decoration and the like, however, the wood still has the defects of easy moisture, flammability, looseness and the like, so that corresponding potential safety hazards are brought, and therefore, the wood needs to be developed and functionally improved to improve the material quality and the optimizing performance.
The impregnation modification is one of effective methods for improving the mechanical strength of wood, reducing dry shrinkage and wet expansion and endowing functionality, and usually accompanies the resin to enter cell walls or cell cavities for in-situ polymerization or chemical crosslinking to achieve the enhancement purpose, but most of modified resin is derived from fossil raw materials or has certain toxicity, is not environment-friendly and has high requirement on permeability. The main method for improving the flame retardance of the wood is to impregnate an organic or inorganic flame retardant, but the method has the limitations of easy loss, deliquescence, large dosage and the like. In the current research, the flame retardant is fixed through chemical crosslinking by compounding the resin and the flame retardant, which is an important means for reducing the loss, but the compatibility of the resin and the flame retardant can limit the common promotion of flame retardance and mechanical property. Therefore, the novel water-based bio-based flame-retardant resin is green in source, mechanical strength and flame retardance of wood are improved, and the defects of poor compatibility, easiness in loss and the like are reduced through chemical bond combination of the flame-retardant group and the resin, so that the novel water-based bio-based flame-retardant resin is a more comprehensive wood functional improvement means.
Li Ming et al (study of silica sol-APP composite flame retardant on flame retardance of radiation pine wood) impregnated modified radiation pine wood by adopting a silica sol and ammonium polyphosphate (APP) composite flame retardant, not only is the preparation process simple and convenient, but also the flame retardance, smoke suppression and heat insulation of the wood are greatly improved, but the weight gain rate and the compatibilization rate are not obviously improved due to limited permeability of the silica sol, so that the physical mechanical properties of the wood are not improved, and meanwhile, the composite flame retardant is easy to run off and deliquesce, so that the stability of the modified wood for long-term use is reduced.
Chen Ling (a research on urea-formaldehyde resin type wood flame retardant) is to prepare urea-formaldehyde resin by adopting urea and formaldehyde, compound and impregnate modified poplar veneer with boric acid to prepare laminated veneer lumber, the strength and water resistance of the obtained modified lumber are improved, and the loss of boric acid is reduced to a certain extent by fixing urea-formaldehyde resin. However, the raw materials of urea-formaldehyde resin are all derived from fossil raw materials, and formaldehyde gas is inevitably released, so that the urea-formaldehyde resin has no environmental friendliness and influences the further popularization of the method.
Kong Lizhuo (furfuryl alcohol resin/monoammonium phosphate composite modified poplar performance research) is to prepare a composite modified material by compounding and impregnating furfuryl alcohol resin and monoammonium phosphate (ADP) modified poplar, the bending strength is slightly reduced, the mechanical strength and the flame retardance are obviously improved, the coating and fixing effects of the furfuryl alcohol resin effectively reduce the loss of the ADP, and the addition of the ADP has no influence on the physical and mechanical properties of the composite modified material. However, in the compounding process, an alcohol solvent is still required to be added to improve the compatibility, furfuryl alcohol is used as a small monomer and is easy to run off in the impregnation and curing processes, and ADP and maleic anhydride serving as a catalyst are acidic to influence the stability of the modified material.
Chinese patent publication CN 114147825A adopts a sol-gel method to prepare the compound flame-retardant wood by sequentially dipping sodium silicate and boric acid solution, solves the problems of poor flame retardance, poor loss of the wood treated by sodium silicate and the like of the existing boric acid, and effectively improves the flame-retardant stability of the wood. However, the process adopts a two-step impregnation method, the dosage is large, the process is tedious, the uncontrollability is high, and the mechanical property and the hydrophilicity of the wood are not improved.
Chinese patent publication CN 114102776A adopts aniline to impregnate and polymerize in situ to load wood to improve flame retardance, has the advantages of small addition amount, low smoke yield, strong binding force and the like, and effectively solves the problems of large addition amount of inorganic flame retardants, weak interface binding, high smoke yield of part of organic flame retardants and the like. However, aniline is not only derived from fossil raw materials and has certain toxicity, but also has low water solubility and needs to be dissolved in hydrochloric acid solution, and too strong acidity can have softening and degradation effects on wood, so that the strength of the wood is reduced.
Chinese patent publication CN111205315A uses cyanuric chloride as matrix, n-hexylamine, 3-aminopropyl triethoxysilane and taurine as modifier to prepare novel flame-retardant compound, and prepares flame-retardant impregnated material by high-temperature high-pressure impregnation and thermal curing. The original color of the wood is maintained, the loss is reduced through chemical grafting with the wood, the nitrogen, sulfur and silicon synergistic flame retardance obviously improves the fire resistance of the wood, and the hydrophilcity of the hydrophobic chain segment is effectively reduced. However, the preparation process of the process is complex, involves multiple steps of reaction and treatment procedures, has various required raw materials and equipment, uses a large amount of toluene, ethanol and strong acid and alkali, has no environmental friendliness and limits further popularization.
Chinese patent publication CN 104816365A is prepared by compounding a water-soluble terpolymer and a melamine formaldehyde prepolymer to prepare the water-based intumescent wood flame retardant, and compared with the traditional flame retardant, the water-based intumescent wood flame retardant has the advantages of high pH, good water solubility, high sample loading rate, excellent flame retardant effect and the like, and prevents the flame retardant from frosting while not damaging the physical properties of wood. However, the preparation steps of the water-based flame retardant are complicated, and a large amount of stone-derived micromolecule compounds and alcohol solvents are used, so that the water-based flame retardant is easy to remain or volatilize to cause pollution.
Aiming at the defects that most of the added flame retardants have large dosage, poor compatibility and easy loss, the mechanical properties of wood are not improved, and most of the resin flame retardants have complex synthesis steps, are not green in source and depend on organic solvents, it is necessary to provide an efficient, convenient, green, environment-friendly and multi-effect wood functionalization improvement mode.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art described above, a primary object of the present invention is to provide a bio-based flame retardant unsaturated polyester for reinforcing modification of wood.
The invention also aims to provide a preparation method of the bio-based flame retardant unsaturated polyester for wood reinforcement modification.
It is a further object of the present invention to provide the use of the bio-based flame retardant unsaturated polyester for wood reinforcement modification as described above.
The aim of the invention is achieved by the following scheme:
a bio-based flame-retardant unsaturated polyester for wood enhancement modification is synthesized by itaconic acid and a flame retardant FRC-6 through a melt polycondensation method in one step.
The preparation method of the bio-based flame-retardant unsaturated polyester for wood reinforcement modification specifically comprises the following steps:
adding itaconic acid, a flame retardant FRC-6, a pre-polycondensation catalyst and a polymerization inhibitor into a reaction container, heating under the protection of inert atmosphere to perform pre-polycondensation, then adding a polycondensation catalyst, performing vacuum decompression on a reaction system, performing polycondensation reaction, cooling after the polycondensation reaction is finished, adding water to dissolve, filtering, and preserving the obtained liquid in a sealing manner to obtain the bio-based flame-retardant unsaturated polyester for wood reinforcement modification.
The mole ratio of itaconic acid to flame retardant FRC-6 is 1:1-3:1.
The pre-polycondensation catalyst is at least one of p-toluenesulfonic acid monohydrate, thionyl chloride, 4-dimethylaminopyridine and dicyclohexylcarbodiimide; the dosage of the pre-polymerization catalyst is 0.2-1 mol% of itaconic acid.
The polymerization inhibitor is at least one of hydroquinone, p-hydroxyanisole, p-benzoquinone, methyl hydroquinone and 2, 5-di-tert-butyl hydroquinone; the dosage of the polymerization inhibitor is 0.2 to 0.8 weight percent of the total mass of the itaconic acid and the flame retardant FRC-6.
The reaction conditions for realizing the pre-polycondensation by the temperature rising reaction are as follows: heating to 100-120 deg.c to react for 1-4 to produce no water.
The polycondensation catalyst is at least one of dibutyl tin dilaurate and dimethyl cyclohexylamine; the dosage of the polycondensation catalyst is 0.2-1 wt% of the total mass of itaconic acid and flame retardant FRC-6.
The vacuum decompression refers to the vacuum decompression until the vacuum degree is between-0.07 and-0.09 MPa; the polycondensation reaction is to react for 1-5 hours at the temperature of between 100 and 120 ℃ after 1-3 hours, then raise the temperature to between 140 and 160 ℃ and stop the reaction when the acid value reaches 130 to 180 mgKOH/g.
The cooling refers to cooling to 50-90 ℃.
The filtering after adding water to dissolve refers to dissolving the bio-based flame-retardant unsaturated polyester for wood enhancement modification by adding water, and then filtering to remove insoluble impurities. In the invention, the bio-based flame-retardant unsaturated polyester for wood enhancement modification is water-soluble, so that the purified bio-based flame-retardant unsaturated polyester for wood enhancement modification can be obtained through water-soluble and filtration, and the impregnating solutions with different solid contents can be prepared by adjusting the water adding amount.
The application of the bio-based flame retardant unsaturated polyester for wood reinforcement modification in impregnating reinforcement modified wood.
The application of the bio-based flame-retardant unsaturated polyester for wood reinforcement modification in impregnating reinforcement modified wood specifically comprises the following steps:
(1) Taking the bio-based flame-retardant unsaturated polyester for wood enhancement modification, adding an initiator, fully and uniformly stirring to obtain a compound impregnating solution, and standing for later use;
(2) Placing wood and the compound impregnating solution obtained in the step (1) into an impregnating tank for vacuum-pressurization impregnating treatment, taking out, wiping, and standing;
(3) And (3) placing the sample in the step (2) into a blast drying box for curing, and transferring the sample to a constant temperature and humidity box for balancing (20 ℃ and 65%RH) after the resin is completely cured to obtain the bio-based flame-retardant unsaturated polyester impregnation reinforced modified wood.
The bio-based flame retardant unsaturated polyester for wood reinforcement modification described in step (1) is an aqueous solution having a solid content of unsaturated polyester of 5 to 60% (i.e., the mass percentage of unsaturated polyester in aqueous solution of 5 to 60%), wherein the solid content is preferably 20 to 50%.
The initiator in the step (1) is at least one of tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, di-tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide; the amount of the initiator is 1-5% of the mass of the polyester in the bio-based flame-retardant unsaturated polyester for wood enhancement modification;
the wood in the step (2) is one of poplar wood, eucalyptus wood, pine wood and rubber wood; the wood is preferably sawed to (130+/-5 mm) x (3+/-0.5 mm) before being used, then ground and polished, and then ultrasonically cleaned by absolute ethyl alcohol for 1-3 h, and then the solvent is removed at 70-100 ℃.
The wood and the compound impregnating solution in the step (2) are used in an amount that the compound impregnating solution submerges the wood: the dipping treatment in the step (2) means that the vacuum degree is pumped to-0.05 to-0.08 MPa, the pressure is kept for 0.5 to 3 hours, the pressure is further increased to 0.4 to 0.8MPa, the pressure is kept for 1 to 5 hours, and then the liquid is discharged and wiped dry.
The standing treatment in the step (2) means standing for 6-12 hours at room temperature.
The curing in the step (3) means curing for 6 to 12 hours at the temperature of 60 to 160 ℃.
The constant temperature and humidity box in the step (3) is 20 ℃ and 65% RH.
Compared with the prior art, the invention has the following advantages:
considering that most of the added flame retardants have large dosage, poor compatibility and easy loss, and the mechanical properties of wood are not improved, and most of the resin flame retardants have complicated synthesis steps, are not green in source and depend on organic solvents, the invention adopts itaconic acid and flame retardant FRC-6 to synthesize the bio-based flame retardant unsaturated polyester in one step by a melt polycondensation method, and is applied to the impregnation enhancement modification of wood.
The invention synthesizes the bio-based flame-retardant unsaturated polyester by using the bio-based dicarboxylic acid itaconic acid and the dihydric alcohol flame retardant FRC-6 through a one-step esterification method, has simple synthesis steps, green raw material sources and no use of any organic solvent, and is environment-friendly resin.
The bio-based unsaturated polyester used by the invention has excellent water dispersibility, is stable after high-speed centrifugation and indoor storage (1-6 months), can be used after the solid content is 5-75%, and has good permeability, high drug loading rate and remarkable modification effect in wood.
The invention adopts the bio-based flame-retardant unsaturated polyester to impregnate the wood and polymerize in situ, thereby not only greatly improving the flame retardance of the wood and reducing the loss of the flame retardant, but also improving the physical and mechanical properties of the wood, realizing multiple effects of one agent and having good application prospect.
Drawings
FIG. 1 is an infrared spectrum of structural characterization of bio-based flame retardant unsaturated polyesters.
Fig. 2 is a scanning electron microscope image of the modified wood after step (7) of example 4 (example 4).
FIG. 3 is a graph showing the oxygen index results of pure wood and modified wood after step (7) of examples 1 to 4 (examples 1 to 4).
Fig. 4 is a graph of flexural strength and flexural modulus of pure wood and modified wood after step (7) of example 3 (example 3).
FIG. 5 is a graph of the loss rate of FRC-6 impregnated modified wood versus modified wood after step (7) of example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
1) Itaconic acid and flame retardant FRC-6 with the molar mass ratio of 1.3:1, catalyst p-toluenesulfonic acid monohydrate (the dosage is 0.5mol% of itaconic acid) and polymerization inhibitor hydroquinone (the dosage is 0.5wt% of the total mass of itaconic acid and flame retardant FRC-6) are respectively added into a three-neck flask provided with a mechanical stirrer, a condenser tube and a nitrogen device, the temperature is gradually increased to 120 ℃, the reaction is carried out for 2 hours until no water is generated basically, and the pre-polycondensation is realized.
2) Adding a polycondensation catalyst dibutyl tin dilaurate (the dosage is 0.5wt% of the total mass of itaconic acid and flame retardant FRC-6), vacuum decompressing the system, keeping the vacuum degree at-0.09 MPa, reacting at 120 ℃ for 2 hours, heating to 140 ℃ for 4 hours, and stopping the reaction when the acid value reaches 150 mgKOH/g.
3) Cooling to 60 ℃, adding deionized water for dissolution, pouring out, filtering, sealing and preserving to obtain the aqueous solution of the water-based bio-based flame-retardant unsaturated polyester.
4) The poplar sample plate is sawed to (130+/-5 mm) x (3+/-0.5 mm), ground and polished, the wood sample is ultrasonically cleaned with absolute ethyl alcohol for 2 hours, and then the solvent is removed through a drying oven at 80 ℃.
5) Taking an aqueous solution of water-based bio-based flame-retardant unsaturated polyester with solid content of 20%, adding 2% of initiator tert-butyl peroxybenzoate (wherein 2% is the amount of the initiator which is 2% of the mass of the unsaturated polyester in the aqueous solution), fully and uniformly stirring, and standing for later use.
6) Placing the treated wood and the compound impregnating solution into an impregnating tank, vacuumizing to-0.08 MPa, maintaining for 0.5h, pressurizing to 0.7MPa, and maintaining for 1h. Taking out the mixture after pressure relief, wiping the mixture, and standing the mixture indoors for 12 hours.
7) And (3) placing the impregnated sample into a blast drying oven, curing for 2 hours at the temperature of 60 ℃/90 ℃/120 ℃/150 ℃ in a gradient way, and transferring the sample to a constant temperature and humidity oven for balancing (20 ℃ and 65% RH) after the resin is completely cured to obtain the bio-based flame retardant unsaturated polyester impregnated reinforced modified wood.
Example 2
1) Itaconic acid and flame retardant FRC-6 with the molar mass ratio of 1.3:1, catalyst p-toluenesulfonic acid monohydrate (the dosage is 0.5mol% of itaconic acid) and polymerization inhibitor hydroquinone (the dosage is 0.5wt% of the total mass of itaconic acid and flame retardant FRC-6) are respectively added into a three-neck flask provided with a mechanical stirrer, a condenser tube and a nitrogen device, the temperature is gradually increased to 120 ℃, the reaction is carried out for 2 hours until no water is generated basically, and the pre-polycondensation is realized.
2) Adding a polycondensation catalyst dibutyl tin dilaurate (the dosage is 0.5wt% of the total mass of itaconic acid and flame retardant FRC-6), vacuum decompressing the system, keeping the vacuum degree at-0.09 MPa, reacting at 120 ℃ for 2 hours, heating to 140 ℃ for 4 hours, and stopping the reaction when the acid value reaches 150 mgKOH/g.
3) Cooling to 60 ℃, adding deionized water for dissolution, pouring out, filtering, sealing and preserving to obtain the aqueous solution of the water-based bio-based flame-retardant unsaturated polyester.
4) The poplar sample plate is sawed to (130+/-5 mm) x (3+/-0.5 mm), ground and polished, the wood sample is ultrasonically cleaned with absolute ethyl alcohol for 2 hours, and then the solvent is removed through a drying oven at 80 ℃.
5) Taking an aqueous solution of water-based bio-based flame-retardant unsaturated polyester with solid content of 30%, adding 2% of initiator tert-butyl peroxybenzoate (wherein 2% is the amount of the initiator which is 2% of the mass of the unsaturated polyester in the aqueous solution), fully and uniformly stirring, and standing for later use.
6) Placing the treated wood and the compound impregnating solution into an impregnating tank, vacuumizing to-0.08 MPa, maintaining for 0.5h, pressurizing to 0.7MPa, and maintaining for 1h. Taking out the mixture after pressure relief, wiping the mixture, and standing the mixture indoors for 12 hours.
7) And (3) placing the impregnated sample into a blast drying oven, curing for 2 hours at the temperature of 60 ℃/90 ℃/120 ℃/150 ℃ in a gradient way, and transferring the sample to a constant temperature and humidity oven for balancing (20 ℃ and 65% RH) after the resin is completely cured to obtain the bio-based flame retardant unsaturated polyester impregnated reinforced modified wood.
Example 3
1) Itaconic acid and flame retardant FRC-6 with the molar mass ratio of 1.3:1, catalyst p-toluenesulfonic acid monohydrate (the dosage is 0.5mol% of itaconic acid) and polymerization inhibitor hydroquinone (the dosage is 0.5wt% of the total mass of itaconic acid and flame retardant FRC-6) are respectively added into a three-neck flask provided with a mechanical stirrer, a condenser tube and a nitrogen device, the temperature is gradually increased to 120 ℃, the reaction is carried out for 2 hours until no water is generated basically, and the pre-polycondensation is realized.
2) Adding a polycondensation catalyst dibutyl tin dilaurate (the dosage is 0.5wt% of the total mass of itaconic acid and flame retardant FRC-6), vacuum decompressing the system, keeping the vacuum degree at-0.09 MPa, reacting at 120 ℃ for 2 hours, heating to 140 ℃ for 4 hours, and stopping the reaction when the acid value reaches 150 mgKOH/g.
3) Cooling to 60 ℃, adding deionized water for dissolution, pouring out, filtering, sealing and preserving to obtain the aqueous solution of the water-based bio-based flame-retardant unsaturated polyester.
4) The poplar sample plate is sawed to (130+/-5 mm) x (3+/-0.5 mm), ground and polished, the wood sample is ultrasonically cleaned with absolute ethyl alcohol for 2 hours, and then the solvent is removed through a drying oven at 80 ℃.
5) Taking an aqueous solution of water-based bio-based flame-retardant unsaturated polyester with solid content of 40%, adding 2% of initiator tert-butyl peroxybenzoate (wherein 2% is the amount of the initiator which is 2% of the mass of the unsaturated polyester in the aqueous solution), fully and uniformly stirring, and standing for later use.
6) Placing the treated wood and the compound impregnating solution into an impregnating tank, vacuumizing to-0.08 MPa, maintaining for 0.5h, pressurizing to 0.7MPa, and maintaining for 1h. Taking out the mixture after pressure relief, wiping the mixture, and standing the mixture indoors for 12 hours.
7) And (3) placing the impregnated sample into a blast drying oven, curing for 2 hours at the temperature of 60 ℃/90 ℃/120 ℃/150 ℃ in a gradient way, and transferring the sample to a constant temperature and humidity oven for balancing (20 ℃ and 65% RH) after the resin is completely cured to obtain the bio-based flame retardant unsaturated polyester impregnated reinforced modified wood.
Example 4
1) Itaconic acid and flame retardant FRC-6 with the molar mass ratio of 1.3:1, catalyst p-toluenesulfonic acid monohydrate (the dosage is 0.5mol% of itaconic acid) and polymerization inhibitor hydroquinone (the dosage is 0.5wt% of the total mass of itaconic acid and flame retardant FRC-6) are respectively added into a three-neck flask provided with a mechanical stirrer, a condenser tube and a nitrogen device, the temperature is gradually increased to 120 ℃, the reaction is carried out for 2 hours until no water is generated basically, and the pre-polycondensation is realized.
2) Adding a polycondensation catalyst dibutyl tin dilaurate (the dosage is 0.5wt% of the total mass of itaconic acid and flame retardant FRC-6), vacuum decompressing the system, keeping the vacuum degree at-0.09 MPa, reacting at 120 ℃ for 2 hours, heating to 140 ℃ for 4 hours, and stopping the reaction when the acid value reaches 150 mgKOH/g.
3) Cooling to 60 ℃, adding deionized water for dissolution, pouring out, filtering, sealing and preserving to obtain the aqueous solution of the water-based bio-based flame-retardant unsaturated polyester.
4) The poplar sample plate is sawed to (130+/-5 mm) x (3+/-0.5 mm), ground and polished, the wood sample is ultrasonically cleaned with absolute ethyl alcohol for 2 hours, and then the solvent is removed through a drying oven at 80 ℃.
5) Taking an aqueous solution of water-based bio-based flame-retardant unsaturated polyester with solid content of 50%, adding 2% of initiator tert-butyl peroxybenzoate (wherein 2% is the amount of the initiator which is 2% of the mass of the unsaturated polyester in the aqueous solution), fully and uniformly stirring, and standing for later use.
6) Placing the treated wood and the compound impregnating solution into an impregnating tank, vacuumizing to-0.08 MPa, maintaining for 0.5h, pressurizing to 0.7MPa, and maintaining for 1h. Taking out the mixture after pressure relief, wiping the mixture, and standing the mixture indoors for 12 hours.
7) And (3) placing the impregnated sample into a blast drying oven, curing for 2 hours at the temperature of 60 ℃/90 ℃/120 ℃/150 ℃ in a gradient way, and transferring the sample to a constant temperature and humidity oven for balancing (20 ℃ and 65% RH) after the resin is completely cured to obtain the bio-based flame retardant unsaturated polyester impregnated reinforced modified wood.
Comparative example 1
1) The poplar sample plate is sawed to (130+/-5 mm) x (3+/-0.5 mm), ground and polished, the wood sample is ultrasonically cleaned with absolute ethyl alcohol for 2 hours, and then the solvent is removed through a drying oven at 80 ℃.
2) Taking a flame retardant FRC-6 water solution with the solid content of 40%, putting the treated wood and the flame retardant impregnating solution into an impregnating tank together, vacuumizing to-0.08 MPa, maintaining for 0.5h, pressurizing to 0.7MPa, and maintaining for 1h. Taking out the mixture after pressure relief, wiping the mixture, and standing the mixture indoors for 12 hours.
3) And (3) placing the impregnated sample into a blast drying oven, respectively drying at 60 ℃/90 ℃/103 ℃ for 2 hours in a gradient way, and then transferring to a constant temperature and humidity oven for balancing (20 ℃ and 65% RH) to obtain the flame retardant FRC-6 impregnated modified wood.
FIG. 1 is an infrared spectrogram of a structural characterization of a bio-based flame retardant unsaturated polyester. As can be seen from the figure, the unsaturated polyesters were indeed successfully synthesized in examples 1 to 4 of the present invention.
FIG. 2 is a scanning electron micrograph of the modified wood after step (7) of example 4 (example 4) in which successful impregnation of the unsaturated polyester into the wood and in situ polymerization was observed.
FIG. 3 is a graph showing the oxygen index results of pure wood and modified wood after step (7) of examples 1 to 4 (examples 1 to 4), with the increase in the solid content of the impregnation liquid, and the subsequent increase in flame retardancy.
Fig. 4 is a graph of flexural strength and flexural modulus of pure wood and modified wood after step (7) of example 3 (example 3), the impregnation modification of unsaturated polyester improves the strength of the wood.
FIG. 5 is a graph of the loss rate of FRC-6 impregnated modified wood versus modified wood after step (7) of example 3 (example 3), the impregnation modification of unsaturated polyester reduced the loss rate of flame retardant. The method for testing the loss rate is developed according to the test method for the loss rate of the wood preservative, but the method is correspondingly adjusted, and is specifically as follows: before testing, the samples were baked to absolute dryness at 103 ℃ and weighed, then the samples were immersed in deionized water at room temperature for 72 hours, the deionized water was replaced every 24 hours, and finally all the test samples were baked to absolute dryness at 103 ℃ and weighed, and the loss rate was calculated.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A preparation method of bio-based flame-retardant unsaturated polyester for wood enhancement modification is characterized in that the unsaturated polyester is synthesized by itaconic acid and flame retardant FRC-6 through a melt polycondensation method;
the method specifically comprises the following steps:
adding itaconic acid, a flame retardant FRC-6, a pre-polycondensation catalyst and a polymerization inhibitor into a reaction container, heating under the protection of inert atmosphere to perform pre-polycondensation, then adding a polycondensation catalyst, performing vacuum decompression on a reaction system, performing polycondensation reaction, cooling after the polycondensation reaction is finished, adding water to dissolve, filtering, and sealing and preserving the obtained liquid to obtain the bio-based flame-retardant unsaturated polyester for wood reinforcement modification;
the filtering after adding water for dissolution refers to dissolving the bio-based flame-retardant unsaturated polyester for wood enhancement modification by adding water, and then filtering to remove insoluble impurities;
the mole ratio of the itaconic acid to the flame retardant FRC-6 is 1:1-3:1;
the pre-polycondensation catalyst is at least one of p-toluenesulfonic acid monohydrate, thionyl chloride, 4-dimethylaminopyridine and dicyclohexylcarbodiimide; the dosage of the catalyst is 0.2-1 mol% of itaconic acid;
the polycondensation catalyst is at least one of dibutyl tin dilaurate and dimethyl cyclohexylamine; the dosage of the polycondensation catalyst is 0.2-1wt% of the total mass of itaconic acid and flame retardant FRC-6;
the reaction conditions for realizing the pre-polycondensation by the temperature rising reaction are as follows: heating to 100-120 ℃, and reacting for 1-4 hours until no water is generated basically;
the vacuum decompression refers to the vacuum decompression until the vacuum degree is between-0.07 and-0.09 MPa; the polycondensation reaction is to react for 1-5 hours at the temperature of 100-120 ℃ after 1-3 hours, then raise the temperature to 140-160 ℃ and stop the reaction when the acid value reaches 130-180 mgKOH/g.
2. A biobased flame retardant unsaturated polyester for wood reinforcement modification prepared according to the method of claim 1.
3. Use of the bio-based flame retardant unsaturated polyester for wood reinforcement modification according to claim 2 for impregnation reinforcement modified wood.
4. Use of a bio-based flame retardant unsaturated polyester for wood reinforcement modification according to claim 3 for impregnation reinforcement modification of wood, characterized by comprising the steps of:
(1) Taking bio-based flame-retardant unsaturated polyester for wood reinforcement modification, adding an initiator, fully and uniformly stirring to obtain a compound impregnating solution, and standing for later use;
(2) Placing wood and the compound impregnating solution obtained in the step (1) into an impregnating tank for vacuum-pressurization impregnating treatment, taking out, wiping, and standing;
(3) And (3) placing the sample in the step (2) into a blast drying box for curing, and transferring the sample to a constant temperature and humidity box for balancing after the resin is completely cured to obtain the bio-based flame-retardant unsaturated polyester impregnating reinforced modified wood.
5. Use of a bio-based flame retardant unsaturated polyester for wood reinforcement modification according to claim 4 for impregnation reinforcement modified wood, characterized in that:
the bio-based flame retardant unsaturated polyester used for wood enhancement modification in the step (1) is an aqueous solution with the solid content of the unsaturated polyester of 5-60%;
the initiator in the step (1) is at least one of tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, di-tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide; the amount of the initiator is 1-5% of the mass of the unsaturated polyester in the aqueous solution.
6. Use of a bio-based flame retardant unsaturated polyester for wood reinforcement modification according to claim 4 for impregnation reinforcement modified wood, characterized in that:
the wood in the step (2) is one of poplar wood, eucalyptus wood, pine wood and rubber wood;
the wood and the compound impregnating solution in the step (2) are used in an amount that the compound impregnating solution submerges the wood: the dipping treatment in the step (2) means that the vacuum degree is pumped to-0.05 to-0.08 MPa, the pressure is kept for 0.5 to 3 hours, the pressure is further increased to 0.4 to 0.8MPa, the pressure is kept for 1 to 5 hours, and then the pressure is relieved, and the liquid is taken out and dried;
the standing treatment in the step (2) refers to standing for 6-12 hours at room temperature.
7. Use of a bio-based flame retardant unsaturated polyester for wood reinforcement modification according to claim 4 for impregnation reinforcement modified wood, characterized in that:
the curing in the step (3) means curing for 6-12 hours at 60-160 ℃;
the constant temperature and humidity box in the step (3) is 20 ℃ and 65% RH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211368353.8A CN115746277B (en) | 2022-11-03 | 2022-11-03 | Bio-based flame-retardant unsaturated polyester for wood enhancement modification and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211368353.8A CN115746277B (en) | 2022-11-03 | 2022-11-03 | Bio-based flame-retardant unsaturated polyester for wood enhancement modification and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115746277A CN115746277A (en) | 2023-03-07 |
| CN115746277B true CN115746277B (en) | 2024-03-12 |
Family
ID=85357133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211368353.8A Active CN115746277B (en) | 2022-11-03 | 2022-11-03 | Bio-based flame-retardant unsaturated polyester for wood enhancement modification and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115746277B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1188466A (en) * | 1967-06-19 | 1970-04-15 | Degussa | A Process for the Production of Synthetic Resin Impregnated Wood |
| CN103333205A (en) * | 2013-06-28 | 2013-10-02 | 青岛富斯林化工科技有限公司 | Phosphorus flame retardant 2,3-dicarboxylic propyl diphenyl phosphine oxide, preparation method and flame-retardant polyester composition thereof |
| CN107599086A (en) * | 2017-08-31 | 2018-01-19 | 中国林业科学研究院木材工业研究所 | A kind of preparation method based on environment-friendly resin enhancing, flame-retardant modified timber |
| CN109666120A (en) * | 2017-10-17 | 2019-04-23 | 翁秋梅 | A kind of energy-absorbing method based on hydridization dynamic aggregation object |
| CN111378263A (en) * | 2018-12-28 | 2020-07-07 | 浙江荣泰科技企业有限公司 | Single-component halogen-free flame-retardant insulating impregnating resin and preparation method thereof |
| CN112157765A (en) * | 2020-10-15 | 2021-01-01 | 桃江县鑫龙阳光木业胶板厂(普通合伙) | Flame-retardant reinforced wood and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170226424A1 (en) * | 2014-08-07 | 2017-08-10 | Ronald Philip Moon | Wood modification to enhance fire retardancy |
-
2022
- 2022-11-03 CN CN202211368353.8A patent/CN115746277B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1188466A (en) * | 1967-06-19 | 1970-04-15 | Degussa | A Process for the Production of Synthetic Resin Impregnated Wood |
| CN103333205A (en) * | 2013-06-28 | 2013-10-02 | 青岛富斯林化工科技有限公司 | Phosphorus flame retardant 2,3-dicarboxylic propyl diphenyl phosphine oxide, preparation method and flame-retardant polyester composition thereof |
| CN107599086A (en) * | 2017-08-31 | 2018-01-19 | 中国林业科学研究院木材工业研究所 | A kind of preparation method based on environment-friendly resin enhancing, flame-retardant modified timber |
| CN109666120A (en) * | 2017-10-17 | 2019-04-23 | 翁秋梅 | A kind of energy-absorbing method based on hydridization dynamic aggregation object |
| CN111378263A (en) * | 2018-12-28 | 2020-07-07 | 浙江荣泰科技企业有限公司 | Single-component halogen-free flame-retardant insulating impregnating resin and preparation method thereof |
| CN112157765A (en) * | 2020-10-15 | 2021-01-01 | 桃江县鑫龙阳光木业胶板厂(普通合伙) | Flame-retardant reinforced wood and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 磷/硅协同阻燃改性水性聚氨酯的性能研究;王萃萃;王秋梅;许戈文;;涂料技术与文摘(第12期);16-21 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115746277A (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2485880B1 (en) | Impregnation of chemicals into wood | |
| CN113305959B (en) | Method for improving size stability of fast-growing wood by using lignin-based modified liquid medicine | |
| CN108407002B (en) | Phosphatized wood and preparation method thereof | |
| CN114804786B (en) | Anti-cracking mortar and preparation method thereof | |
| CN113696291B (en) | Method for improving wood performance through mild furfuryl alcohol modification and synergistic densification treatment | |
| CN110655620B (en) | Aqueous hyperbranched polyacrylate emulsion, preparation method and application thereof | |
| CN114179182A (en) | Resin-reinforced wood-based composite material and preparation method thereof | |
| CN110156989A (en) | A kind of modified quartz fibre/cyanate composite material, preparation method and application | |
| US20060293440A1 (en) | Methods of preparing organic-inorganic hybrid binder compositions and nonwoven products | |
| CN115746277B (en) | Bio-based flame-retardant unsaturated polyester for wood enhancement modification and preparation and application thereof | |
| CN107599093B (en) | Water-borne functional wood modifier and treatment method thereof | |
| CN112920691B (en) | High-strength anti-aging optical fiber outer coating and preparation method thereof | |
| CN101434080B (en) | Waterglass-polymer homogeneous phase hybrid modified precursor liquid for lumber and preparation method thereof | |
| CN115972329A (en) | Surface treatment process of flame-retardant wood board | |
| CN110627968B (en) | Aqueous organic montmorillonite modifier emulsion, preparation method and application thereof | |
| Pandey et al. | Study of dimensional stability, decay resistance, and light stability of phenylisothiocyanate modified rubberwood | |
| CN110408358B (en) | Acid and alkali resistant bio-based adhesive and preparation method thereof | |
| CN116215028A (en) | Environment-friendly composite board based on recycled fibers and manufacturing process thereof | |
| CN115322311A (en) | Lignin-based acrylic resin and preparation method thereof | |
| JPH056481B2 (en) | ||
| CN112647347A (en) | Preparation method of heat-resistant auxiliary agent for heat-resistant insulating paper | |
| CN115922861B (en) | Composition for wood impregnation, wood prepreg, modified wood, and method for producing same | |
| CN113214622B (en) | Alloy resin and glass fiber reinforced plastic plate using same | |
| CN110669441A (en) | Preparation method of PVA-phosphorus-aluminum adhesive for artificial board | |
| CN116835913B (en) | Light high-strength soft stone brick and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |