CN104357009B - Lignin flame-retardant fiber board adhesive and production method thereof - Google Patents
Lignin flame-retardant fiber board adhesive and production method thereof Download PDFInfo
- Publication number
- CN104357009B CN104357009B CN201410634459.7A CN201410634459A CN104357009B CN 104357009 B CN104357009 B CN 104357009B CN 201410634459 A CN201410634459 A CN 201410634459A CN 104357009 B CN104357009 B CN 104357009B
- Authority
- CN
- China
- Prior art keywords
- lignin
- parts
- adhesive
- flame
- production method
- 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
- 229920005610 lignin Polymers 0.000 title claims abstract description 108
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 62
- 239000000853 adhesive Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000003063 flame retardant Substances 0.000 title claims abstract description 19
- 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 abstract description 11
- 239000011094 fiberboard Substances 0.000 title abstract 4
- 239000002994 raw material Substances 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 34
- 239000002244 precipitate Substances 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000001117 sulphuric acid Substances 0.000 claims description 15
- 235000011149 sulphuric acid Nutrition 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000013530 defoamer Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 8
- 241000609240 Ambelania acida Species 0.000 claims description 7
- 239000010905 bagasse Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- -1 polydimethylsiloxane Polymers 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy 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
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 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
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 2
- 239000002518 antifoaming agent Substances 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 81
- 235000019256 formaldehyde Nutrition 0.000 description 27
- 229960004279 formaldehyde Drugs 0.000 description 26
- 238000012545 processing Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 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
- 239000000203 mixture Substances 0.000 description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229920000388 Polyphosphate Polymers 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
- 235000013877 carbamide Nutrition 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 238000004026 adhesive bonding Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-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
- 239000004254 Ammonium phosphate Substances 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
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes 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
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 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
- 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
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction 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
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- MGCQZNBCJBRZDT-UHFFFAOYSA-N midodrine hydrochloride Chemical compound [H+].[Cl-].COC1=CC=C(OC)C(C(O)CNC(=O)CN)=C1 MGCQZNBCJBRZDT-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 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
- 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
- 238000000746 purification Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 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
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a lignin flame-retardant fiber board adhesive and a production method thereof. The lignin flame-retardant fiber board adhesive is prepared from the following raw materials in parts by weight: 20-30 parts of lignin, 20-30 parts of phenol, 15-20 parts of starch, 1-5 parts of silane coupling agent, 8-10 parts of flame retardant and 0.1-0.2 part of defoaming agent. The production method comprises the following steps: carrying out pretreatment reaction on the lignin to obtain a lignin modification product, adding the starch, flame retardant, silane coupling agent and defoaming agent into the stirring reaction kettle according to the formula proportion, uniformly mixing, and grinding for 1-2 hours with a three-roller grinder to obtain the adhesive of which the viscosity is 0.15-0.60 Pa.s at 18-20 DEG C. The lignin flame-retardant fiber board adhesive has the advantages of excellent flame-retardant effect, low cost and favorable adhesive effect, and is suitable for wide-range popularization and application.
Description
Technical field
The present invention relates to adhesive field, particularly a kind of lignin flame redardant fibre board adhesive and its production method.
Background technology
Fibre board is by the molding of lignin fibre intertexture and using its wood-based plate made by intrinsic gluing performance.Fibre board is most
Conventional adhesive is Lauxite or modified urea-formaldehyde resin.Lauxite simple production process, low cost, but resistance to water and strong
Degree is relatively low, through tripolycyanamide, phenol or resorcinol, acrylate copolymer, isocyanates, polyvinyl alcohol or lignin etc.
Modified Lauxite significantly improves resistance to water and adhesion strength.One of raw materials for production of Lauxite or modified urea-formaldehyde resin
Formaldehyde, therefore, using Lauxite or modified urea-formaldehyde resin as adhesive wood-based plate inevitable release formaldehyde.
Formaldehyde is the stealthy killer of health, and indoor concentration of formaldehyde is more than 0.5mg/m, and people stays 5 hours in such environment, will feel
To dizziness.Concentration of formaldehyde is in for a long time more than 0.5mg/m, will be carcinogenic, therefore burst size of methanal is that restriction industry of artificial boards is sent out
One key factor of exhibition.
Guangxi Nanning Green Park Beilin Wood Industry Co., Ltd. has been carried out for low residual formaldehyde urea-formaldehyde resin adhesive in a large number
Research, and applied for Patents, the patent of application publication number CN103450432A：A kind of low residual formaldehyde Lauxite
Production method, its primary raw material are formaldehyde and carbamide, and disposably to feed intake, carbamide feeds intake formaldehyde in three times；The life of Lauxite
Product 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 are low.Application publication number is
The patent of CN103450832A：A kind of glutinous agent of modified urea-formaldehyde resin glue of low residual formaldehyde and its production method, by using
Modified urea-formaldehyde resin, reinforcing agent and defoamer be primary raw material, made by adhesive residual formaldehyde ＜ 0.1mg/L, 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 are formaldehyde, carbamide
And polyvinyl alcohol, the low adhesive of residual formaldehyde is gone out by prepolymerization, polymerization and later stage polymerization three phases final production.To the greatest extent
Pipe is thus, as formaldehyde is one of main raw materials for production, with the inevitable release formaldehyde of wood-based plate made by Lauxite, use up
It is low that Gutron crosses above technical controlling residual formaldehyde, but still has room for improvement.Meanwhile, Lauxite due to industrialization degree compared with
Height, production technology are more ripe, and cost is difficult to reduce, and cause 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, is distributed widely in and has
In higher plant more than fascicular pteridophyte plant, it is that a class is connected by ehter bond and carbon-carbon bond by benzene oxide unit
Unformed high polymer, lignin have wide variety of potential quality, first lignin itself in adhesive due to its molecular characterization
With caking property, adhesive can be directly used as.Authorize Publication No.：The patent of CN100381534C：A kind of lignin environmental protection
Type binding agent and preparation method thereof, obtains lignin binding agent by the method washed lignin, prepare lignin liquor, though it is main
Raw material is wanted for lignin, but still with formaldehyde as one of raw material, made by adhesive still have a small amount of Form aldehyde release；Application publication number
For the invention of CN101928536A：A kind of flame retardant modified lignin resin glue and preparation method thereof, is obtained by following components raw material：It is dense
Formalin 20-30wt% for 30-50% is spent, the aldehydes matter 8-12wt% containing three-functionality-degree is balance of with draft lignin to be
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 the glutinous agent of melamine-formaldehyde resin adhesive, but same presence
The free problem of formaldehyde.Inventor is studied to anti-flammability adhesive on this basis, for low residues of formaldehyde, fire retardancy
The development of strong type fibre board or other wood-based plates is had laid a good foundation.
The content of the invention
The purpose of the present invention is supplied for above technology, there is provided a kind of lignin flame redardant fibre board adhesive and its production
Method, solves current fibre board adhesive and has residues of formaldehyde harm environment, and lignin is that adhesive made by main material is same
Problem containing formaldehyde, a kind of adhesion strength of exploitation is high, adhesive speed is fast, the fibre board adhesive of good flame resistance.
Technical scheme is as follows：
Lignin flame redardant fibre board adhesive, is made up of the raw material of following parts by weight：
Lignin 20-30 parts；
Phenol 20-30 parts；
Starch 15-20 parts；
Silane coupler 1-5 parts；
Fire retardant 5-10 parts；
0.1～0.2 part of defoamer.
The starch is tapioca, potato starch, the one kind in flour or combinations thereof.
The silane coupler is VTES, three tert-butoxy vinyl silanes, three second of anilinomethyl
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 combinations thereof in TMOS.Inventor find the present invention develop lignin flame redardant fibre board adhesive with compared with
Good wettability, it is relatively low relative to traditional Lauxite, phenolic resin or its modifier adhesive surface tension, and add and send out
Bright described silane coupler, can more preferably effectively improve the adhesive property of lignin adhesive of the present invention.This is because：Silane
Both contained organic group in the molecular structure of coupling agent, contained inorganic structure again, this special molecular structure make its with
The characteristic and function of machine thing and inorganic matters, using silane coupler combined with lignin adhesive it is rear with excellent resistance to water,
Thermostability, weatherability, chemical-resistant and low surface tension, this is possibly due to one end siloxanes hydrolysis life in silane coupler
Into silanol can react to form chemical bond with the hydroxyl on adherend and filler surface or oxide, organic active functional group and glue
Glutinous agent reaction also forms chemical bond, and the sub- intermolecular forces of chemical bond energy score want the high 1-2 order of magnitude；Meanwhile, silane coupler
The other end is connected with the active group after lignin modification, forms preferable chemical affinity, two ends bridging, as erected
Bridge, plays irreversible cementation after solidification, obtain naturally the bond effect of high intensity.
The fire retardant is APP, magnesium hydroxide, aluminium hydroxide, triphenyl phosphate, melamine cyanurate,
Melamine polyphosphate, Firebrake ZB, red phosphorus, one kind of antimony oxide or combinations thereof.
The defoamer is polydimethylsiloxane or tributyl phosphate.
The production method of lignin flame redardant fibre board adhesive, carries out pretreatment reaction to lignin first, is obtained wooden
Plain modifier, then according to pressing formula proportion adds starch, fire retardant, silane coupler and defoamer in stirred autoclave,
Mix homogeneously, then 1-2 hours are ground with three-roll grinder, adhesive of the viscosity for 0.15-0.60Pas at obtaining 18-20 DEG C.
The modified lignin is obtained by the following method：
（1）It is prepared by lignin：By adding acid in the black liquor to the alkaline boiling method slurrying with bagasse as raw material, examine
Consider the overall merits such as cost, production ease for operation, sulphuric acid, hydrochloric acid, carbon dioxide and aluminum sulfate are selected to add acid, adjust black liquor
PH to less than 6, preferably in pH1-4, place to insoluble matter all precipitating, standing time is 24-72h, then will precipitation
Thing is separated with the material beyond precipitate, and separation can be carried out by routine filtration device or Suction filtration device, the precipitate for obtaining
It is dried, obtains the lignin product that purity is 50-80wt%；To obtain the lignin of higher purity, the precipitate to obtaining make into
One step purification process, concrete technology is：Add water in precipitate acid adding again, adjusts pH1-4, is dried after washing, repeats at this
Reason process more than 2 times, can make more than 80wt% high-purity lignin products, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulphuric acid is added in the lignin for obtaining, after stirring, 140-160 DEG C is warming up to, sulphur
Change reaction 1-2 hours；Through evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, control discharging moisture
For 30wt%, precipitation, it is 15wt% that Jing is filtered, is dried to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control
Temperature 85-95 DEG C, insulation reaction 1 hour finally adjust pH with 30wt% sodium hydroxide and obtain final product modified lignin to 6.5-7.0.
Step（2）Sulfonation modifying is carried out to lignin first in reaction, phenolate is then carried out and is modified, final obtained modified lignin is lived
Property group it is many, organic active is high, is combined the function of being more beneficial for performance adhesive with silane coupler.
Beneficial effects of the present invention are：
First, the problem containing formaldehyde in traditional fibre plate adhesive, the lignin flame redardant fiber that the present invention is developed are changed
Plate adhesive is primary raw material using lignin, through a series of modified, is combined with fire retardant, silane coupler,
The gluing performance of adhesive can be significantly improved, the lignin adhesive has viscosity low, low to adherend surface tension, easily
Moistening, the advantages of adhesion strength is big；This is because the active group after lignin modification is easy to silane coupler formed together
Chemical interactions, and the other end combines to form chemical bond with adherend surface, is much stronger than 1-2 quantity of intermolecular force
Level, and has the advantages that waterproof, high temperature resistant, makes adhesive and fibre board formation " bridge " structure, reach be tightly combined, firmly,
Irreversible as closely linked as flesh and blood bond effect.
2nd, fire retardancy is strong.The lignin adhesive skeleton of the present invention is modified lignin, and by rationally addition resistance
Combustion agent composition and ratio so that the lignin adhesive of the present invention has outstanding fire resistance, lignin skeleton, active group
, on the basis of adhesive performance is given full play to, fire resistance is higher, is suitable for for group, silane coupler and effectively cooperation fire retardant
The preparation of Flame retardant staple's plate.
3rd, the lignin flame redardant fibre board adhesive viscosity scope of application that the present invention is developed is big, from 0.15～0.60Pas
Good using effect can be played, is suitable for the bonding demand of various different demands fibre boardes.
4th, low production cost, easily realizes.The lignin adhesive of the present invention is using the alkaline boiling method with bagasse as raw material
The high-load lignin that the black liquor Jing process of slurrying is obtained, belongs to refuse reclamation, reduces the cost of raw material, while
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.
Specific embodiment
1 lignin flame redardant fibre board adhesive factory formula of embodiment and method 1
Formula is constituted：
25 parts of lignin；
25 parts of phenol；
15 parts of tapioca；
0.5 part of VTES；
0.5 part of anilinomethyl triethoxysilane；
5 parts of APP；
0.1 part of polydimethylsiloxane.
Production method：Lignin first to obtaining carries out pretreatment reaction, modified lignin is obtained, then according to matching somebody with somebody
Square ratio adds tapioca, VTES and anilinomethyl triethoxysilane in stirred autoclave, gathers
Ammonium phosphate and defoamer, mix homogeneously, then ground 1 hour with three-roll grinder, at obtaining 18-20 DEG C, viscosity is 0.15Pas
Adhesive
Modified lignin is obtained by the following method：
（1）It is prepared by lignin：By adding 50wt% in the black liquor to the alkaline boiling method slurrying with bagasse as raw material
Sulphuric acid, adjusts black liquor pH6, places to insoluble matter all precipitating, and standing time is 72h, then by precipitate and precipitate
Material in addition is separated, the drying precipitate for obtaining；Precipitate to obtaining is further purified process：In precipitate again
Add water 50wt% sulphuric acid, adjusts pH2, is dried after washing, repeats the processing procedure 3 times, can make the high-purity of 83.5wt%
Lignin product, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulphuric acid is added in the lignin for obtaining, after stirring, 140 DEG C is warming up to, sulfonation is anti-
Answer 1 hour；Through evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/, controls discharging moisture and is
30wt%, precipitation, it is 15wt% that Jing is filtered, is dried to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control temperature
85 DEG C of degree, insulation reaction 1 hour finally adjust pH with 30% sodium hydroxide and obtain final product modified lignin to 6.8.
2 lignin flame redardant fibre board adhesive factory formula of embodiment and method 2
Formula is constituted：
20 parts of lignin；
20 parts of phenol；
18 parts of potato starch；
1 part of anilinomethyl triethoxysilane
1 part of γ-r-chloropropyl trimethoxyl silane；
10 parts of magnesium hydroxide；
0.1 part of tributyl phosphate
Production method：Lignin first to obtaining carries out pretreatment reaction, modified lignin is obtained, then according to matching somebody with somebody
Square ratio adds potato starch, anilinomethyl triethoxysilane and γ-r-chloropropyl trimethoxyl silicon in stirred autoclave
Alkane, magnesium hydroxide and defoamer, mix homogeneously, then ground 1 hour with three-roll grinder, at obtaining 18-20 DEG C, viscosity is
The adhesive of 0.35Pas.
Modified lignin is obtained by the following method：
（1）It is prepared by lignin：By adding 50wt% in the black liquor to the alkaline boiling method slurrying with bagasse as raw material
Sulphuric acid, adjusts black liquor pH5, places to insoluble matter all precipitating, and standing time is 48h, then by precipitate and precipitate
Material in addition is separated, the drying precipitate for obtaining；Precipitate to obtaining is further purified process：In precipitate again
Add water 50wt% sulphuric acid, adjusts pH2.5, is dried after washing, repeats the processing procedure 5 times, can make the high-purity of 87.1wt%
Degree lignin product, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulphuric acid is added in the lignin for obtaining, after stirring, 150 DEG C is warming up to, sulfonation is anti-
Answer 1.5 hours；Through evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, controls discharging moisture and is
30wt%, precipitation, it is 15wt% that Jing is filtered, is dried to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control temperature
85 DEG C of degree, insulation reaction 1 hour finally adjust pH with 30wt% sodium hydroxide and obtain final product modified lignin to 6.7.
3 lignin flame redardant fibre board adhesive factory formula of embodiment and method 3
Formula is constituted：
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；
3 parts of triphenyl phosphate；
4 parts of melamine cyanurate；
0.18 part of polydimethylsiloxane.
Production method：Lignin first to obtaining carries out pretreatment reaction, modified lignin is obtained, then according to pressing
Formula proportion add in stirred autoclave flour, gamma-methyl allyl acyloxypropyl trimethoxysilane and 3-（2,3 epoxies third
Oxygen）Propyl trimethoxy silicane, mercaptopropyl trimethoxysilane, melamine cyanurate, triphenyl phosphate and defoamer, mix
Close uniform, then ground 2 hours with three-roll grinder, adhesive of the viscosity for 0.50Pas at obtaining 18-20 DEG C.
Modified lignin is obtained by the following method：
（1）It is prepared by lignin：By adding 50wt% in the black liquor to the alkaline boiling method slurrying with bagasse as raw material
Sulphuric acid, adjusts black liquor pH4, places to insoluble matter all precipitating, and standing time is 72h, then by precipitate and precipitate
Material in addition is separated, the drying precipitate for obtaining；Precipitate to obtaining is further purified process：In precipitate again
Add water 50wt% sulphuric acid, adjusts pH1, is dried after washing, repeats the processing procedure 4 times, can make the high-purity of 85.1wt%
Lignin product, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulphuric acid is added in the lignin for obtaining, after stirring, 150 DEG C is warming up to, sulfonation is anti-
Answer 2 hours；Through evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, controls discharging moisture and is
30wt%, precipitation, it is 15wt% that Jing is filtered, is dried to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control temperature
90 DEG C of degree, insulation reaction 1 hour finally adjust pH with 30wt% sodium hydroxide and obtain final product modified lignin to 6.8.
4 lignin flame redardant fibre board adhesive factory formula of embodiment and method 3
Formula is constituted：
28 parts of lignin；
28 parts of phenol；
20 parts of potato starch；
1 part of methyl vinyl diethoxysilane；
2 parts of mercapto hydroxypropyl methyl dimethoxysilane；
1 part of mercaptopropyl trimethoxysilane；
4 parts of melamine polyphosphate；
5 parts of Firebrake ZB；
0.15 part of tributyl phosphate.
Production method：Lignin first to obtaining carries out pretreatment reaction, modified lignin is obtained, then according to pressing
Formula proportion adds potato starch, methyl vinyl diethoxysilane and mercapto hydroxypropyl methyl dimethoxy in stirred autoclave
Base silane, mercaptopropyl trimethoxysilane, melamine polyphosphate, Firebrake ZB and defoamer, mix homogeneously, then ground with three rollers
Grinding machine grinds 2 hours, adhesive of the viscosity for 0.60Pas at obtaining 18-20 DEG C.
Modified lignin is obtained by the following method：
（1）It is prepared by lignin：By adding 50wt% in the black liquor to the alkaline boiling method slurrying with bagasse as raw material
Sulphuric acid, adjusts black liquor pH4, places to insoluble matter all precipitating, and standing time is 72h, then by precipitate and precipitate
Material in addition is separated, the drying precipitate for obtaining；Precipitate to obtaining is further purified process：In precipitate again
Add water 50wt% sulphuric acid, adjusts pH1, is dried after washing, repeats the processing procedure 6 times, can make the high-purity of 88.5wt%
Lignin product, subsequently into subsequent production processing procedure.
（2）In step（1）70wt% sulphuric acid is added in the lignin for obtaining, after stirring, 160 DEG C is warming up to, sulfonation is anti-
Answer 2 hours；Through evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, controls discharging moisture and is
30wt%, precipitation, it is 15wt% that Jing is filtered, is dried to water content；By lignin：Phenol 1:1（Weight ratio）Add phenol, control temperature
90 DEG C of degree, insulation reaction 1 hour finally adjust pH with 30wt% sodium hydroxide and obtain final product modified lignin to 6.8.
Embodiment 5
The measure of the residual quantity of formaldehyde is carried out to the lignin flame redardant fibre board adhesive obtained by embodiment 1-4, and is pressed
According to the regulation detection bonding strength in GB/T9846.1- 9846.8-2004.Formaldehyde determination adopts acetylacetone,2,4-pentanedione spectrophotography,
Residual formaldehyde %=measured value/example weight × %, and its flame retardant effect is tested, it is as a result as shown in the table：
As seen from the above table, the lignin flame redardant fibre board adhesive residues of formaldehyde that the present invention is developed is 0, using safety coefficient
It is high compared with Lauxite, while bonding strength is also more excellent relative to Lauxite, this is because silane coupler is played wherein
Important function.Fire resistance test shows：The lignin adhesive oxygen index (OI) ﹥ 30 of the present invention, while energy self-extinguishment, and do not produce
Raw cigarette, possesses preferable fire resistance.It can be seen that, the lignin adhesive of the present invention not only has bonding strength height, uses safety
The advantages of, and flame-retardant adhesive can be reached use standard.
Claims (1)
1. the production method of lignin flame redardant fibre board adhesive, it is characterised in that：Raw material group of the raw material by following parts by weight
Into：
Lignin 20-30 parts；
Phenol 20-30 parts；
Starch 15-20 parts；
Silane coupler 1-5 parts；
Fire retardant 5-10 parts；
0.1～0.2 part of defoamer；
The starch is tapioca, potato starch, the one kind in flour or combinations thereof；
The silane coupler is VTES, three tert-butoxy vinyl silanes, anilinomethyl triethoxy
Silane, γ-r-chloropropyl trimethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, 3-（2,3 the third oxygen of epoxy）Third
Base trimethoxy silane, mercaptopropyl trimethoxysilane, methyl vinyl diethoxysilane and mercapto hydroxypropyl methyl dimethoxy
One kind or combinations thereof in silane；
The fire retardant is APP, magnesium hydroxide, aluminium hydroxide, triphenyl phosphate, melamine cyanurate, melamine
Amine Quadrafos, Firebrake ZB, red phosphorus, one kind of antimony oxide or combinations thereof；
Described production method is to carry out pretreatment reaction to lignin first, modified lignin is obtained, then according to formula
Ratio adds starch, fire retardant, silane coupler and defoamer, mix homogeneously in stirred autoclave, then uses three-roll grinder
Grinding 1-2 hours, at obtaining 18-20 DEG C, viscosity is the adhesive of 0.15～0.60Pas；
The defoamer is polydimethylsiloxane or tributyl phosphate；
The modified lignin is obtained by the following method：
（1）It is prepared by lignin：Add acid in the black liquor of the alkaline boiling method slurrying with bagasse as raw material so as to have
The acidity of below pH6, places to insoluble matter all precipitating, then precipitate is separated with the material beyond precipitate, is obtained
The drying precipitate for arriving, makes high-purity lignin product；
（2）In step（1）70wt% sulphuric acid is added in the lignin for obtaining, after stirring, 140-160 DEG C is warming up to, sulfonation is anti-
Answer 1-2 hours；Through evaporator with central downcomer, circulation rate is 0.4m/s-0.5m/s, controls discharging moisture and is
30wt%, precipitation, it is 15wt% that Jing is filtered, is dried to water content；By lignin：Phenol weight is frequently 1:1 adds phenol, control
Temperature 85-95 DEG C, insulation reaction 1 hour finally adjust pH with 30wt% sodium hydroxide and obtain final product modified lignin to 6.5-7.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410634459.7A CN104357009B (en) | 2014-11-12 | 2014-11-12 | Lignin flame-retardant fiber board adhesive and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410634459.7A CN104357009B (en) | 2014-11-12 | 2014-11-12 | Lignin flame-retardant fiber board adhesive and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104357009A CN104357009A (en) | 2015-02-18 |
| CN104357009B true CN104357009B (en) | 2017-04-12 |
Family
ID=52524328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410634459.7A Active CN104357009B (en) | 2014-11-12 | 2014-11-12 | Lignin flame-retardant fiber board adhesive and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104357009B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106346584A (en) * | 2016-08-29 | 2017-01-25 | 南宁市林润木业有限公司 | Method for producing full-eucalyptus parquet with flame-retardant composite urea-formaldehyde resin |
| CN106313259B (en) * | 2016-08-29 | 2019-01-15 | 广西横县新威林板业有限公司 | Using the method for fire-retardant composite urea formaldehyde resin production particieboard |
| CN106182316A (en) * | 2016-08-29 | 2016-12-07 | 广西横县新威林板业有限公司 | The method that full Eucalyptus leftover pieces produce fire-retardant oriented wood chipboard |
| CN106346568A (en) * | 2016-08-29 | 2017-01-25 | 南宁市创锦胶合板有限责任公司 | Method for producing full-eucalyptus plywood with flame-retardant composite urea-formaldehyde resin |
| CN106363760B (en) * | 2016-08-29 | 2018-10-09 | 广西横县新威林板业有限公司 | The method that particieboard is produced using Vermins-proof mildew-proof composite urea formaldehyde resin |
| CN108060616A (en) * | 2017-12-28 | 2018-05-22 | 常德金德新材料科技股份有限公司 | High-barrier coating paper prepared by a kind of biological adhesive by lignin modification |
| CN114000215B (en) * | 2021-12-17 | 2023-10-17 | 广东华凯科技股份有限公司 | Antibacterial flame-retardant chopped polypropylene fiber composite material and preparation method thereof |
| CN115287038B (en) * | 2022-07-07 | 2023-07-14 | 浙江升华云峰新材股份有限公司 | Modified layered silicate-based formaldehyde-free flame-retardant adhesive and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6747076B2 (en) * | 2001-02-27 | 2004-06-08 | The University Of New Brunswick | Furfuryl alcohol and lignin adhesive composition |
| CN103360984A (en) * | 2012-03-26 | 2013-10-23 | 李林刚 | Preparation method of corn starch adhesive through cannabis degummed waste liquor |
-
2014
- 2014-11-12 CN CN201410634459.7A patent/CN104357009B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6747076B2 (en) * | 2001-02-27 | 2004-06-08 | The University Of New Brunswick | Furfuryl alcohol and lignin adhesive composition |
| CN103360984A (en) * | 2012-03-26 | 2013-10-23 | 李林刚 | Preparation method of corn starch adhesive through cannabis degummed waste liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104357009A (en) | 2015-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104357009B (en) | Lignin flame-retardant fiber board adhesive and production method thereof | |
| CN104312535B (en) | Lignin weatherability fiberboard adhesive and its production method | |
| Zhao et al. | State of research and trends in development of wood adhesives | |
| CN106883366B (en) | A kind of E0Grade cyanurotriamide modified urea resin adhesive | |
| CN104762045A (en) | Production method of modified urea resin adhesive | |
| CN102086367A (en) | Plate alignment adhesive for surface plate lamination of engineered wood flooring and preparation method thereof | |
| CN106349987B (en) | Special modified phenolic resin adhesive for bamboo floor and preparation method thereof | |
| CN112662135A (en) | Epoxy resin insulating board and preparation method thereof | |
| CN104017519A (en) | Binding agent for plywood and preparation method thereof | |
| CN104293287A (en) | Lignin damp-proof fiberboard adhesive and producing method thereof | |
| CN108690541A (en) | A kind of outdoor version fibre board use modified urea-formaldehyde resin adhesive and preparation method thereof | |
| CN105461874A (en) | Method for preparing modified composite adhesive | |
| CN103804619B (en) | Xylogen-phenol-urea-formaldehyde condensation copolymerization resin tackiness agent and preparation method | |
| CN108587057A (en) | A kind of daylighting weather-resistant composite, plane skylight and preparation method thereof | |
| CN107778767A (en) | A kind of preparation method of lignin phenol formaldehyde resin foamed material | |
| CN104388044A (en) | High-adhesive-strength lignin fiberboard adhesive and production method thereof | |
| CN105131223A (en) | Melamine modified resin adhesive for flax chip shaving boards, and preparation method thereof | |
| CN102585129B (en) | Urea-formaldehyde resin for artificial board and modification modulation method thereof | |
| CN106752003A (en) | Modified waterproof flame-retardant type biomass board of the compound woodcare paint enhancing of a kind of nano silicon/polyurethane and preparation method thereof | |
| CN104628977A (en) | Preparation method of tripolycyanamide-carbamide-formaldehyde resin adhesive | |
| CN104293288A (en) | Lignin thermostable fiberboard adhesive and producing method thereof | |
| CN116376485A (en) | Environment-friendly flame-retardant adhesive, preparation method thereof and application thereof in plywood | |
| CN106752004A (en) | A kind of waterproof flame-retardant type biomass board of multi-walled carbon nano-tubes activeness and quietness and preparation method thereof | |
| CN102391408B (en) | Synthesis method for preparing polyvinyl acetate/alpha-pinene copolymer emulsion by modifying nano attapulgite | |
| CN102850497B (en) | Method for preparing urea-formaldehyde resin adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 530300 the Guangxi Zhuang Autonomous Region Nanning Hengxian City Heng Zhou Zhen Cha Jiang Road No. 121 Patentee after: Guangxi Nanning Luyuan Beilin Wood Industry Co., Ltd. Address before: 530104 the Guangxi Zhuang Autonomous Region Nanning Yilin Industrial Zone Chengnan Industrial Park No. B-56 (Pinglu bridge) Patentee before: Guangxi Nanning Luyuan Beilin Wood Industry Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201009 Address after: 530300 the Guangxi Zhuang Autonomous Region Nanning Hengxian City Heng Zhou Zhen Cha Jiang Road No. 121 Patentee after: Mo Mingxin Address before: 530300 the Guangxi Zhuang Autonomous Region Nanning Hengxian City Heng Zhou Zhen Cha Jiang Road No. 121 Patentee before: GUANGXI NANNING LVYUAN BEILIN WOOD INDUSTRY Co.,Ltd. |