CN105176490A - Adhesive composition for wood - Google Patents
Adhesive composition for wood Download PDFInfo
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- CN105176490A CN105176490A CN201510696989.9A CN201510696989A CN105176490A CN 105176490 A CN105176490 A CN 105176490A CN 201510696989 A CN201510696989 A CN 201510696989A CN 105176490 A CN105176490 A CN 105176490A
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Abstract
The invention relates to an adhesive composition for wood, which comprises the following components in parts by weight: 10-100 parts of polymer disclosed as Formula I, 50-300 parts of matrix and 60-100 parts of liquefier. The adhesive composition for wood does not relate to formaldehyde or any other toxic raw material, does not contain free formaldehyde, and can still achieve the technical performance indexes of the traditional wood adhesive on the premise of greenness and environment friendliness.
Description
Technical field
The present invention relates to a kind of wood adhesive and preparation method thereof, particularly relate to a kind of wood adhesive be made up of bio-matrix material and nontoxic polymer and its preparation method and application.
Background technology
As everyone knows, wood industry needs to use a large amount of tackiness agent for Product processing.Wood adhesive the most frequently used in current industry is phenol-formaldehyde resin (PF), urea-formaldehyde resins (UF) and carbamide glue (MF).These three kinds of glue are referred to as three-aldehyde glue, have respective relative merits.Wherein, most popular is urea-formaldehyde glue (UF), is characterized in cheap, excellent property, but poor water resistance.Phenolic glue (PF) although water-tolerant, its dark brown color and its scope of application of higher price decision comparatively limited, be generally outdoor.Melamine glue (MF) excellent property, water-tolerant, but price is high, and therefore its market acceptance is lower.Meanwhile, because three-aldehyde glue all employs aldehyde compound, the finished product be therefore made up of it, and these products all can produce volatile organic compounds (VOC) in production, transport, use procedure.In recent years, receive increasing concern for the VOC distributed, the particularly formaldehyde impact on HUMAN HEALTH, the World Health Organization (WHO) confirms that formaldehyde has the harm such as murder by poisoning, carcinogenic, teratogenesis shape to people.Use three-aldehyde glue particularly urea-formaldehyde glue produce furniture and floor, sustainable release formaldehyde 10-15.Meanwhile, traditional three-aldehyde glue consumes a large amount of petroleum productss in process of production, and reserves is also necessarily limited.Therefore, in order to fundamentally address these problems, just must develop a kind of asepsis environment-protecting adhesive products, its production process is from raw material to product and it uses and does not relate to any poisonous and material not environmentally and process.
At present, the optimal candidate of environment-protecting asepsis glue is exactly the protein-base adhesive based on natural legume protein.Protein-base adhesive appears at last century 20, the '30s the earliest, and people made at that time
Wood adhesive is made with soybean protein and other additive.Nontoxic and the environmental protection of this tackiness agent; But the technology be limited at that time, the intensity of this kind of tackiness agent is low, and water resistance is poor.Five sixties, along with the development of petrochemical complex, protein-base adhesive rapidly substitute by three-aldehyde glue.
In the last few years, increasingly deep along with environmental consciousness, the requirement of people to environmental protection was also more and more higher.2007 U.S. CaliforniaAirResourcesBoard (CARB) had strict environment protection control standard to the tackiness agent used in timber products, and this standard all came into effect in 2013 in the whole America.Therefore, protein-based glue has entered into the sight line of people again, the R&D work that many R&D institutions are correlated with.The wherein technically relatively outstanding natural bean gum product having Dr.Li research group, such as US7,722,712B2 etc.; The bonding strength of product and the water tolerance of its report have all exceeded urea-formaldehyde glue, now large-scale commercial production.But, because this glue paste uses polymeric amide polyamine-epichlorohydrin (Polyamidoamine-Epichlorohydrin, PAE) as solidifying agent, considerably increase the cost of product, make final timber finished product price commercially higher.Therefore the another research direction that various alternative solidifying agent becomes protein-based glue is sought.
Because epoxy resin is the organic high score and the compound that contain two or more epoxide groups in molecule, therefore epoxy resin can react with the functional group such as such as hydroxyl, amino, sulfydryl, carboxyl of a lot of functional groups in soybean protein, and these features make epoxy resin become a kind of potential solidifying agent.But due to traditional epoxy resin, to there is price higher, and the factors such as long reaction time, therefore few people are applied in sheet fabrication industry.1996, Dolbey group report (DolbeyR.etc.Recentdevelopmentsinepoxyresins.RapraRev.Rep .8:176pp, 1996), the reaction of quaternary ammonium salt, ammonium salt energy intensifier ring epoxy resins; This report makes epoxy resin have to be applied to the possibility of sheet fabrication industry.
Summary of the invention
The object of the invention is to for deficiency of the prior art, and to provide a kind of take bio-matrix as wood adhesive of jointly forming of base-material and nontoxic polymer and preparation method thereof.Tackiness agent of the present invention does not relate to the composition such as any formaldehyde, phenolic aldehyde gummed urea-formaldehyde glue, also the detecting of the composition such as formaldehydeless and phenol, in preparation process, also do not have adding of solid catalyst, all technical of invention adhesive all can reach the technical performance index of traditional tackiness agent simultaneously simultaneously.
The present invention realizes the object of the invention by following concrete technical scheme:
A kind of Wood Adhesive composition, it comprises formula I polymkeric substance 10 ~ 100 weight part, matrix 50 ~ 300 weight part, liquefying agent 60 ~ 100 weight part; Its Chinese style I polymkeric substance is as follows:
Wherein M
wbe 9.08 × 10
6, M
nbe 5.8 × 10
6, molecular weight distributing index is 1.6.
Preferably, described matrix is one or more in maize straw, straw, straw, wood chip, W-Gum, cotton and paper pulp; Liquefying agent is selected from one or more in Xylitol, sorbyl alcohol, polyoxyethylene glycol, ethylene glycol, propylene glycol, glycerol and tetramethylolmethane.
Preferably, formula I polymkeric substance 50 ~ 100 weight part, matrix 100 ~ 300 weight part, liquefying agent 80 ~ 100 weight part.
Preferably, formula I polymkeric substance 80 ~ 100 weight part, matrix 200 ~ 300 weight part, liquefying agent 80 ~ 100 weight part.
Present invention also offers the preparation method of above-mentioned composition.
Described preparation method, comprises the steps: matrix removal of impurities, pulverizing, add liquefying agent 100 ~ 200 DEG C, under normal pressure ~ 15atm pressure, liquefaction 0.5 ~ 10h, then add formula I polymkeric substance, heat fused, stirs and obtains described composition.
Present invention also offers the polymkeric substance shown in a kind of formula I, it is characterized in that as follows
Wherein M
wbe 9.08 × 10
6, M
nbe 5.8 × 10
6, molecular weight distributing index is 1.6.
Formula I polymkeric substance can be used for wood adhesive field.
The application of above-mentioned wood adhesive, described wood adhesive can be used for that wood-base fibre and particle panel material such as glued board, woodwork plate, bamboo plywood, shaving board (OSB), flake board, fiberboard (comprising Midst density and high density fiberboard), parallel become a useful person (PSL), interlayer are become a useful person (LSL), laminated veneer lumber (LVL), and all kinds of composite floor board, bamboo flooring, consolidated floor etc.
The using method of above-mentioned wood adhesive in bonding timber, by described wood adhesive by roller coat, scraper for coating, curtain coating, or sprays the veneer surface being applied to wood-base fibre and particle panel material; Then multiple described veneer is piled up with the sheet material forming desired thickness; Again resulting sheet is displayed, cold pressing, hot pressing obtains composite wood wood-based plate.
Described wood-base fibre and particle panel material comprises glued board, woodwork plate, bamboo plywood, shaving board, flake board, fiberboard, parallelly to become a useful person, interlayer is become a useful person, laminated veneer lumber, all kinds of composite floor board, bamboo flooring or consolidated floor.
Described hot pressing time is 0.5-0.8min/mm, and hot pressing temperature is 100 DEG C-190 DEG C, and hot pressing pressure is 9-15 kg/cm.
Wood adhesive of the present invention, when for bonding production glued board, by roller coat, scraper for coating, curtain coating, or sprays the surface being applied to wood-base fibre and particle panel material veneer; Then multiple veneer is piled up with the sheet material forming desired thickness; Again sheet material displayed, cold pressing, hot pressing obtains composite wood wood-based plate.Fiberboard is by wet felt/wetpressing, dry felt/dry compression methodology, or wet felt/dry compression methodology obtains.
The assembly time of above-mentioned sheet material is 1-3 hour under room temperature; Pressure of colding pressing is generally 6-10 kg/cm (room temperature), and hot pressing pressure is generally 9-15 kg/cm.Wherein hot pressing time is 0.5-0.8min/mm, and hot pressing temperature can change between 90 DEG C-200 DEG C, is preferably 100 DEG C-190 DEG C.The dry shape bonding strength > 4MPa of gained composite wood wood-based plate, in general, wetting after soaking 3h in 60 DEG C of hot water can reach more than 1.2MPa by force, reaches the use standard of two class glue completely.In the art, according to the regulation of wood-based plate in national standard and face artificial board physicochemical property testing method, in wet method detects, the dry shape bonding strength > 2MPa of gained glued board is qualified glued board; Further, illustrate that the adhesive capacity of this glue paste is fine when the dry shape bonding strength of glued board is 4-5MPa.
The synthetic method of Chinese style I polymkeric substance of the present invention is simple, cheaper starting materials, good water solubility.Therefore, the wood adhesive for preparing for raw material with it of the present invention is with low cost; And it is pollution-free in production and use procedure; Its main raw material is all from renewable resources; Bonding strength is high; Wet tenacity after boiling water boiling can compared with phenolic glue; And the advantages such as operating procedure is simple, energy-conservation.Therefore, wood adhesive of the present invention is a kind of wood adhesive product with applications well prospect.
Wood adhesive of the present invention by bio-matrix material and the organic polymer etc. not containing formaldehyde formulated; Wood adhesive of the present invention is a kind of asepsis environment-protecting tackiness agent, no matter is in production, and transport, application process does not still all have the release of formaldehyde or toxic organic compound in finished product uses.Further, the bonding strength of wood adhesive of the present invention is high, water-tolerant; After testing, use the dry shape bonding strength > 4MPa of the composite wood wood-based plate of protein-based wood adhesive gained of the present invention, the intensity after its boiling water boiling can reach the use standard of two class glue compared with the performance of phenolic glue and completely.The preparation technology of wood adhesive of the present invention is simple, and hot pressing time is far smaller than three-aldehyde glue, greatly saves the energy.
Embodiment
Below by embodiment, the invention will be further described.The method described in the embodiment of the present invention that it should be understood that is only used for the present invention is described, instead of limitation of the present invention, under concept thereof of the present invention, all belong to the scope of protection of present invention to the simple modifications of preparation method of the present invention.The all raw materials used in embodiment and solvent are all purchased from SigmaBiochemicalandOrganicCompoundsforResearchandDiagnos ticClinicalReagents company.
Embodiment 1: the preparation of formula I polymkeric substance
The preparation of (1) 2,8-dibromo dibenzopyridine: dibenzopyridine (27.1mmol) is dissolved in 30mL chloroform, dropwise adds bromine (3.1mL, 60.5mmol) under 0 DEG C of ice-water bath condition; Under nitrogen atmosphere, reaction mixture is at room temperature stirred 12 hours; Leached by crude product, by methanol wash, obtain white powder 2,8-dibromo dibenzopyridine, productive rate is 85%;
(2) 4-tributylstamlyl-2-methyl-benzo [d] [1; 2; 3] preparation of triazole: under argon shield; 2-methyl-benzo [d] [1 will be dissolved with; 2; 3] anhydrous THF (100mL) solution of triazole (20mmol) is cooled to-78 DEG C, lentamente by the n-BuLi (2.5molL of 2 times of equivalents in 30 minutes
-1hexane solution) dropwise join in above-mentioned solution.At-78 DEG C, stir this mixture 1.5 hours, then temperature is adjusted to-40 DEG C, and 2 times of equivalent tributyltin chlorides slowly join in this solution, slowly temperature are risen to room temperature, and mixture is at room temperature stirred 12 hours.After reaction terminates, resistates is filtered, then solvent being obtained product by rotary evaporation decompression removing, without the need to being further purified in next step Stille linked reaction, can directly use.
(3) preparation of polymer precursor: by 2,8-dibromo dibenzopyridine (2.9mmol) and 4-tributylstamlyl-2-methyl-benzo [d] [1,2,3] triazole (14.5mmol) is dissolved in anhydrous THF (100mL), add four triphenyl phosphorus palladiums of 0.2% mass parts as catalyzer, stirring at room temperature activation under nitrogen atmosphere.After half an hour, mixture is heated to backflow, vigorous stirring 24 hours, then under reduced pressure concentrate and obtain thick product, finally, column chromatography carrys out this reaction mixture of purifying, and obtain white powder, productive rate is approximately 55%.
(4) preparation of formula I polymkeric substance: with refining DCM9mL, acetonitrile 1mL is electrolytic solution, and concentration is 0.01molL
-1the product of step (3) be polymerization single polymerization monomer, 0.1molL
-1phosphorus hexafluoride TBuA be ionogen; Stir, continue to pass into nitrogen protection after 20 minutes, keep solution under nitrogen atmosphere; with ITO conductive glass for working electrode, platinized platinum is to electrode, and Ag/AgCl is reference electrode; under corresponding voltage, constant potential polymerization, obtains the polymkeric substance of white solid.Described formula I polymkeric substance is as follows:
Wherein M
wbe 9.08 × 10
6, M
nbe 5.8 × 10
6, molecular weight distributing index is 1.6.
1HNMR(300MHz，DMSO，ppm)：δ：8.33(s，2H，CH)；8.07(d，2H，CH)；7.99(s，2H，CH)；7.98(s，H，CH)；7.88(d，2H，CH)；7.74(s，2H，CH)；3.63(s，6H，CH
3).
Embodiment 2: BIOLOGICAL ACTIVITY EXAMPLES
The maximum feature of formula I polymkeric substance is exactly nontoxicity, environmental protection.
The active detection by transfection of the PPAR δ of the polymkeric substance represented by formula I of the present invention is confirmed.In addition, the selectivity for PPAR hypotype PPAR α and PPAR γ is also tested.Test cell toxicity is detected, by animal experiment study activity in vivo by MTT.
CV-1 cell is used in this detection.Described cell is seeded in 96 orifice plates containing the DMEM being added with 10%FBS, DBS (DBS, through degreasing) and 1% penicillin/streptomycin, and at 37 DEG C, 5%CO
2incubator in cultivate.Test and carry out according to the step of inoculation, transfection, sample administration and confirmation.Specifically, CV-1 cell is seeded to 96 orifice plates (5000 cells/well), transfection after 24 hours.By total length PPAR plasmid DNA, can confirm because having uciferase activity PPAR activity reporter dna, provide about the beta-galactosidase enzymes DNA of transfection efficiency information and transfection reagent are used for transfection.By sample dissolution in methyl-sulphoxide (DMSO), by medium, it is administered in cell with different concns.In incubator, culturing cell is after 24 hours, makes lysis by using lysis buffer.Photometer and microplate reader is used to measure uciferase activity and betagalactosidase activity.The value of the luciferase using the value correction of beta-galactosidase enzymes to obtain.Utilize these value graphings, and calculate EC
50.
| Polymkeric substance | hPPARδ | hPPARα | hPPARγ |
| Polymkeric substance | hPPARδ | hPPARα | hPPARγ |
| I | 2.3nM | ia | ia |
Polymkeric substance of the present invention has highly selective for PPAR δ as can be seen here.
Execution MTT detection is the cytotoxicity in order to test the polymkeric substance represented by formula I of the present invention.MTT is water-soluble yellow substance, but can be become the insoluble crystal of purple by the desaturase in plastosome when it is introduced in viable cell.MTT is being dissolved in after in methyl-sulphoxide and can confirming cytotoxicity by measuring OD550.Experiment is carried out as follows.
CV-1 cell is inoculated in (5000 cells/well) in 96 orifice plates.At 37 DEG C, 5%CO
2incubator in cultivate described cell 24 hours, and it is used to the sample of different concns.Then, again by described cell cultures 24 hours, MTT reagent is added wherein.Cultivate after 15 minutes, the purple crystals of generation is dissolved in methyl-sulphoxide.Microplate reader is used to measure optical density(OD), to confirm cytotoxicity.
As a result, the polymkeric substance represented by formula I is identified does not have cytotoxicity for PPAR, even if be EC in its concentration
50value 100 times ~ 1000 times time also like this.
Embodiment 3: prepared by Adhesive composition
Take the maize straw of 50 weight parts, after removal of impurities, pulverization process, add 40 weight part ethylene glycol and 40 weight part glycerol, 150 DEG C, under 2atm pressure, liquefy 50 minutes, through colloidal mill, add 20 weight part formula I polymkeric substance again, heat fused, stirs.Tackiness agent can be obtained after cooling.
Embodiment 4: prepared by Adhesive composition
Take the straw of 80 weight parts, after removal of impurities, pulverization process, add 90 weight part polyoxyethylene glycol, 180 DEG C, under 5atm pressure, liquefy 2 hours, through colloidal mill, then add 30 weight part formula I polymkeric substance, heat fused, stirs.Tackiness agent can be obtained after cooling.
Embodiment 5: prepared by Adhesive composition
Take the wood chip of 100 weight parts, after removal of impurities, pulverization process, add 50 weight part glycerol and 50 weight part tetramethylolmethanes, 200 DEG C, under 10atm pressure, liquefy 6 hours, through colloidal mill, add 50 weight part formula I polymkeric substance again, heat fused, stirs.Tackiness agent can be obtained after cooling.
Compacting glued board is well-known to those skilled in the art, and design parameter is as follows:
Sample sheet material: board using poplar board;
Model specification: 400mm × 400mm × 2.1mm;
Water ratio: 12%;
Amount of spread (containing additive): 280g/m
2;
Precompressed pressure: 8-10Kg/cm
2;
Squeeze time: 30min;
Hot pressing temperature: 90-100 DEG C;
Hot pressing pressure: 10-12Kg/cm
2;
Hot pressing time: 1min/mm.
According to the method test bonding strength in GB/T14074-2006 and burst size of methanal, result is as follows:
Claims (7)
1. a Wood Adhesive composition, is characterized in that comprising formula I polymkeric substance 10 ~ 100 weight part, matrix 50 ~ 300 weight part, liquefying agent 60 ~ 100 weight part; Its Chinese style I polymkeric substance is as follows:
Wherein M
wbe 9.08 × 10
6, M
nbe 5.8 × 10
6, molecular weight distributing index is 1.6.
2. Wood Adhesive composition according to claim 1, is characterized in that described matrix is one or more in maize straw, straw, straw, wood chip, W-Gum, cotton and paper pulp; Liquefying agent is selected from one or more in Xylitol, sorbyl alcohol, polyoxyethylene glycol, ethylene glycol, propylene glycol, glycerol and tetramethylolmethane.
3. Wood Adhesive composition according to claim 1, is characterized in that formula I polymkeric substance 50 ~ 100 weight part, matrix 100 ~ 300 weight part, liquefying agent 80 ~ 100 weight part.
4. Wood Adhesive composition according to claim 1, is characterized in that formula I polymkeric substance 80 ~ 100 weight part, matrix 200 ~ 300 weight part, liquefying agent 80 ~ 100 weight part.
5. the preparation method of the arbitrary described Wood Adhesive composition of claim 1-4, it is characterized in that comprising the steps: matrix removal of impurities, pulverizing, add liquefying agent 100 ~ 200 DEG C, under normal pressure ~ 15atm pressure, liquefaction 0.5 ~ 10h, add formula I polymkeric substance again, heat fused, stirs and obtains described composition.
6. the polymkeric substance shown in formula I, is characterized in that as follows:
Wherein M
wbe 9.08 × 10
6, M
nbe 5.8 × 10
6, molecular weight distributing index is 1.6.
7. the purposes of formula I polymkeric substance in wood adhesive field.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106047280A (en) * | 2016-06-30 | 2016-10-26 | 上海东和胶粘剂有限公司 | Artificial veneer composite formaldehyde-free adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778858A (en) * | 2004-11-26 | 2006-05-31 | 江西南大中德食品工程中心 | Biomass-base and waterproof wooden adhesive without formaldehyde and its production |
| CN101265401A (en) * | 2008-04-23 | 2008-09-17 | 中国科学院广州化学研究所 | Method for preparing biomass polyurethane adhesive |
| US20130202905A1 (en) * | 2009-10-23 | 2013-08-08 | David H. Blount | Delignification of biomass containing lignin and production of adhesive compositions and methods of making lignin cellulose compositions |
| CN103320081A (en) * | 2013-05-23 | 2013-09-25 | 济南大学 | High-molecular composite adhesive, and preparation method and application thereof |
-
2015
- 2015-10-26 CN CN201510696989.9A patent/CN105176490B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778858A (en) * | 2004-11-26 | 2006-05-31 | 江西南大中德食品工程中心 | Biomass-base and waterproof wooden adhesive without formaldehyde and its production |
| CN101265401A (en) * | 2008-04-23 | 2008-09-17 | 中国科学院广州化学研究所 | Method for preparing biomass polyurethane adhesive |
| US20130202905A1 (en) * | 2009-10-23 | 2013-08-08 | David H. Blount | Delignification of biomass containing lignin and production of adhesive compositions and methods of making lignin cellulose compositions |
| CN103320081A (en) * | 2013-05-23 | 2013-09-25 | 济南大学 | High-molecular composite adhesive, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张玉龙等: "《胶黏剂配方精选》", 31 January 2009, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106047280A (en) * | 2016-06-30 | 2016-10-26 | 上海东和胶粘剂有限公司 | Artificial veneer composite formaldehyde-free adhesive and preparation method thereof |
| CN106047280B (en) * | 2016-06-30 | 2019-02-26 | 上海东和胶粘剂有限公司 | Compound no aldehyde glue of manufactured veneer and preparation method thereof |
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