CN104388044A - High-adhesive-strength lignin fiberboard adhesive and production method thereof - Google Patents
High-adhesive-strength lignin fiberboard adhesive and production method thereof Download PDFInfo
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- CN104388044A CN104388044A CN201410633187.9A CN201410633187A CN104388044A CN 104388044 A CN104388044 A CN 104388044A CN 201410633187 A CN201410633187 A CN 201410633187A CN 104388044 A CN104388044 A CN 104388044A
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Abstract
The invention discloses a high-adhesive-strength lignin fiberboard adhesive and a production method thereof. The 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 a silane coupling agent and 0.1-0.2 part of a defoaming agent. The production method comprises the following steps: pretreating the lignin to prepare a modified lignin product; subsequently adding the starch, the silane coupling agent and the defoaming agent into a stirring reaction kettle according to the proportion in formula, uniformly mixing and then grinding for 1-2 hours by using a three-roller grinder to obtain the adhesive of which the viscosity is 0.15-0.60Pa*s at the temperature of 18-20 DEG C. The lignin fiberboard adhesive disclosed by the invention is excellent in adhesion effect, low in cost, good in adhesion effect and applicable to large-scale popularization and application.
Description
Technical field
The present invention relates to sizing agent field, particularly a kind of lignin fibre plate sizing agent and production method thereof with high bond strength.
Background technology
Fiberboard interweaves shaping by lignin fibre and utilizes the wood-based plate that its intrinsic gluing performance is made.The most frequently used sizing agent of fiberboard is urea-formaldehyde resin or modified urea-formaldehyde resin.Urea-formaldehyde resin production technique is simple, cost is low, but water tolerance and intensity lower, significantly improve water tolerance and cohesive strength through modified urea-formaldehyde resins such as trimeric cyanamide, phenol or Resorcinol, acrylate copolymer, isocyanic ester, polyvinyl alcohol or xylogen.One of raw materials for production of urea-formaldehyde resin or modified urea-formaldehyde resin are formaldehyde, therefore, adopt urea-formaldehyde resin or modified urea-formaldehyde resin as the wood-based plate all inevitably release formaldehyde of sizing agent.Formaldehyde is healthy stealthy killer, and indoor concentration of formaldehyde is greater than 0.5mg/m3, and people stays 5 hours at such environment, will feel dizzy.Be in concentration of formaldehyde for a long time and be greater than 0.5mg/m3, will be carcinogenic, therefore burst size of methanal is an important factor of restriction industry of artificial boards development.
Guangxi Nanning Green Park Beilin Wood Industry Co., Ltd. has carried out large quantity research for low residual formaldehyde urea-formaldehyde resin adhesive, and applied for Patents, the patent of application publication number CN103450432A: a kind of production method of low residual formaldehyde urea-formaldehyde resin, its main raw material is formaldehyde and urea, formaldehyde is disposable feeding intake, and urea divides and feeds intake for three times; The production of urea-formaldehyde resin is divided into prepolymerization, polymerization and later stage polymerization three phases, and by controlling each stage charging capacity and temperature of reaction, avoid the generation of polymerization process embedding phenomenon, the urea-formaldehyde resin narrow molecular weight distribution of gained, residual formaldehyde is low.Application publication number is the patent of CN103450832A: a kind of modified urea-formaldehyde resin glue of low residual formaldehyde sticks agent and production method thereof; by using modified urea-formaldehyde resin, toughener and defoamer to be main raw material; the sizing agent residual formaldehyde < 0.1mg/L made; as the sizing agent of wood-based plate; burst size of methanal is extremely low, protects the health of human consumer.Application publication number is the patent of CN 103408712A: a kind of production method of low residual formaldehyde polyvinyl alcohol modification glue urea formaldehyde sizing agent, its main raw material is formaldehyde, urea and polyvinyl alcohol, goes out the low sizing agent of residual formaldehyde by prepolymerization, polymerization and later stage polymerization three phases final production.However, because formaldehyde is one of main raw materials for production, the inevitable release formaldehyde of the wood-based plate made with urea-formaldehyde resin, although residual formaldehyde is low by above technical controlling, still has room for improvement.Meanwhile, urea-formaldehyde resin due to industrialization degree higher, production technology is more ripe, cost be difficult to reduce, cause the harmful competition of current urea-formaldehyde resin adhesive market value.
Xylogen is that vegitabilia is only second to the abundantest and most important cellulosic organic polymer, be distributed widely in the higher plant with more than fascicular pteridophyte plant, it is the unformed superpolymer that a class is connected with carbon-carbon bond by ehter bond by benzene oxide unit, xylogen has the potential quality of widespread use due to its molecular characterization in sizing agent, first xylogen itself has cohesiveness, directly can be used as sizing agent.Mandate publication number is: the patent of CN100381534C: a kind of lignin Environmental-protection type adhesive and preparation method thereof, xylogen tackiness agent is obtained by washing xylogen, the method for preparing lignin liquor, though main raw material is xylogen, but still with formaldehyde as one of raw material, the sizing agent made still has a small amount of Form aldehyde release; Application publication number is the invention of CN101928536A: a kind of flame retardant modified lignin resin glue and preparation method thereof, obtained by following component raw material: concentration is the formaldehyde solution 20-30wt% of 30-50%, containing the aldehydes matter 8-12wt% of three-functionality-degree, the papermaking wastewater that surplus is is main active substances with draft xylogen, visible, still use formaldehyde as main raw material in this invention, unavoidablely have residues of formaldehyde; Meanwhile, xylogen sticks in agent at resol and melamine-formaldehyde resin adhesive and is widely used equally, but same all there is the free problem of formaldehyde.
And current wood-based plate mostly is multi-layered bonded, along with time lengthening, the plank of multi-layered bonded occur aging, bond the phenomenon such as insecure, the plank of especially super multi-layered bonded requires higher to sizing agent, in order to pursue better bond effect, more make the sizing agent of high formaldehyde content, not only increase cost, also bring potential safety hazard.
Summary of the invention
The object of the invention is to supply for above technology, a kind of lignin fibre plate sizing agent and the production method thereof with high bond strength are provided, solve current fiberboard sizing agent and there is residues of formaldehyde harm environment, xylogen is the problem of the sizing agent made of main raw material equally containing formaldehyde, develops the high and low cost of a kind of security, fiberboard sizing agent that cohesive strength is high.
Technical scheme of the present invention is as follows:
Lignin flame redardant fiberboard sizing agent, is made up of the raw material of following parts by weight:
Xylogen 20-30 part;
Phenol 20-30 part;
Starch 15-20 part;
Silane coupling agent 1-5 part;
Defoamer 0.1-0.2 part.
Described starch is one in tapioca (flour), yam starch, flour or its composition.
Described silane coupling agent is vinyltriethoxysilane, three tert.-butoxy vinyl silanes, anilinomethyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, 3-(2,3 epoxy third oxygen) one in propyl trimethoxy silicane, mercaptopropyl trimethoxysilane, methyl vinyl diethoxysilane and mercapto hydroxypropyl methyl dimethoxysilane or its composition.Contriver finds that the lignin flame redardant fiberboard sizing agent that the present invention develops has good wettability, lower relative to traditional urea-formaldehyde resin, resol or its modifier sizing agent surface tension, and the silane coupling agent added described in invention, can the adhesive property of better effective raising xylogen sizing agent of the present invention.This is because: both containing organic group in the molecular structure of silane coupling agent, again containing inorganic structure, this special molecular structure makes its characteristic having organism and inorganics concurrently and function, after using silane coupling agent to be combined with xylogen sizing agent, there is excellent water tolerance, thermotolerance, weathering resistance, chemical-resistant and low surface tension, this may be because the silanol that in silane coupling agent, siloxanes hydrolysis in one end generates can react with the hydroxyl on adherend and filling surface or oxide compound form chemical bond, organic active functional group and sizing agent react and also form chemical bond, the sub-intermolecular forces of chemistry bond energy score wants a high 1-2 order of magnitude, meanwhile, the other end of silane coupling agent is connected with the active group after lignin modification, forms good chemical affinity, two ends bridging, as erected a bridge block, plays irreversible cohesive action after solidification, naturally obtains the bond effect of high strength.
Described defoamer is polydimethylsiloxane or tributyl phosphate.
There is the production method of the lignin fibre plate sizing agent of high bond strength, first pretreatment reaction is carried out to xylogen, obtained modified lignin, then in stirred autoclave, starch, fire retardant, silane coupling agent and defoamer is added according to by formula rate, mix, again with three-roll grinder grinding 1-2 hour, obtaining viscosity at 18-20 DEG C is the sizing agent of 0.15-0.60Pas.
Described modified lignin obtains by the following method:
(1) xylogen preparation: by bagasse be raw material the slurrying of alkaline boiling method black liquor in add acid, consider cost, the comprehensive evaluations such as production ease for operation, select sulfuric acid, hydrochloric acid, carbonic acid gas and Tai-Ace S 150 are for adding acid, regulate below the pH to 6 of black liquor, preferably at pH1-4, be placed to till insolubles all precipitates, storage period is 24-72h, then by the separating substances beyond throw out and throw out, separation can be undertaken by routine filtration device or Suction filtration device, the drying precipitate obtained, obtain the lignin product that purity is 50-80wt%, for obtaining more highly purified xylogen, process is further purified to the throw out obtained, concrete technology is: again add water acid adding in throw out, regulate pH1-4, dry after washing, repeat this treating processes more than 2 times, more than 80% high purity lignin product can be made, then enter subsequent production treating processes.
(2) add 70wt% sulfuric acid in the xylogen obtained in step (1), after stirring, be warming up to 140-160 DEG C, sulfonation reaction 1-2 hour; Through evaporator with central downcomer, speed of circulation is 0.4m/s-0.5m/s, and controlling discharging moisture content is 30wt%, precipitation, and after filtration, to be dried to water content be 15wt%; By xylogen: phenol 1:1(weight ratio) add phenol, control temperature 85-95 DEG C, insulation reaction 1 hour, finally regulate pH to 6.5-7.0 namely to obtain modified lignin with 30wt% sodium hydroxide.First carry out sulfonation modifying to xylogen in step (2) reaction, then carry out phenolate modification, final obtained modified lignin active group is many, and organic active is high, is combined the function being more conducive to playing sizing agent with silane coupling agent.
Beneficial effect of the present invention is:
One, the problem containing formaldehyde in traditional fibre plate sizing agent is changed, the lignin flame redardant fiberboard sizing agent of the present invention's development uses xylogen to be main raw material, through a series of modified, combine with fire retardant, silane coupling agent, can significantly improve the gluing performance of sizing agent, it is low that this xylogen sizing agent has viscosity, low to adherend surface tension, easily wetting, the advantages such as cohesive strength is large; This is because the active group after lignin modification is easy to silane coupling agent form chemical interactions together, and the other end and adherend surface bonding form chemical bond, greatly be better than an Intermolecular Forces 1-2 order of magnitude, and there is waterproof, the advantage such as high temperature resistant, make sizing agent and fiberboard form " bridge " structure, reach in conjunction with tight, firm, irreversible as closely linked as flesh and blood bond effect.
Two, the lignin fibre plate sizing agent viscosity scope of application with high strength bond performance of the present invention's development is large, all can play good result of use, be suitable for the bonding demand of multiple different demand fiberboard from 0.15-0.60Pas.
Four, production cost is low, easily realizes.High bond strength lignin binder of the present invention uses with bagasse the treated high-content xylogen obtained of black liquor of the alkaline boiling method slurrying being raw material, belong to refuse reclamation, reduce raw-material cost, reduce waste discharge simultaneously, walk the road of sustained development, there is important value and meaning; In addition, the preparation process industrialized condition of this xylogen sizing agent is ripe, easily realizes large production, possesses the basis of large-scale promotion.
Embodiment
embodiment 1 high bond strength lignin fibre plate sizing agent production formula and method 1
Formula composition:
25 parts, xylogen;
Tapioca (flour) 15 parts;
Vinyltriethoxysilane 0.5 part;
Anilinomethyl triethoxysilane 0.5 part;
Polydimethylsiloxane 0.1 part.
Production method: first pretreatment reaction is carried out to the xylogen obtained, obtained modified lignin, then in stirred autoclave, tapioca (flour), vinyltriethoxysilane and anilinomethyl triethoxysilane and defoamer is added according to formula rate, mix, grind 1 hour with three-roll grinder again, obtaining viscosity at 18-20 DEG C is the sizing agent of 0.15Pas
Modified lignin obtains by the following method:
(1) xylogen preparation: by bagasse be raw material the slurrying of alkaline boiling method black liquor in add 50wt% sulfuric acid, regulate black liquor pH6, be placed to till insolubles all precipitates, storage period is 72h, then by the separating substances beyond throw out and throw out, the drying precipitate obtained; Process is further purified to the throw out obtained: again add water 50wt% sulfuric acid in throw out, regulates pH2, dry after washing, repeat this treating processes 3 times, the high purity lignin product of 83.5wt% can be made, then enter subsequent production treating processes.
(2) add 70wt% sulfuric acid in the xylogen obtained in step (1), after stirring, be warming up to 140 DEG C, sulfonation reaction 1 hour; Through evaporator with central downcomer, speed of circulation is 0.4m/s-0.5m/s, and controlling discharging moisture content is 30wt%, precipitation, and after filtration, to be dried to water content be 15%; By xylogen: phenol 1:1(weight ratio) add phenol, control temperature 85 DEG C, insulation reaction 1 hour, finally regulate pH to 6.8 namely to obtain modified lignin with 30wt% sodium hydroxide.
embodiment 2 high bond strength lignin fibre plate sizing agent production formula and method 2
Formula composition:
20 parts, xylogen;
Phenol 20 parts;
Yam starch 18 parts;
Anilinomethyl triethoxysilane 1 part;
γ-r-chloropropyl trimethoxyl silane 1 part;
Tributyl phosphate 0.2 part.
Production method: first pretreatment reaction is carried out to the xylogen obtained, obtained modified lignin, then in stirred autoclave, yam starch, anilinomethyl triethoxysilane and γ-r-chloropropyl trimethoxyl silane and defoamer is added according to formula rate, mix, grind 1 hour with three-roll grinder again, obtaining viscosity at 18-20 DEG C is the sizing agent of 0.35Pas.
Modified lignin obtains by the following method:
(1) xylogen preparation: by bagasse be raw material the slurrying of alkaline boiling method black liquor in add 50wt% sulfuric acid, regulate black liquor pH5, be placed to till insolubles all precipitates, storage period is 48h, then by the separating substances beyond throw out and throw out, the drying precipitate obtained; Process is further purified to the throw out obtained: again adding water in throw out adds 50wt% sulfuric acid, regulate pH2.5, dry after washing, repeat this treating processes 5 times, the high purity lignin product of 87.1wt% can be made, then enter subsequent production treating processes.
(2) add 70wt% sulfuric acid in the xylogen obtained in step (1), after stirring, be warming up to 150 DEG C, sulfonation reaction 1.5 hours; Through evaporator with central downcomer, speed of circulation is 0.4m/s-0.5m/s, and controlling discharging moisture content is 30wt%, precipitation, and after filtration, to be dried to water content be 15wt%; By xylogen: phenol 1:1(weight ratio) add phenol, control temperature 85 DEG C, insulation reaction 1 hour, finally regulate pH to 6.7 namely to obtain modified lignin with 30wt% sodium hydroxide.
embodiment 3 high bond strength lignin fibre plate sizing agent production formula and method 3
Formula composition:
30 parts, xylogen;
Phenol 30 parts;
20 parts, flour;
Gamma-methyl allyl acyloxypropyl trimethoxysilane 2 parts;
3-(2,3 epoxy third oxygen) propyl trimethoxy silicanes 1 part;
Mercaptopropyl trimethoxysilane 2 parts;
Tributyl phosphate 0.15 part.
Production method: first pretreatment reaction is carried out to the xylogen obtained, obtained modified lignin, then in stirred autoclave, flour, gamma-methyl allyl acyloxypropyl trimethoxysilane and 3-(2 are added according to formula rate, 3 epoxy third oxygen) propyl trimethoxy silicane, mercaptopropyl trimethoxysilane and defoamer, mix, grind 2 hours with three-roll grinder again, obtaining viscosity at 18-20 DEG C is the sizing agent of 0.50Pas.
Modified lignin obtains by the following method:
(1) xylogen preparation: by bagasse be raw material the slurrying of alkaline boiling method black liquor in add 50wt% sulfuric acid, regulate black liquor pH4, be placed to till insolubles all precipitates, storage period is 72h, then by the separating substances beyond throw out and throw out, the drying precipitate obtained; Process is further purified to the throw out obtained: again add water 50wt% sulfuric acid in throw out, regulates pH1, dry after washing, repeat this treating processes 4 times, the high purity lignin product of 85.1% can be made, then enter subsequent production treating processes.
(2) add 70wt% sulfuric acid in the xylogen obtained in step (1), after stirring, be warming up to 150 DEG C, sulfonation reaction 2 hours; Through evaporator with central downcomer, speed of circulation is 0.4m/s-0.5m/s, and controlling discharging moisture content is 30wt%, precipitation, and after filtration, to be dried to water content be 15wt%; By xylogen: phenol 1:1(weight ratio) add phenol, control temperature 90 DEG C, insulation reaction 1 hour, finally regulate pH to 6.8 namely to obtain modified lignin with 30wt% sodium hydroxide.
embodiment 4 high bond strength lignin fibre plate sizing agent production formula and method 3
Formula composition:
28 parts, xylogen;
Phenol 28 parts;
Yam starch 4 parts;
Tapioca (flour) 7 parts;
6 parts, flour;
Methyl vinyl diethoxysilane 1 part;
Mercapto hydroxypropyl methyl dimethoxysilane 2 parts;
Mercaptopropyl trimethoxysilane 1 part;
Tributyl phosphate 0.09 part;
Polydimethylsiloxane 0.07 part.
Production method: first pretreatment reaction is carried out to the xylogen obtained, obtained modified lignin, then in stirred autoclave, starch, methyl vinyl diethoxysilane and mercapto hydroxypropyl methyl dimethoxysilane, mercaptopropyl trimethoxysilane and defoamer is added according to formula rate, mix, grind 2 hours with three-roll grinder again, obtaining viscosity at 18-20 DEG C is the sizing agent of 0.60Pas.
Modified lignin obtains by the following method:
(1) xylogen preparation: by bagasse be raw material the slurrying of alkaline boiling method black liquor in add 50wt% sulfuric acid, regulate black liquor pH4, be placed to till insolubles all precipitates, storage period is 72h, then by the separating substances beyond throw out and throw out, the drying precipitate obtained; Process is further purified to the throw out obtained: again add water 50wt% sulfuric acid in throw out, regulates pH1, dry after washing, repeat this treating processes 6 times, the high purity lignin product of 88.5wt% can be made, then enter subsequent production treating processes.
(2) add 70wt% sulfuric acid in the xylogen obtained in step (1), after stirring, be warming up to 160 DEG C, sulfonation reaction 2 hours; Through evaporator with central downcomer, speed of circulation is 0.4m/s-0.5m/s, and controlling discharging moisture content is 30wt%, precipitation, and after filtration, to be dried to water content be 15%; By xylogen: phenol 1:1(weight ratio) add phenol, control temperature 90 DEG C, insulation reaction 1 hour, finally regulate pH to 6.8 namely to obtain modified lignin with 30wt% sodium hydroxide.
embodiment 5
The lignin fibre plate sizing agent of the high bond strength obtained by embodiment 1-4 is carried out to the mensuration of the residual quantity of formaldehyde, and detect bonding strength according to the regulation in GB/T9846.1-9846.8-2004.Formaldehyde determination adopts methyl ethyl diketone spectrophotometry, residual formaldehyde %=measured value/example weight × %, and result is as shown in the table:
As seen from the above table, the lignin flame redardant fiberboard sizing agent residues of formaldehyde of the present invention's development is 0, use safety coefficient comparatively urea-formaldehyde resin is high, simultaneously bonding strength is also more excellent relative to urea-formaldehyde resin, this is because the active function groups crosslinking reaction after silane coupling agent and lignin modification serves vital role.
Claims (6)
1. there is a lignin fibre plate sizing agent for high bond strength, it is characterized in that: be made up of the raw material of following parts by weight:
Xylogen 20-30 part;
Phenol 20-30 part;
Starch 15-20 part;
Silane coupling agent 1-5 part;
Defoamer 0.1-0.2 part.
2. the lignin fibre plate sizing agent with high bond strength according to claim 1, is characterized in that: described starch is one in tapioca (flour), yam starch, flour or its composition.
3. the lignin fibre plate sizing agent with high bond strength according to claim 1, it is characterized in that: described silane coupling agent is vinyltriethoxysilane, three tert.-butoxy vinyl silanes, anilinomethyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, 3-(2,3 epoxy third oxygen) one in propyl trimethoxy silicane, mercaptopropyl trimethoxysilane, methyl vinyl diethoxysilane and mercapto hydroxypropyl methyl dimethoxysilane or its composition.
4. the lignin fibre plate sizing agent with high bond strength according to claim 1, is characterized in that: described defoamer is polydimethylsiloxane or tributyl phosphate.
5. the production method with the lignin fibre plate sizing agent of high bond strength according to claim 1, it is characterized in that: first pretreatment reaction is carried out to xylogen, obtained modified lignin, then in stirred autoclave, starch, fire retardant, silane coupling agent and defoamer is added according to formula rate, mix, again with three-roll grinder grinding 1-2 hour, obtaining viscosity at 18-20 DEG C is the sizing agent of 0.15-0.60Pas.
6. the production method with the lignin fibre plate sizing agent of high bond strength according to claim 5, is characterized in that: described modified lignin obtains by the following method:
(1) xylogen preparation: to bagasse be raw material the slurrying of alkaline boiling method black liquor in add acid, make it have the acidity of below pH6, be placed to till insolubles all precipitates, then by the separating substances beyond throw out and throw out, the drying precipitate obtained, makes high purity lignin product;
(2) add 70wt% sulfuric acid in the xylogen obtained in step (1), after stirring, be warming up to 140-160 DEG C, sulfonation reaction 1-2 hour; Through evaporator with central downcomer, speed of circulation is 0.4m/s-0.5m/s, and controlling discharging moisture content is 30wt%, precipitation, and after filtration, to be dried to water content be 15wt%; By xylogen: phenol weight ratio is that 1:1 adds phenol, control temperature 85-95 DEG C, insulation reaction 1 hour, finally pH to 6.5-7.0 is regulated namely to obtain modified lignin with 30wt% sodium hydroxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108582398A (en) * | 2018-06-29 | 2018-09-28 | 广西浙缘农业科技有限公司 | A kind of technique preparing wood-based plate using agricultural wastes |
| CN111793454A (en) * | 2020-08-17 | 2020-10-20 | 广西龙酉商贸有限公司 | Green non-formaldehyde wood adhesive and preparation method thereof |
| CN114438315A (en) * | 2022-02-10 | 2022-05-06 | 贵州理工学院 | Formula of micro silicon powder pellet binder |
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| CN1850933A (en) * | 2006-05-09 | 2006-10-25 | 山东泉林纸业有限责任公司 | Lignin Environmental-protection type adhesive and its preparing method |
| CN103360984A (en) * | 2012-03-26 | 2013-10-23 | 李林刚 | Preparation method of corn starch adhesive through cannabis degummed waste liquor |
| CN104087217A (en) * | 2014-06-25 | 2014-10-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing hydroxymethylated stalk ethanol byproduct and composite wood adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1850933A (en) * | 2006-05-09 | 2006-10-25 | 山东泉林纸业有限责任公司 | Lignin Environmental-protection type adhesive and its preparing method |
| CN103360984A (en) * | 2012-03-26 | 2013-10-23 | 李林刚 | Preparation method of corn starch adhesive through cannabis degummed waste liquor |
| CN104087217A (en) * | 2014-06-25 | 2014-10-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing hydroxymethylated stalk ethanol byproduct and composite wood adhesive |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108582398A (en) * | 2018-06-29 | 2018-09-28 | 广西浙缘农业科技有限公司 | A kind of technique preparing wood-based plate using agricultural wastes |
| CN111793454A (en) * | 2020-08-17 | 2020-10-20 | 广西龙酉商贸有限公司 | Green non-formaldehyde wood adhesive and preparation method thereof |
| CN114438315A (en) * | 2022-02-10 | 2022-05-06 | 贵州理工学院 | Formula of micro silicon powder pellet binder |
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Application publication date: 20150304 |