CN104312535B - Lignin weatherability fiberboard adhesive and its production method - Google Patents
Lignin weatherability fiberboard adhesive and its production method Download PDFInfo
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- CN104312535B CN104312535B CN201410634441.7A CN201410634441A CN104312535B CN 104312535 B CN104312535 B CN 104312535B CN 201410634441 A CN201410634441 A CN 201410634441A CN 104312535 B CN104312535 B CN 104312535B
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- lignin
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- weatherability
- fiberboard
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- 229920005610 lignin Polymers 0.000 title claims abstract description 105
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 66
- 239000000853 adhesive Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000011094 fiberboard Substances 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910000077 silane Inorganic materials 0.000 claims abstract description 18
- 239000013530 defoamer Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 8
- 239000008107 starch Substances 0.000 claims abstract description 8
- 235000019698 starch Nutrition 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000013049 sediment Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 13
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- -1 phenyl ester Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 241000609240 Ambelania acida Species 0.000 claims description 7
- 235000006708 antioxidants Nutrition 0.000 claims description 7
- 239000010905 bagasse Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical group OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 6
- 229930003427 Vitamin E Natural products 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 6
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 6
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 6
- 235000019165 vitamin E Nutrition 0.000 claims description 6
- 229940046009 vitamin E Drugs 0.000 claims description 6
- 239000011709 vitamin E Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004255 Butylated hydroxyanisole Substances 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 4
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 235000019282 butylated hydroxyanisole Nutrition 0.000 claims description 4
- 229940043253 butylated hydroxyanisole Drugs 0.000 claims description 4
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- UNDNWWXFDBUETQ-UHFFFAOYSA-N ethenyl-[(2-methylpropan-2-yl)oxy]silane Chemical class CC(C)(C)O[SiH2]C=C UNDNWWXFDBUETQ-UHFFFAOYSA-N 0.000 claims description 2
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 claims 1
- 239000012965 benzophenone Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 84
- 235000019256 formaldehyde Nutrition 0.000 description 28
- 229960004279 formaldehyde Drugs 0.000 description 27
- 238000012545 processing Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 8
- 239000002023 wood Substances 0.000 description 7
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- WDFZWSZNOFELJY-OLQVQODUSA-N (1R,6S)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical group C1=CC=C[C@H]2O[C@H]21 WDFZWSZNOFELJY-OLQVQODUSA-N 0.000 description 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 description 1
- GMIMEXBGMYDQTO-UHFFFAOYSA-N C=O.C=O.NC(N)=O Chemical compound C=O.C=O.NC(N)=O GMIMEXBGMYDQTO-UHFFFAOYSA-N 0.000 description 1
- IGQLTMLBFFIKBR-UHFFFAOYSA-N SCO[Si](OC)(C)CCCO Chemical compound SCO[Si](OC)(C)CCCO IGQLTMLBFFIKBR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of lignin weatherability fiberboard adhesive and its production method, it is made up of the raw material of following parts by weight：20 30 parts of lignin；20 30 parts of phenol；15 20 parts of starch；15 parts of silane coupler；15 parts of antioxidant；0.1 0.2 parts of 35 parts of ultra-violet absorber and defoamer.Production method is：Pretreatment reaction is carried out to lignin, modified lignin is made, then starch, antioxidant and ultra-violet absorber, silane coupler and defoamer are added in stirred autoclave according to formula rate, it is well mixed, ground 1~2 hour with three-roll grinder again, obtain the adhesive that viscosity at 18 20 DEG C is 0.20~0.50Pas.The lignin weatherability fiberboard adhesive weatherability excellent effect of the present invention, it is with low cost and bond effect is good, it is suitable for large-scale promotion and application.
Description
Technical field
The present invention relates to adhesive field, particularly a kind of lignin weatherability fiberboard adhesive and its production method.
Background technology
Fiberboard is the wood-based plate for being molded and being made using its intrinsic gluing performance that interweaved by lignin fibre.Fiberboard is most
Conventional adhesive is Lauxite or modified urea-formaldehyde resin.Lauxite simple production process, cost is low, but water resistance and strong
Degree is relatively low, by melamine, phenol or resorcinol, acrylate copolymer, isocyanates, polyvinyl alcohol or lignin etc.
Modified Lauxite significantly improves water resistance and adhesion strength.One of raw materials for production of Lauxite or modified urea-formaldehyde resin
It is formaldehyde, therefore, using the inevitable release formaldehyde of wood-based plate of Lauxite or modified urea-formaldehyde resin as adhesive.
Formaldehyde is the stealthy killer of health, and indoor concentration of formaldehyde is more than 0.5mg/m3, and people stays 5 hours in such environment, will felt
To dizziness.The long-term concentration of formaldehyde that is in, will be carcinogenic more than 0.5mg/m3, therefore burst size of methanal is restriction industry of artificial boards hair
One key factor of exhibition.
Guangxi Nanning Green Park Beilin Wood Industry Co., Ltd. has been carried out largely for low residual formaldehyde urea-formaldehyde resin adhesive
Research, and applied for Patents, application publication number CN103450432A patent：A kind of low residual formaldehyde Lauxite
Production method, its primary raw material is formaldehyde and urea, and formaldehyde is disposably feeds intake, and urea feeds intake in three times；The life of Lauxite
Production is divided into prepolymerization, polymerization and later stage polymerization three phases, by controlling each stage inventory and reaction temperature, it is to avoid poly-
Conjunction process embeds the generation of phenomenon, and the Lauxite narrow molecular weight distribution of gained, residual formaldehyde is low.Application publication number is
CN103450832A patent：A kind of modified urea-formaldehyde resin glue of low residual formaldehyde sticks agent and its production method, by using
Modified urea-formaldehyde resin, reinforcing agent and defoamer are primary raw material, the adhesive residual formaldehyde ＜ 0.1mg/L being made, as people
The adhesive of plate is made, burst size of methanal is extremely low, protect the health of consumer.Application publication number is special for CN 103408712A's
Profit：A kind of production method of low residual formaldehyde polyvinyl alcohol modification glue urea formaldehyde adhesive, its primary raw material is formaldehyde, urea
And polyvinyl alcohol, three phases final production is polymerize by prepolymerization, polymerization and later stage and goes out the low adhesive of residual formaldehyde.To the greatest extent
Pipe is in this way, because formaldehyde is one of main raw materials for production, the inevitable release formaldehyde of wood-based plate being made of Lauxite is most
Manage by the above technical controlling residual formaldehyde low, but still have room for improvement.Meanwhile, Lauxite due to industrialization degree compared with
Height, production technology is more ripe, and cost is difficult to reduce, and causes current urea-formaldehyde resin adhesive market price harmful competition.
Lignin is the most abundant and most important organic polymer that plant kingdom is only second to cellulose, and being distributed widely in has
In higher plant more than the pteridophyte plant of vascular bundle, it is that a class is connected by benzene oxide unit by ehter bond and carbon-carbon bond
Unformed high polymer, lignin has wide variety of potential quality, first lignin in itself due to its molecular characterization in adhesive
With caking property, adhesive can be directly used as.Authorize Publication No.：CN100381534C patent：A kind of lignin environmental protection
Type adhesive and preparation method thereof, lignin adhesive is obtained by the method washed lignin, prepare lignin liquor, though it is main
It is lignin to want raw material, but still with formaldehyde as one of raw material, the adhesive being made still has a small amount of Form aldehyde release；Application publication number
For CN101928536A invention：A kind of flame retardant modified lignin resin glue and preparation method thereof, is made by following components raw material：It is dense
Spend the formalin 20-30wt% for 30-50%, the aldehydes matter 8-12wt% containing three-functionality-degree, surplus be using draft lignin as
The papermaking wastewater of main active substances, it is seen then that still with formaldehyde as main raw material in the invention, unavoidable to have formaldehyde residual
Stay；Meanwhile, lignin is equally widely used in phenolic resin and melamine-formaldehyde resin adhesive stick agent, but same is existed
The problem of formaldehyde dissociates.
In addition, containing a small amount of active group in adhesive universal at present, easily by the oxygen or light in environment
Oxidation Decomposition, causes adhesive aging to lose effect, causes the wood-based plate or fiberboard quality of outdoor outdoor application to go wrong.
And many start with from the structure of raw material of researcher is furtherd investigate, weatherability is improved, the cost of adhesive is substantially increased.
Therefore, how using lignin excellent specific property, give full play to it as the effect of adhesive main material, protect simultaneously
There is card adhesive stronger environmental disruption ability of standing to be a worth research and valuable class after fiberboard bonding
Topic.
The content of the invention
The purpose of the present invention is to supply that there is provided a kind of lignin weatherability fiberboard adhesive and its life for above technology
Production method, solving current fiberboard adhesive, there is residues of formaldehyde to endanger environment, and lignin is that the adhesive that main material is made is same
The problem of sample contains formaldehyde, develop a kind of with low cost, good weatherability and the fiberboard adhesive with preferable adhesive property.
Technical scheme is as follows：
The anti-weatherability fiberboard adhesive of lignin, is made up of the raw material of following parts by weight：
20-30 parts of lignin；
20-30 parts of phenol；
15-20 parts of starch；
1-5 parts of silane coupler；
1-5 parts of antioxidant；
3-5 parts of ultra-violet absorber；
0.1-0.2 parts of defoamer.
The starch is one kind or its composition in tapioca, farina, flour.
The silane coupler is VTES, three tert-butoxy vinyl silanes, the second of anilinomethyl three
TMOS, γ-r-chloropropyl trimethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, 3-（2,3 epoxies third
Oxygen）Propyl trimethoxy silicane, mercaptopropyl trimethoxysilane, methyl vinyl diethoxysilane and mercapto hydroxypropyl methyl diformazan
One kind or its composition in TMOS.Inventor has found that the lignin weatherability fiberboard adhesive that the present invention is developed has
Preferable wetability, it is relatively low relative to traditional Lauxite, phenolic resin or its modifier adhesive surface tension, and add
The described silane coupler of invention, can more preferably effectively improve the adhesive property of lignin adhesive of the present invention.Because：Silicon
Both contain organic group in the molecular structure of alkane coupling agent, inorganic structure is contained again, this special molecular structure has it concurrently
The characteristic and function of organic matter and inorganic matter, are had excellent water-fast after being combined using silane coupler with lignin adhesive
Property, heat resistance, weatherability, chemical-resistant and low surface tension, this is probably because one end siloxanes water in silane coupler
The silanol of solution generation can react to form chemical bond with the hydroxyl on adherend and filler surface or oxide, organic active functional group
Chemical bond is also formed with adhesive reaction, the chemical sub- intermolecular forces of bond energy score want the high 1-2 order of magnitude；Meanwhile, it is silane coupled
Active group connection after the other end and lignin modification of agent, forms preferable chemical affinity, two ends bridging, as erected
Irreversible cementation is played after one bridge block, solidification, the bond effect of high intensity is obtained naturally.
The antioxidant is in dibutyl hydroxy toluene, butylated hydroxy anisole, vitamin E and tert-butylhydroquinone
One kind or its composition.
The ultra-violet absorber is septichen phenyl ester, 2-（2 ˊ-the ˊ of hydroxyl-5-aminomethyl phenyl）BTA,
One kind or its composition of 2,4-DihydroxyBenzophenone and 2-hydroxy-4-n-octoxybenzophenone.
The defoamer is dimethyl silicone polymer or tributyl phosphate.
The production method of lignin weatherability fiberboard adhesive, carries out pretreatment reaction to lignin first, and wood is made
Quality modifier, then adds starch, antioxidant, ultra-violet absorber, silicon according to by formula rate in stirred autoclave
Alkane coupling agent and defoamer, are well mixed, then are ground 1-2 hours with three-roll grinder, and it is 0.20- to obtain viscosity at 18-20 DEG C
0.50Pas adhesive.
The modified lignin is made by the following method：
（1）It is prepared by lignin：By adding acid in the black liquor to the alkaline boiling method slurrying using bagasse as raw material, examine
Consider the overall merits such as cost, production ease for operation, selection sulfuric acid, hydrochloric acid, carbon dioxide and aluminum sulfate are addition acid, adjust black liquor
PH to less than 6, preferably in pH1-4, place to insoluble matter all precipitation untill, standing time is 24-72h, then will precipitation
Material separation beyond thing and sediment, separation can be carried out by routine filtration device or Suction filtration device, obtained sediment
Dry, obtain the lignin product that purity is 50-80wt%；To obtain the lignin of higher purity, obtained sediment is made into
One step purification process, concrete technology is：Add water acid adding again in sediment, adjusts pH1-4, is dried after washing, repeats at this
Reason process more than 2 times, can be made more than 80% high-purity lignin product, subsequently into subsequent production processing procedure；
（2）In step（1）70wt% sulfuric acid is added in obtained lignin, after stirring, 140-160 DEG C, sulphur is warming up to
Change reaction 1-2 hours；By evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, control discharging moisture
For 30wt%, precipitation is 15wt% through filtering, drying to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control
85-95 DEG C of temperature, insulation reaction 1 hour finally produces modified lignin with 30% sodium hydroxide regulation pH to 6.5-7.0.Step
Suddenly（2）Sulfonation modifying first is carried out to lignin in reaction, phenolate modification, final obtained modified lignin activity is then carried out
Group is more, and organic active is high, and the function of being more beneficial for playing adhesive is combined with silane coupler.
Beneficial effects of the present invention are：
First, using lignin as adhesive skeleton, add antioxidant and ultra-violet absorber to improve adhesive
Weatherability, not only reduces production cost, and unharmful substance is discharged, with higher Social benefit and economic benefit.
2nd, the problem of containing formaldehyde in traditional fibre plate adhesive is changed, the lignin weatherability that the present invention is developed is fine
It is primary raw material that plate adhesive, which is tieed up, using lignin, by a series of modified, is combined with water resistance auxiliary agent, silane coupler
Together, the gluing performance of adhesive can be significantly improved, the lignin adhesive has viscosity low, to adherend surface tension
It is low, easily wetting, the advantages of adhesion strength is big；Because the active group after lignin modification is easy to silane coupler together
Chemical interactions are formed, and the other end combines to form chemical bond with adherend surface, is much stronger than intermolecular force 1-2 numbers
Magnitude, and with excellent waterproof advantage, make adhesive and fiberboard formation " bridge " structure, reach and be tightly combined, firmly, no
Reversible as closely linked as flesh and blood bond effect.
3rd, production cost is low, easily realizes.The lignin adhesive of the present invention uses the alkaline boiling method using bagasse as raw material
The black liquor of slurrying belongs to refuse reclamation, reduces the cost of raw material, simultaneously through handling obtained high content lignin
Waste discharge is reduced, the road of sustained development is walked, with important value and meaning；In addition, the preparation process of this lignin adhesive
Industrialized condition is ripe, easily realizes big production, possesses the basis of large-scale promotion.
Embodiment
The lignin weatherability fiberboard adhesive factory formula of embodiment 1 and method 1
Formula composition：
25 parts of lignin；
25 parts of phenol；
15 parts of tapioca；
0.5 part of VTES；
0.5 part of anilinomethyl triethoxysilane；
0.5 part of dibutyl hydroxy toluene；
0.5 part of butylated hydroxy anisole；
3 parts of septichen phenyl ester；
0.1 part of dimethyl silicone polymer.
Production method：Pretreatment reaction is carried out to obtained lignin first, modified lignin is made, then according to
Square ratio adds tapioca, silane coupler, dibutyl hydroxy toluene, butylated hydroxy anisole, neighbour in stirred autoclave
MPHB and defoamer, are well mixed, then are ground 1 hour with three-roll grinder, and obtaining viscosity at 18-20 DEG C is
0.20Pas adhesive.
Modified lignin is made by the following method：
（1）It is prepared by lignin：By adding 50wt% in the black liquor to the alkaline boiling method slurrying using bagasse as raw material
Sulfuric acid, adjusts black liquor pH6, places untill insoluble matter all precipitation, standing time is 72h, then by sediment and sediment
Material separation in addition, obtained drying precipitate；Processing is further purified to obtained sediment：In sediment again
Add water 50wt% sulfuric acid, adjusts pH2, is dried after washing, repeats the processing procedure 3 times, and 83.5% high-purity wood can be made
Lignin products, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulfuric acid is added in obtained lignin, after stirring, 140 DEG C are warming up to, sulfonation is anti-
Answer 1 hour；By evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, control discharging moisture be
30wt%, precipitation is 15wt% through filtering, drying to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control temperature
85 DEG C of degree, insulation reaction 1 hour finally produces modified lignin with 30wt% sodium hydroxides regulation pH to 6.8.
The lignin weatherability fiberboard adhesive factory formula of embodiment 2 and method 2
Formula composition：
20 parts of lignin；
20 parts of phenol；
18 parts of farina；
1 part of anilinomethyl triethoxysilane
2 parts of γ-r-chloropropyl trimethoxyl silane；
1 part of vitamin E；
1 part of tert-butylhydroquinone；
2-（2 ˊ-the ˊ of hydroxyl-5-aminomethyl phenyl）1 part of BTA；
3 parts of 2,4-DihydroxyBenzophenone；
0.2 part of tributyl phosphate.
Production method：Pretreatment reaction is carried out to obtained lignin first, modified lignin is made, then according to by
Formula rate adds farina, silane coupler, vitamin E, tert-butylhydroquinone, 2- in stirred autoclave（2ˊ-
The ˊ of hydroxyl-5-aminomethyl phenyl）BTA, 2,4-DihydroxyBenzophenone and defoamer, are well mixed, then are ground with three rollers
Machine is ground 1 hour, obtains the adhesive that viscosity at 18-20 DEG C is 0.40Pas.
Modified lignin is made by the following method：
（1）It is prepared by lignin：By adding 50wt% in the black liquor to the alkaline boiling method slurrying using bagasse as raw material
Sulfuric acid, adjusts black liquor pH5, places untill insoluble matter all precipitation, standing time is 48h, then by sediment and sediment
Material separation in addition, obtained drying precipitate；Processing is further purified to obtained sediment：In sediment again
Add water 50wt% sulfuric acid, adjusts pH2.5, is dried after washing, repeats the processing procedure 5 times, and 87.1% high-purity can be made
Lignin product, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulfuric acid is added in obtained lignin, after stirring, 150 DEG C are warming up to, sulfonation is anti-
Answer 1.5 hours；By evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, control discharging moisture be
30wt%, precipitation is 15wt% through filtering, drying to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control temperature
85 DEG C of degree, insulation reaction 1 hour finally produces modified lignin with 30wt% sodium hydroxides regulation pH to 6.7.
The lignin weatherability fiberboard adhesive factory formula of embodiment 3 and method 3
Formula composition：
30 parts of lignin；
30 parts of phenol；
20 parts of flour；
2 parts of gamma-methyl allyl acyloxypropyl trimethoxysilane；
3—（2,3 the third oxygen of epoxy）1 part of propyl trimethoxy silicane；
2 parts of mercaptopropyl trimethoxysilane；
5 parts of tert-butylhydroquinone；
5 parts of 2-hydroxy-4-n-octoxybenzophenone；
0.15 part of tributyl phosphate.
Production method：Pretreatment reaction is carried out to obtained lignin first, modified lignin is made, then according to
Square ratio adds flour, silane coupler, tert-butylhydroquinone, 2- hydroxyl -4- n-octyloxy hexichol in stirred autoclave
Ketone and defoamer, are well mixed, then are ground 2 hours with three-roll grinder, and it is 0.50Pas's to obtain viscosity at 18-20 DEG C
Adhesive.
Modified lignin is made by the following method：
（1）It is prepared by lignin：By adding 50wt% in the black liquor to the alkaline boiling method slurrying using bagasse as raw material
Sulfuric acid, adjusts black liquor pH4, places untill insoluble matter all precipitation, standing time is 72h, then by sediment and sediment
Material separation in addition, obtained drying precipitate；Processing is further purified to obtained sediment：In sediment again
Add water 50wt% sulfuric acid, adjusts pH1, is dried after washing, repeats the processing procedure 4 times, and 85.1wt% high-purity can be made
Lignin product, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulfuric acid is added in obtained lignin, after stirring, 150 DEG C are warming up to, sulfonation is anti-
Answer 2 hours；By evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, control discharging moisture be
30wt%, precipitation is 15wt% through filtering, drying to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control temperature
90 DEG C of degree, insulation reaction 1 hour finally produces modified lignin with 30wt% sodium hydroxides regulation pH to 6.8.
The lignin weatherability fiberboard adhesive factory formula of embodiment 4 and method 3
Formula composition：
28 parts of lignin；
28 parts of phenol；
9 parts of farina；
9 parts of flour；
2 parts of methyl vinyl diethoxysilane；
1 part of mercapto hydroxypropyl methyl dimethoxysilane；
1 part of mercaptopropyl trimethoxysilane；
4 parts of vitamin E；
2-（2 ˊ-the ˊ of hydroxyl-5-aminomethyl phenyl）2 parts of BTA；
3 parts of 2,4-DihydroxyBenzophenone；
0.07 part of dimethyl silicone polymer；
0.09 part of tributyl phosphate.
Production method：Pretreatment reaction is carried out to obtained lignin first, modified lignin is made, then according to by
Formula rate adds farina, flour, silane coupler, vitamin E, 2- in stirred autoclave（2 ˊ-the ˊ of hydroxyl-5-first
Base phenyl）BTA, 2,4-DihydroxyBenzophenone and defoamer, are well mixed, then small with three-roll grinder grinding 2
When, obtain the adhesive that viscosity at 18-20 DEG C is 0.30Pas.
Modified lignin is made by the following method：
（1）It is prepared by lignin：By adding 50wt% in the black liquor to the alkaline boiling method slurrying using bagasse as raw material
Sulfuric acid, adjusts black liquor pH4, places untill insoluble matter all precipitation, standing time is 72h, then by sediment and sediment
Material separation in addition, obtained drying precipitate；Processing is further purified to obtained sediment：In sediment again
Add water 50wt% sulfuric acid, adjusts pH1, is dried after washing, repeats the processing procedure 6 times, and 88.5wt% high-purity can be made
Lignin product, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulfuric acid is added in obtained lignin, after stirring, 160 DEG C are warming up to, sulfonation is anti-
Answer 2 hours；By evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, control discharging moisture be
30wt%, precipitation is 15wt% through filtering, drying to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control temperature
90 DEG C of degree, insulation reaction 1 hour finally produces modified lignin with 30wt% sodium hydroxides regulation pH to 6.8.
Embodiment 5
The measure of the residual quantity of formaldehyde is carried out to the lignin weatherability fiberboard adhesive obtained by embodiment 1-4, it is resistance to
High temperature test, and detect bonding strength according to the regulation in GB/T9846.1- 9846.8-2004.Formaldehyde determination uses levulinic
Ketone AAS, residual formaldehyde %=measured value/example weight × %, 25mm）, detect and dig according to GB/T4897.7-2003
Card 24h thickness swelling rates, it is as a result as shown in the table：As a result it is as shown in the table：
As seen from the above table, lignin weatherability fiberboard adhesive residues of formaldehyde of the invention be 0, using safety coefficient compared with
Lauxite is high, while bonding strength is also more excellent relative to Lauxite；Meanwhile, lignin weatherability fiberboard of the invention
The required equipment of adhesive is simple, and processing technology is easy to operate, easily realizes.It can be seen that, lignin adhesive of the invention not only has
Bonding strength is high, using it is safe the advantages of, also moderate with shear strength, viscosity is handling strong, and the characteristics of weatherability is strong has
Great promotional value.
Claims (1)
1. the production method of lignin weatherability fiberboard adhesive, it is characterised in that：Adhesive by following parts by weight original
Material is made：
20-30 parts of lignin；
20-30 parts of phenol；
15-20 parts of starch；
1-5 parts of silane coupler；
1-5 parts of antioxidant；
3-5 parts of ultra-violet absorber；
0.1-0.2 parts of defoamer；
The starch is one kind or its composition in tapioca, farina, flour；
The silane coupler is VTES, three tert-butoxy vinyl silanes, anilinomethyl triethoxy
Silane, γ-r-chloropropyl trimethoxyl silane, γ-methyl allyl acyloxypropyl trimethoxysilane, 3-（2,3 the third oxygen of epoxy）
Propyl trimethoxy silicane, mercaptopropyl trimethoxysilane, methyl vinyl diethoxysilane and mercapto hydroxypropyl methyl dimethoxy
One kind or its composition in base silane；
The antioxidant is in dibutyl hydroxy toluene, butylated hydroxy anisole, vitamin E and tert-butylhydroquinone
One kind or its composition；
The ultra-violet absorber is septichen phenyl ester, 2-（2 ˊ-the ˊ of hydroxyl-5-aminomethyl phenyl）BTA,
One kind or its composition of 2,4-DihydroxyBenzophenone and 2- hydroxyl -4- oxy-octyl benzophenones；
The production method of described lignin weatherability fiberboard adhesive：Pretreatment reaction is carried out to lignin first, is made
Modified lignin, then adds starch, antioxidant, ultra-violet absorber, silicon according to formula rate in stirred autoclave
Alkane coupling agent and defoamer, are well mixed, then are ground 1-2 hours with three-roll grinder, and obtaining viscosity at 18-20 DEG C is
0.20-0.50Pas adhesive；
The defoamer is dimethyl silicone polymer or tributyl phosphate；
The modified lignin is made by the following method：
（1）It is prepared by lignin：Acid is added in the black liquor of the alkaline boiling method slurrying using bagasse as raw material, is made it have
Below pH6 acidity, places untill insoluble matter all precipitation, then separates the material beyond sediment and sediment,
Obtained drying precipitate, is made high-purity lignin product；
（2）In step（1）70wt% sulfuric acid is added in obtained lignin, after stirring, 140-160 DEG C is warming up to,
Sulfonating reaction 1-2 hours；By evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, control discharging water
It is 30wt% to divide content, and precipitation is 15wt% through filtering, drying to water content；By lignin:Phenol weight ratio is 1:1 adds benzene
Phenol, controls 85-95 DEG C of temperature, and insulation reaction 1 hour finally produces lignin with 30wt% sodium hydroxides regulation pH to 6.5-7.0
Modifier.
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