CN104774588B - A kind of albumen base timber adhesive and its preparation method and application and application method - Google Patents
A kind of albumen base timber adhesive and its preparation method and application and application method Download PDFInfo
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- CN104774588B CN104774588B CN201510016168.6A CN201510016168A CN104774588B CN 104774588 B CN104774588 B CN 104774588B CN 201510016168 A CN201510016168 A CN 201510016168A CN 104774588 B CN104774588 B CN 104774588B
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Abstract
The present invention relates to a kind of wood adhesive and preparation method thereof, more particularly to one kind albumen base timber adhesive and its preparation method and application and application method made of vegetable protein and non-toxic epoxy, it is formulated by natural plant protein and formaldehydeless epoxy curing agent and filler etc., the albumen base timber adhesive of the present invention is a kind of asepsis environment-protecting adhesive, either producing, transport, application process is still all without the release of formaldehyde or toxic organic compound in finished product use；Meanwhile the bonding strength of the adhesive is high, compared with the performance of phenol glue and the use standards of two class glue can be fully achieved in water-tolerant, intensity after boiling water boiling.The preparation technology of the albumen base timber adhesive of the present invention is simple, and hot pressing time is far smaller than three-aldehyde glue, greatlys save the energy.
Description
Technical field
The present invention relates to a kind of wood adhesive and preparation method thereof, more particularly to one kind is by vegetable protein and nontoxic epoxy
Albumen base timber adhesive and its preparation method and application and application method made of resin.
Background technology
It is well known that wood industry needs to use substantial amounts of adhesive to be used for Product processing.It is the most frequently used in industry at present
Wood adhesive is phenol-formaldehyde resin（PF）, urea-formaldehyde resins（UF）With carbamide glue（MF）.These three glue are united
Referred to as three-aldehyde glue, there are respective advantage and disadvantage.Wherein, most popular is urea-formaldehyde glue（UF）, it is characterized in cheap, property
Can be excellent, but poor water resistance.Phenol glue（PF）Although water-tolerant, its deep brown color and higher price decision its be applicable model
Enclose it is relatively limited, generally outdoor.Melamine glue（MF）Function admirable, water-tolerant, but price is high, therefore its market connects
It is relatively low by spending.Simultaneously as three-aldehyde glue has used aldehyde compound, therefore the finished product being made from it, and these products exist
VOC can be all produced during production, transport, use（VOC）.In recent years, for the VOC distributed, it is particularly
Influence of the formaldehyde to health receives more and more attention, the World Health Organization（WHO）Confirm formaldehyde to people have poison,
Carcinogenic, teratogenesis shape etc. endangers.The furniture produced using three-aldehyde glue particularly urea-formaldehyde glue and floor, sustainable release formaldehyde 10-15
Year.Meanwhile traditional three-aldehyde glue consumes substantial amounts of oil product in process of production, reserves is also necessarily limited.
Therefore, in order to fundamentally solve these problems, a kind of asepsis environment-protecting adhesive products must be just developed, its production process is
From raw material to product and it uses and is not related to any poisonous and material not environmentally and process.
At present, the optimal candidate of environment-protecting and non-poisonous glue is namely based on the protein-base adhesive of natural peas protein.Albumen
Base adhesive appears in last century 20, the '30s earliest, and wood was made using soybean protein and other additives in people at that time
Material adhesive.This adhesive is nontoxic and environmentally friendly；But technology at that time is limited to, the low intensity of this kind of adhesive, water proofing property
Can be poor.In five sixties, with the development of petrochemical industry, protein-base adhesive is substituted rapidly by three-aldehyde glue.
In the last few years, it is increasingly deep with environmental consciousness, requirement of the people to environmental protection also more and more higher.The U.S. in 2007
California Air Resources Board（CARB）There is strict environmental protection control to the adhesive used in timber products
Standard processed, and this standard all came into effect in 2013 in the whole America.Therefore, albumen base rubber has entered into regarding for people again
Line, many R＆D institutions have carried out the R＆D work of correlation.Wherein technically than the more prominent day for having Dr. Li research groups
Right bean gum product, such as B2 of US 7,722,712 etc.；The bonding strength and water resistance of its product reported have been above ureaformaldehyde
Glue, large-scale industrial production.But because the adhesive uses polyamide polyamine-epoxychloropropane
（Polyamidoamine-Epichlorohydrin, PAE）As curing agent, the cost of product is considerably increased so that final
Timber finished product price commercially it is higher.Therefore seeking the curing agent of various replacements turns into the another research side of albumen base rubber
To.
Because epoxy resin is organic high score and compound containing two or more epoxide groups in molecule, therefore
Epoxy resin can react with functional group such as hydroxyl, amino, sulfydryl, carboxyl of many functional groups in soybean protein, this
A little features cause epoxy resin to turn into a kind of potential curing agent.But due to traditional epoxy resin, price to be present higher, instead
The factor such as long between seasonable, therefore few people are applied in sheet fabrication industry.1996, Dolbey groups report
（Dolbey R. etc. Recent developments in epoxy resins. Rapra Rev. Rep. 8:176pp,
1996）, quaternary ammonium salt, ammonium salt can accelerate the reaction of epoxy resin；This report causes epoxy resin to be applied to sheet fabrication
The possibility of industry.
The content of the invention
It is an object of the invention to for deficiency of the prior art, and provide that a kind of cost is cheap, prepares simple and nothing
Novel protein base timber adhesive of pollution and its preparation method and application and application method, one kind has been provided in particular in by planting
Albumen base timber adhesive and preparation method thereof made of thing albumen and non-toxic epoxy, albumen base timber adhesive utilize plant
Thing albumen, and free of contamination epoxy resin albumen sill material glue is prepared using cheap quaternary ammonium salt epoxy resin as curing agent
Stick, in addition, the preparation method of albumen base timber adhesive is not only simple to operate, and reduce albumen base timber adhesive
Product cost.
The technical solution adopted in the present invention：
A kind of albumen base timber adhesive, including vegetable protein, lignin, without aldehyde curing agent, alkali and filler；Based on institute
The gross weight of albumen base timber adhesive is stated,
The content of the vegetable protein is 5-50wt%；
The content of the lignin is 0-30wt%；
The content of the no aldehyde curing agent is 1-30wt%；
The content of the alkali is 0.1-15wt%；
The content of the filler is 0-20wt%.
The gross weight of the albumen base timber adhesive is preferably based on, the content of vegetable protein is 10%-45 wt%.
It is highly preferred that the gross weight based on the albumen base timber adhesive, the content of vegetable protein is 25-45 wt%；
The content of lignin is 0-20wt%；Content without aldehyde curing agent is 3-25wt%；The content of alkali is 0.2-12wt%；Filler contains
Measure as 0-20wt%.
The formaldehydeless curing agent includes polynary expoxy propane chain quaternary ammonium salt epoxy resin, such as with DMP30- epoxy chlorine
Propane（DMP30-Epichlorohydrin）For the quaternary ammonium salt epoxy resin of representative；Polynary expoxy propane chain quaternary amine epoxy
Resin refers to the aromatic series or aliphatic quaternary ammonium salt epoxy resin of the expoxy propane containing 2 or more than 2；Wherein, aromatic series
Quaternary ammonium salt epoxy resin is the phenol ring substituted containing 2-3 expoxy propane side chain, general structure such as molecular formula（I）It is shown；Or
Aromatic ester quaternary ammonium resin containing the expoxy propane side chain of 2 or more than 2；
（I）；
Wherein, n is integer, and n=2-3.Preferably, aromatic series quaternary ammonium salt epoxy resin is commercially available DMP30- epoxies
Chloropropane, its structural formula such as molecular formula（IA）It is shown：
（IA）.
Aliphatic quaternary ammonium salt epoxy resin is the carbon chain lengths of the 2-10 carbon containing straight or branched and has multiple epoxies
The quaternary ammonium salt epoxy resin of propane side chain, its structure such as molecular formula（II）It is shown,
（II）；
Wherein, m is integer, and m=2-10.
Preferably, aliphatic quaternary ammonium salt epoxy resin is EMTDA- epoxychloropropane or tetramethyl -1,6- hexamethylene diamine-ring
Oxygen chloropropane etc..
The no aldehyde curing agent is polynary expoxy propane chain quaternary amine salt epoxy resin or the polynary expoxy propane chain season
Amine salt epoxy resin and the mixture of other compounds, such as aliphatic polyhydroxy compound, multi-carboxy compound or how aminated
The mixture of compound.
Preferably, aliphatic polyamine based compound is the aliphatic polymer containing 2 or more than 2 amidos, such as existing
Known polyamide polyamine in technology（Molecular formula IIIA）Or its reaction product with epoxy alkyl halide, such as polyamide polyamine ring
Oxygen chloropropane（PAE）（Molecular formula IIIB）Compound etc..
The expression formula of polyamide polyamine is as follows：
（IIIA）；
Wherein, R1And R2For the methylene of 2-10, preferably adipic acid and diethylenetriamine copolymer.
The expression formula of polyamide polyamine epichlorhydrin is as follows：
（IIIB）.
Aliphatic multi-carboxy compound is CMC（Carboxymethyl cellulose）Or starch after improvement etc..Preferably, aliphatic is more
Hydroxy compounds is glycerine or starch etc..It is highly preferred that aliphatic polyhydroxy compound is glycerine.
When the no aldehyde curing agent is polynary expoxy propane chain quaternary amine salt epoxy resin, the no aldehyde curing agent contains
Measure the 1-30 wt% for adhesive weight；When without aldehyde curing agent be polynary expoxy propane chain quaternary amine salt epoxy resin with other change
During the mixture of compound, polynary expoxy propane chain quaternary amine salt epoxy resin and the weight ratio of other compounds are 1.5-8:1.
The polymerized monomer of traditional epoxy resin typically comprises only an expoxy propane structure, and epoxy of the present invention
The polymerized monomer of propane is using aromatic rings or short carbon chain as molecule core, and from going out multiple expoxy propane chains derived from core.It is this
Polymerization efficiency is greatly improved in structure so that the degree of polymerization is multiplied, and so as to reduce the usage amount of polymerized monomer, reduces
Cost.Simultaneously as each polymerized monomer contains multiple expoxy propane chains, therefore the netted of complexity is more likely formed after polymerisation
Paradigmatic structure, and then improve performance.Specifically by taking DMP30- epoxychloropropane as an example, the DMP30- epoxychloropropane of per molecule contains
Three propylene oxide units, therefore after polymerization, in three different directions chainings and complicated space network can be formed,
So the theoretical performance after the polymerization of its unit molal quantity monomer is 3 times of the single epichlorohydrin resin of tradition, actual performance
Test is then 2.1 times of the single epichlorohydrin resin of tradition.And under conditions of same cost, performance can improve 80%.In addition by
Contain 3 quaternary amine structures in each molecule, therefore its water solubility greatly improves, and is 1.5-2 times of general expoxy propane.To sum up
Described, polynary expoxy propane chain quaternary amine salt epoxy resin of the present invention has the characteristics that：
1st, it is soluble in water；
2nd, can be reacted in itself with protein molecular and solidification agent molecule；
The 3rd, the cohesive reaction site of wood fiber base material can be provided.
Therefore, no aldehyde curing agent of the invention is water miscible difunctional curing agent.In other words, difunctional curing agent
The Part I of available reaction site on molecule can with other difunctionals solidify agent molecule reaction or with protein
Functional group（Particularly carboxylic acid and amino）Reaction.The Part II of available reaction site on difunctional solidification agent molecule can
To be connected to form covalent bond and/or hydrogen bond with wood fibre substrate.Also, this based epoxy resin is cheap, with wood fibre
Element and soy meal reaction time are short, and reaction temperature is low, efficiency high, can be widely applied in a variety of wood-processing industries.
The vegetable protein is the one or more in little Mai paddy Yuan albumen, zeins and peas protein；It is preferred that
Ground, it is peas protein；It is highly preferred that it is soybean protein；The soybean protein is preferably SPI or soy meal；More preferably soybean
Powder.
Soybean protein is the Exemplary protein used in adhesive example disclosed in this invention, presently disclosed
Albumen base timber adhesive any type of soy protein products can be used.Mesh first three most common soy protein products point
It is not soy meal, soybean protein concentrate, and soybean protein isolate（SPI）.Maximum difference between these products is protein
Content.Typically, soy meal includes about 45 wt% protein, and soybean protein concentrate includes at least about 65 wt% egg
White matter（Dry weight）, SPI includes at least about 85 wt% protein（Dry weight）.
The lignin generally refers to assign the novolac polymer race of vegetable material strength and stiffness.The lignin includes
Analysis lignin preparation for example BRAUNS lignin, cellulase lignin, dioxanes acidolysis lignin, grind wood lignin,
Klason lignin or periodic acid lignin, and industrial lignin preparation such as kraft lignin or lignosulfonates.
Because kraft lignin has the features such as cost is low, and performance is good, in the case of equal usage amount, obtained using kraft lignin
The performance comparable of the product arrived uses the high 5%-10% of properties of product of other lignin.Its product in the case of equal cost
Performance can improve more than 10%.Therefore, in the present invention, lignin is preferably kraft lignin.
The alkali is inorganic base or lewis base.The inorganic base is the oxide or hydroxide of IA races, or Group IIA
Oxide, hydroxide or borate；Preferably, inorganic base is sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or boron
Sour sodium.The lewis base is preferably triethylamine or calcium acetate.
The filler is silica, paraffin, wheat flour, bark powder, shuck powder or its analog.
The turnaround time of albumen base timber adhesive is generally 1-2 hours in the present invention, will be crosslinked solidification afterwards, but
The turnaround time generally required during industrial mass production is 6-8 hours.Therefore, in order to be greatly improved the present invention
The turnaround time of adhesive, albumen base timber adhesive of the present invention also include farina, reached by adding farina
To the purpose for extending the turnaround time；The performance of adhesive and other characteristics are kept not to change simultaneously.Preferably, the albumen
Base timber adhesive replaces traditional inorganic base with lewis base, and adds farina.
Preferably, a kind of albumen base timber adhesive include vegetable protein, lignin, without aldehyde curing agent, farina,
Inorganic base and filler；Based on the gross weight of the albumen base timber adhesive,
The content of vegetable protein is 5-50wt%；
The content of farina is 5-15wt%；
The content of lignin is 0-30wt%；
Content without aldehyde curing agent is 1-30wt%；
The content of inorganic base is 0.1-15wt%；
The content of filler is 0-20wt%.
Preferably, a kind of albumen base timber adhesive include vegetable protein, lignin, without aldehyde curing agent, farina,
Lewis base and filler；Gross weight based on the albumen base timber adhesive；
The content of vegetable protein is 5-50wt%；
The content of farina is 5-15wt%；
The content of lignin is 0-30wt%；
Content without aldehyde curing agent is 1-30wt%；
The content of lewis base is 0.1-15wt%；
The content of filler is 0-20wt%；
Wherein, lewis base is preferably triethylamine or calcium acetate.
It is highly preferred that the gross weight based on the albumen base timber adhesive；The content of vegetable protein is 5-40 wt%；Horse
The content of bell sweet potato starch is 5-15 wt%；The content of lignin is 0-20 wt%；Content without aldehyde curing agent is 3-25 wt%；
The content of lewis base is 0.2-12 wt%；The content of filler is 0-20 wt%；Wherein, lewis base is preferably triethylamine or second
Sour calcium.
The farina is the starch product after the drying of edible or feed rank；Can by adding farina
The turnaround time of adhesive is extended into 6-8 hours by 1-2 hours before, so that such adhesive adapts to industry significantly
The needs of production.
A kind of method for preparing above-mentioned albumen base timber adhesive, comprises the following steps：
Step 1）, the inorganic base that is added to the mixture of vegetable protein or vegetable protein and lignin or Louis's alkali soluble
In liquid, stirring is until albumen and lignin are completely dispersed in the solution；
Step 2）, to step 1）Formaldehydeless curing agent is added in solution after scattered or adds formaldehydeless curing agent and Ma Ling
Sweet potato starch, stir；
Step 3）, to step 2）Filler is added in solution after stirring, adds and stirs, so as to obtain albumen base
Wood adhesive.
In above-mentioned preparation method, also inorganic base first can be added to no aldehyde curing agent solution when preparing albumen base timber adhesive
In stir, add the mixture of vegetable protein or vegetable protein and lignin, filler added after stirring.
A kind of application of above-mentioned albumen base timber adhesive, described albumen base timber adhesive can be used for wood-base fibre and particle panel material
Such as glued board, woodwork plate, bamboo plywood, particieboard（OSB）, flake board, fiberboard（It is fine including Midst density and high density
Tie up plate）, parallel become a useful person（PSL）, interlayer becomes a useful person（LSL）, laminated veneer lumber（LVL）, and it is all kinds of composite floor boards, bamboo flooring, strong
Change floor etc..
Application method of a kind of above-mentioned albumen base timber adhesive in timber is bonded, by the albumen base timber adhesive
The veneer surface of wood-base fibre and particle panel material is applied to by roller coat, scraper for coating, curtain coating, or sprinkling；Then multiple veneer heaps
Accumulate to form the sheet material of required thickness；Resulting sheet is displayed again, cold pressing, hot pressing obtain composite wood wood-based plate.
The wood-base fibre and particle panel material includes glued board, woodwork plate, bamboo plywood, particieboard, flake board, fiberboard, flat
Row is become a useful person, interlayer is become a useful person, laminated veneer lumber, all kinds of composite floor boards, bamboo flooring or consolidated floor.
Described hot pressing time is 0.5-0.8 min/mm, and hot pressing temperature is 100 DEG C -190 DEG C, and hot pressing pressure is 9-15 public
Jin/square centimeter.
Albumen base timber adhesive of the present invention for bond produce glued board when, by roller coat, scraper for coating,
Curtain coating, or sprinkling are applied to the surface of wood-base fibre and particle panel material veneer；Then multiple veneers are accumulated to form the sheet material of required thickness；
Sheet material is displayed again, is cold-pressed, hot pressing obtains composite wood wood-based plate.Fiberboard can pass through wet felt/wetpressing, dry felt/dry-pressing side
Method, or wet felt/dry compression methodology are made.
The assembly time of above-mentioned sheet material is 1-3 hours at room temperature；Cold pressing pressure is generally 6-10 kg/cms（Room
Temperature）, hot pressing pressure is generally 9-15 kg/cms.Wherein hot pressing time is 0.5-0.8 min/mm, and hot pressing temperature can be with
Change between 90 DEG C -200 DEG C, preferably 100 DEG C -190 DEG C.The dry shape bonding strength of gained composite wood wood-based plate> 4
MPa, in general, wet after soaking 3 h in 60 DEG C of hot water can reach 1.2 more than MPa, the completely use up to two class glue by force
Standard.In the art, according to wood-based plate in national standard and the regulation of face artificial board physicochemical property method of testing, wet
In method detection, the dry shape bonding strength of gained glued board>2 MPa are qualified glued board；Also, the dry shape glue of glued board
Close when intensity is 4-5 MPa and illustrate that the adhesive power of the adhesive is fine.
A kind of albumen base timber adhesive is in specifically used, due to the quaternary ammonium salt ring in the albumen base timber adhesive
Oxygen resin curing agent has the longer open hour.Therefore, before applied to timber is bonded, the very short time by curing agent and
The other compositions of binding agent are mixed, and a week is up to about so as to which the binding agent formed has before timber is bonded
Open hour.
The synthetic method of polynary expoxy propane chain quaternary amine salt epoxy resin is simple in the present invention, and raw material is cheap, water-soluble
It is good；And its temperature with the reaction of albumen base can be greatly reduced, shorten the time with the reaction of albumen base.Therefore, the present invention with
It is that the cost for the albumen base timber adhesive that curing agent is prepared is cheap；It is and pollution-free in the production and use process；
Its primary raw material is all from renewable resource；Bonding strength is high；Wet strength after boiling water boiling can be compared with phenol glue；And operate
Technique is simple, the advantages that energy-conservation.Therefore, albumen base timber adhesive of the present invention is that a kind of have applications well prospect
Wood adhesive product.
Albumen base timber adhesive of the present invention is by natural plant protein and the epoxy curing agent without formaldehyde and fills out
Material etc. is formulated；The albumen base timber adhesive of the present invention is a kind of asepsis environment-protecting adhesive, is either being produced, and is transported,
Application process is still all without the release of formaldehyde or toxic organic compound in finished product use.Also, albumen sill of the present invention
The bonding strength of material adhesive is high, water-tolerant；After testing, using the present invention albumen base timber adhesive obtained by wood composite
The dry shape bonding strength of matter wood-based plate>4MPa, intensity after its boiling water boiling compared with the performance of phenol glue and can be fully achieved two
The use standard of class glue.The preparation technology of the albumen base timber adhesive of the present invention is simple, and hot pressing time is far smaller than three-aldehyde glue,
Greatly save the energy.The wherein environmental protection of product, technique and performance characteristics are compared as follows shown in list.
Wherein, hot pressing time is calculated by taking 18mm glued boards as an example.The primary raw material of urea-formaldehyde resin adhesive refers to ureaformaldehyde and first
Aldehyde, the primary raw material in phenolic resin glue refer to phenolic aldehyde and formaldehyde, the primary raw material in melamine resin adehsive refer to melamine and
Formaldehyde and albumen powder and curing agent in the present invention.
Design, concrete structure and the caused technique effect of the present invention are described further below with reference to embodiment,
To be fully understood from the purpose of the present invention, feature and effect.
Embodiment
A kind of albumen base timber adhesive, the albumen base timber adhesive include vegetable protein, lignin, solidified without aldehyde
Agent, inorganic base and filler.Wherein, the gross weight based on the albumen base timber adhesive；
The content of vegetable protein is 5-50wt%；
The content of lignin is 0-30wt%；
Content without aldehyde curing agent is 1-30wt%；
The content of inorganic base is 0.1-15wt%；
The content of filler is 0-20wt%.
In a preferred embodiment of the invention, the gross weight based on the albumen base timber adhesive, vegetable protein
Content is 10%-45wt%.
It is highly preferred that the gross weight based on the albumen base timber adhesive, the content of vegetable protein is 25-45 wt%；
The content of lignin is 0-20wt%；Content without aldehyde curing agent is 3-25wt%；The content of inorganic base is 0.2-12wt%；Filler
Content be 0-20wt%.
In the embodiment of the present invention, the no aldehyde curing agent includes polynary expoxy propane chain quaternary ammonium salt epoxy
Resin, such as with DMP30- epoxychloropropane（DMP30-Epichlorohydrin）For the quaternary ammonium salt epoxy resin of representative.
In the present invention, polynary expoxy propane chain quaternary amine salt epoxy resin refers to the epoxy third containing 2 or more than 2
The aromatic series or aliphatic quaternary ammonium salt epoxy resin of alkane.Wherein, aromatic series quaternary ammonium salt epoxy resin is to contain 2-3 expoxy propane
The phenol ring of side chain substitution, general structure such as molecular formula（I）It is shown；Or the virtue of the expoxy propane side chain containing 2 or more than 2
Fragrant ester quat resin；
（I）；
Wherein, n is integer, and n=2-3.Preferably, aromatic series quaternary ammonium salt epoxy resin is commercially available DMP30- epoxies
Chloropropane, its structural formula such as molecular formula（IA）It is shown：
（IA）.
Aliphatic quaternary ammonium salt epoxy resin is the carbon chain lengths of the 2-10 carbon containing straight or branched and has multiple epoxies
The quaternary ammonium salt epoxy resin of propane side chain, its structure such as molecular formula（II）It is shown,
（II）；
Wherein, m is integer, and m=2-10.Preferably, aliphatic quaternary ammonium salt epoxy resin is EMTDA- epoxy chloropropionates
Alkane or tetramethyl -1,6- hexamethylene diamines-epoxychloropropane etc..
In the embodiment of the present invention, the no aldehyde curing agent is polynary expoxy propane chain quaternary amine asphalt mixtures modified by epoxy resin
Fat or the polynary expoxy propane chain quaternary amine salt epoxy resin and other compounds（Such as aliphatic polyhydroxy compound, more carboxyls
Compound or more amine compounds）Mixture.
Preferably, aliphatic polyamine based compound is the aliphatic polymer containing 2 or more than 2 amidos, such as existing
There is known polyamide polyamine in technology（Molecular formula IIIA）Or its reaction product with epoxy alkyl halide, such as polyamide polyamine
Epoxychloropropane（PAE）（Molecular formula IIIB）Compound etc..
The expression formula of polyamide polyamine is as follows：
（IIIA）；
Wherein, R1And R2For the methylene of 2-10, preferably adipic acid and diethylenetriamine copolymer.
The expression formula of polyamide polyamine epichlorhydrin is as follows：
（IIIB）.
In another preferred embodiment of the present invention, aliphatic multi-carboxy compound is CMC（Carboxymethyl cellulose）Or
Starch after improvement etc..Aliphatic polyhydroxy compound is glycerine or starch etc..It is highly preferred that aliphatic polyhydroxy compound
For glycerine.
In the embodiment of the present invention, when being polynary expoxy propane chain quaternary amine salt epoxy resin without aldehyde curing agent
When, the content of the no aldehyde curing agent is 1-30 wt % of adhesive weight.When being polynary expoxy propane chain without aldehyde curing agent
When type quaternary amine salt epoxy resin and the mixture of other compounds, polynary expoxy propane chain quaternary amine salt epoxy resin and other changes
The weight ratio of compound is 1.5-8:1.
The polymerized monomer of traditional epoxy resin typically comprises only an expoxy propane structure, and epoxy of the present invention
The polymerized monomer of propane is using aromatic rings or short carbon chain as molecule core, and from going out multiple expoxy propane chains derived from core.It is this
Polymerization efficiency is greatly improved in structure so that the degree of polymerization is multiplied, and so as to reduce the usage amount of polymerized monomer, reduces
Cost.Simultaneously as each polymerized monomer contains multiple expoxy propane chains, therefore the netted of complexity is more likely formed after polymerisation
Paradigmatic structure, and then improve performance.Specifically by taking DMP30- epoxychloropropane as an example, the DMP30- epoxychloropropane of per molecule contains
Three propylene oxide units, therefore after polymerization, in three different directions chainings and complicated space network can be formed,
So the theoretical performance after the polymerization of its unit molal quantity monomer is 3 times of the single epichlorohydrin resin of tradition, actual performance
Test is then 2.1 times of the single epichlorohydrin resin of tradition.And under conditions of same cost, performance can improve 80%.In addition by
Contain 3 quaternary amine structures in each molecule, therefore its water solubility greatly improves, and is 1.5-2 times of general expoxy propane.To sum up
Described, polynary expoxy propane chain quaternary amine salt epoxy resin of the present invention has the characteristics that：
1st, it is soluble in water；
2nd, can be reacted in itself with protein molecular and solidification agent molecule；
The 3rd, the cohesive reaction site of wood fiber base material can be provided.
Therefore, no aldehyde curing agent of the invention is water miscible difunctional curing agent.In other words, difunctional curing agent
The Part I of available reaction site on molecule can with other difunctionals solidify agent molecule reaction or with protein
Functional group（Particularly carboxylic acid and amino）Reaction.The Part II of available reaction site on difunctional solidification agent molecule can
To be connected to form covalent bond and/or hydrogen bond with wood fibre substrate.Also, this based epoxy resin is cheap, with wood fibre
Element and soy meal reaction time are short, and reaction temperature is low, efficiency high, can be widely applied in a variety of wood-processing industries.
In the embodiment of the present invention, vegetable protein is little Mai paddy Yuan albumen, zeins and beans egg
One or more in white.Preferably, it is peas protein；It is highly preferred that it is soybean protein.
Soybean protein is the Exemplary protein used in adhesive example disclosed in this invention, presently disclosed
Albumen base timber adhesive any type of soy protein products can be used.Mesh first three most common soy protein products point
It is not soy meal, soybean protein concentrate, and soybean protein isolate（SPI）.Maximum difference between these products is protein
Content.Typically, soy meal includes about 45 wt% protein, and soybean protein concentrate includes at least about 65 wt% egg
White matter（Dry weight）, SPI includes at least about 85 wt% protein（Dry weight）.
In some embodiments of the present invention, soybean protein is preferably SPI or soy meal；More preferably soybean
Powder.
In the present invention, the lignin generally refers to assign the novolac polymer race of vegetable material strength and stiffness.Institute
State lignin can include analysis lignin preparation for example BRAUNS lignin, cellulase lignin, dioxanes acidolysis lignin,
Grind wood lignin, Klason lignin or periodic acid lignin etc., and industrial lignin preparation such as brown paper is wooden
Element or lignosulfonates etc..Because kraft lignin has the features such as cost is low, and performance is good, the situation of equal usage amount
Under, the performance comparable of the product obtained using kraft lignin uses the high 5%-10% of properties of product of other lignin.Same
Its properties of product can improve more than 10% in the case of etc. cost.Therefore, in the embodiment of the present invention, lignin is excellent
Elect kraft lignin as.
In the present invention, the inorganic base is the oxide or hydroxide of IA races, or the oxide of Group IIA, hydroxide
Thing or borate.Preferably, inorganic base is sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or Boratex.
Filler is silica, paraffin, wheat flour, bark powder, nut in the albumen base timber adhesive of the present invention
Shell powder or its analog.
Because the synthetic method of polynary expoxy propane chain quaternary amine salt epoxy resin of the present invention is simple, raw material is honest and clean
Valency, good water solubility；And its temperature with the reaction of albumen base can be greatly reduced, shorten the time with the reaction of albumen base.Therefore,
The present invention is cheap using the cost of its albumen base timber adhesive being prepared as curing agent；And in the production and use process
It is pollution-free；Its primary raw material is all from renewable resource；Bonding strength is high；Wet strength after boiling water boiling can be compared with phenol glue；
And operating procedure is simple, the advantages that energy-conservation.Therefore, albumen base timber adhesive of the present invention is that one kind has good answer
With the wood adhesive product of prospect.
In the present invention, the turnaround time of albumen base timber adhesive is generally 1-2 hours, will be crosslinked solidification afterwards.
But the turnaround time generally required during industrial mass production is 6-8 hours.Therefore, in order to this hair is greatly improved
The turnaround time of bright adhesive, present invention also offers the preparation and application of another albumen base timber adhesive.Should
Albumen base timber adhesive reaches the purpose of extension turnaround time by adding farina；The performance of adhesive is kept simultaneously
Do not changed with other characteristics.Preferably, the albumen base timber adhesive replaces traditional inorganic base with lewis base, and
Add farina.
In the embodiment of the present invention, albumen base timber adhesive includes vegetable protein, lignin, solidified without aldehyde
Agent, farina, inorganic base and filler.Wherein, the gross weight based on the albumen base timber adhesive；
The content of vegetable protein is 5-50wt%；
The content of farina is 5-15wt%；
The content of lignin is 0-30wt%；
Content without aldehyde curing agent is 1-30wt%；
The content of inorganic base is 0.1-15wt%；
The content of filler is 0-20wt%.
In a preferred embodiment of the invention, albumen base timber adhesive includes vegetable protein, lignin, solidified without aldehyde
Agent, farina, lewis base and filler.Wherein, the gross weight based on the albumen base timber adhesive；
The content of vegetable protein is 5-50wt%；
The content of farina is 5-15wt%；
The content of lignin is 0-30wt%；
Content without aldehyde curing agent is 1-30wt%；
The content of lewis base is 0.1-15wt%；
The content of filler is 0-20wt%.
Wherein, lewis base is preferably triethylamine or calcium acetate.
In a preferred embodiment of the invention, the gross weight based on the albumen base timber adhesive；Vegetable protein
Content is 5-40 wt%；The content of farina is 5-15 wt%；The content of lignin is 0-20 wt%；Without aldehyde curing agent
Content be 3-25wt%；The content of lewis base is 0.2-12wt%；The content of filler is 0-20wt%.
Farina used in the present invention is the starch product after the drying of edible or feed rank.Pass through addition
The turnaround time of adhesive can be extended to 6-8 hours by farina by 1-2 hours before, so that such adhesive is fitted
The needs that industrial should significantly produce.
On the other hand, present invention also offers a kind of method for preparing above-mentioned this kind of nontoxic protein base timber adhesive, bag
Include following steps：
Step 1）, the inorganic base that is added to the mixture of vegetable protein or vegetable protein and lignin or Louis's alkali soluble
In liquid, stirring is until albumen and lignin are completely dispersed in the solution；
Step 2）, to step 1）Formaldehydeless curing agent is added in solution after scattered or adds formaldehydeless curing agent and Ma Ling
Sweet potato starch, stir；
Step 3）, to step 2）Filler is added in solution after stirring, adds and stirs, so as to obtain albumen base
Wood adhesive.
In the preparation process in accordance with the present invention, also inorganic base first can be added into no aldehyde when preparing albumen base timber adhesive to solidify
Stirred in agent solution, add the mixture of vegetable protein or vegetable protein and lignin, after stirring again on demand
Add filler.
On the other hand, present invention also offers a kind of application of above-mentioned albumen base timber adhesive.
Albumen base timber adhesive of the present invention can be used for wood-base fibre and particle panel material such as glued board, woodwork plate, bamboo glued
Plate, particieboard（OSB）, flake board, fiberboard（Including Midst density and high density fiberboard）, parallel become a useful person（PSL）, interlayer
Become a useful person（LSL）, laminated veneer lumber（LVL）, and all kinds of composite floor boards, bamboo flooring, consolidated floor etc..
Application method of a kind of above-mentioned albumen base timber adhesive in timber is bonded, by the albumen base timber adhesive
The veneer surface of wood-base fibre and particle panel material is applied to by roller coat, scraper for coating, curtain coating, or sprinkling；Then multiple veneer heaps
Accumulate to form the sheet material of required thickness；Resulting sheet is displayed again, cold pressing, hot pressing obtain composite wood wood-based plate.
Above-mentioned wood-base fibre and particle panel material includes glued board, woodwork plate, bamboo plywood, particieboard, flake board, fiberboard, flat
Row is become a useful person, interlayer is become a useful person, laminated veneer lumber, all kinds of composite floor boards, bamboo flooring or consolidated floor.
Above-mentioned hot pressing time is 0.5-0.8 min/mm, and hot pressing temperature is 100 DEG C -190 DEG C, and hot pressing pressure is 9-15 public
Jin/square centimeter.
In the present invention, can be with by albumen base timber adhesive of the present invention when producing glued board for bonding
The surface of wood-base fibre and particle panel material veneer is applied to by roller coat, scraper for coating, curtain coating, or sprinkling；Then the accumulation of multiple veneers with
The sheet material of thickness needed for formation；Sheet material is displayed again, is cold-pressed, hot pressing obtains composite wood wood-based plate.Fiberboard can by wet felt/
Wetpressing, dry felt/dry compression methodology, or wet felt/dry compression methodology are made.
In the embodiment of the present invention, the assembly time of sheet material is 1-3 hours at room temperature；Cold pressing pressure is generally
6-10 kg/cms（Room temperature）, hot pressing pressure is generally 9-15 kg/cms.Wherein hot pressing time is 0.5-0.8
Min/mm, hot pressing temperature can change between 90 DEG C -200 DEG C, preferably 100 DEG C -190 DEG C.Gained composite wood wood-based plate
Dry shape bonding strength>4 MPa, in general, wet after soaking 3 h in 60 DEG C of hot water can reach 1.2 more than MPa by force,
Completely up to the use standard of two class glue.In the art, according to wood-based plate in national standard and face artificial board physicochemical property
The regulation of method of testing, in wet method detection, the dry shape bonding strength of gained glued board>2 MPa are qualified glued board；
Also, the dry shape bonding strength of glued board illustrates that the adhesive power of the adhesive is fine when being 4-5 MPa.
On the other hand, the user present invention also offers a kind of above-mentioned albumen base timber adhesive in timber is bonded
Method.In specifically used method, because the quaternary ammonium salt epoxy curing agent in the albumen base timber adhesive is with longer
Open hour.Therefore, before applied to timber is bonded, the other compositions of curing agent and binding agent are mixed in the very short time
Together, so as to which the binding agent formed has the open hour for being up to about a week before timber is bonded.
In the present invention, when the adhesive of embodiment synthesis is used to bond timber as wood adhesive, the timber is
By taking glued board as an example, the surface of plywood single board can be applied to by roller coat, scraper for coating, curtain coating, or sprinkling；Then it is more
Individual veneer is accumulated to form the sheet material of required thickness；Finally resulting sheet is displayed, cold pressing, hot pressing obtain composite plywood.Its
In, the detection method of the composite plywood of synthesis is according to specified in wood-based plate and face artificial board physicochemical property method of testing
What wet method detection method was carried out.Resulting sheet assembly time is 1 hour at room temperature, and cold pressing pressure is 6-10 kg/cms（Room
Temperature）；Hot pressing time is 0.5-0.8 min/mm, and hot pressing temperature is 100 DEG C -150 DEG C, and hot pressing pressure is 9-12 kilograms/square li
Rice.
Quaternary ammonium salt epoxy resin and its synthesis：
1st, compound IA
（IA）
1404.4 g water are added in 2000 mL there-necked flask, then are slowly added into 2,4,6- tri--(dimethylamino methyl) benzene
Phenol（DMP30,167.5 g, 661 mmol, 95%）.Add and solution is cooled to 0 DEG C, slowly instill epoxychloropropane（174.8 g,
1.89 mol）, control temperature to be less than 25 DEG C during dropwise addition.2 h are stirred after dripping off at this temperature, then temperature is risen into 30 DEG C of stirrings
1 h, obtain aromatic curing agent DMP30- epoxychloropropane IA.
2nd, compound IB
（IB）
1048.8 g water are added in 2000 mL there-necked flask, then are slowly added into 3,5- bis--(dimethylamino methyl) phenol
（137.5 g, 661 mmol）.Add and solution is cooled to 0 DEG C, slowly instill epoxychloropropane（124.7 g, 1.22 mol）, drop
Added-time control temperature is less than 25 DEG C.2 h are stirred after dripping off at this temperature, then temperature is risen into 30 DEG C of 1 h of stirring, obtain fragrance
Race curing agent 3,5- bis--(dimethylamino methyl) phenol-epoxy chloropropane IB.
3rd, compound IC
（IC）
1048.8 g water are added in 2000 mL there-necked flask, then are slowly added into 2,4- bis--(dimethylamino methyl) phenol
（137.5 g, 661 mmol）.Add and solution is cooled to 0 DEG C, slowly instill epoxychloropropane（124.7 g, 1.22 mol）, drop
Added-time control temperature is less than 25 DEG C.2 h are stirred after dripping off at this temperature, then temperature is risen into 30 DEG C of 1 h of stirring, obtain fragrance
Race curing agent 2,4- bis--(dimethylamino methyl) phenol-epoxy chloropropane IC.
4th, compound IIA
（IIA）
856 g water are added in 2000 mL there-necked flask, then are slowly added into N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine
（103.4 g, 0.6 mol）Add and solution is cooled to 0 DEG C, slowly instill epoxychloropropane（110.6 g, 1.2mol）, during dropwise addition
Temperature is controlled to be less than 25 DEG C.2 h are stirred after dripping off at this temperature, then temperature is risen into 30 DEG C of 1 h of stirring, aliphatic is obtained and consolidates
Agent tetramethyl -1,6- hexamethylene diamines-epoxychloropropane IIA.
5th, compound IIB
（IIB）
628.8 g water are added in 2000 mL there-necked flask, then are slowly added into N, N, N ', N '-tetramethylethylenediamine
（EMTDA, 28.2 g, 0.7 mol）.Add and solution is cooled to 0 DEG C, slowly instill epoxychloropropane（129 g, 1.4 mol）,
Temperature is controlled to be less than 25 DEG C during dropwise addition.2 h are stirred after dripping off at this temperature, then temperature is risen into 30 DEG C of 1 h of stirring, obtain fat
Fat race curing agent tetramethyl-ethylenediamine-epoxychloropropane（EMTDA- epoxychloropropane）IIB.
6th, compound IIC
（IIC）
989.6 g water are added in 2000 mL there-necked flask, then are slowly added into tetramethyl-positive certain herbaceous plants with big flowers diamines（136.8 g,
0.6 mol）Add and solution is cooled to 0 DEG C, slowly instill epoxychloropropane（110.6 g, 1.2mol）, control during dropwise addition temperature small
In 25 DEG C.2 h are stirred after dripping off at this temperature, then temperature is risen into 30 DEG C of 1 h of stirring, obtain aliphatic firming agent tetramethyl
Base-positive decamethylene diamine-epoxychloropropane IIC.
7th, compound IID
（IID）
922.4 g water are added in 2000 mL there-necked flask, then are slowly added into tetramethyl -4,6 dimethylhexanediamine（120
G, 0.6 mol）Add and solution is cooled to 0 DEG C, slowly instill epoxychloropropane（110.6 g, 1.2mol）, temperature is controlled during dropwise addition
Less than 25 DEG C.2 h are stirred after dripping off at this temperature, then temperature is risen into 30 DEG C of 1 h of stirring, obtain aliphatic firming agent tetramethyl
The dimethylhexanediamine of base-4,6-epoxychloropropane IID.
8th, compound IIE
（IIE）
848.8 g water, tetramethyl -3- propyl succinimide amine are added in 2000 mL there-necked flask（111.6 g, 0.6 mol）
Add and solution is cooled to 0 DEG C, slowly instill epoxychloropropane（110.6 g, 1.2mol）, control temperature to be less than 25 DEG C during dropwise addition.
2 h are stirred after dripping off at this temperature, then temperature is risen into 30 DEG C of 1 h of stirring, obtain aliphatic firming agent tetramethyl -3- propyl group
Butanediamine-epoxychloropropane IIE.
Embodiment 1
Synthetic proteins base timber adhesive A
In 500 mL beakers, by soy meal（20 grams）36 grams of water being slowly added in stirring, slowly instill 20 wt%
NaOH solution, the pH to 10 of big soybean milk liquid is adjusted, after continuing stirring 10 minutes, 40 are added into the alkaline soy meal mixed solution
Gram 10 wt% DMP30- epoxychloropropane（IA）The aqueous solution, add and continue 10 minutes obtained mixed solutions of stirring as using
In the adhesive A for bonding timber.After tested, the dry shape bonding strength of gained composite plywood is 5 MPa, through being soaked in 60 DEG C of hot water
Steep after 3 h it is wet it is strong be 1.5 MPa.
Embodiment 2
Synthetic proteins base timber adhesive B
In 500 mL beakers, 40 gram of 10 wt% DMP30- epoxychloropropane（IA）The aqueous solution be added to stirring in 36
In gram water, with vigorous stirring, 0.2 gram of CaO is slowly added into, stirred 10 minutes.20 grams of bean powderes are slowly added into again, add continuation
20 minutes obtained mixed solutions of stirring are as the adhesive B for bonding timber.After tested, the dry shape of gained composite plywood
Bonding strength is 4.6 MPa, after soaking 3 h in 60 DEG C of hot water it is wet it is strong be 1.6 MPa.
Embodiment 3
Synthetic proteins base timber adhesive C
In 500 mL beakers, 30 gram of 10 wt% DMP30- epoxychloropropane（IA）The aqueous solution be added to stirring in 60
In gram water, with vigorous stirring, 0.2 gram of NaOH is slowly added into, adds 30 grams of bean powderes and MgO mixture（That is 24 grams of bean powderes
With 6 grams of MgO）, add and continue to stir 20 minutes obtained mixed solutions as the adhesive C for bonding timber.After tested, institute
The dry shape bonding strength of composite plywood be 4.8 MPa, wet after soaking 3 h in 60 DEG C of hot water is by force 1.5 MPa.
Embodiment 4
Synthetic proteins base timber adhesive D
In 500 mL beakers, by soy meal（20 grams）36 grams of water being slowly added in stirring, slowly instill 20 wt%
NaOH solution, the pH to 10 of big soybean milk liquid is adjusted, after continuing stirring 10 minutes, added into the mixed solution of the alkaline soy meal
40 gram of 10 wt% aliphatic firming agent（EMTDA- epoxychloropropane IIB）The aqueous solution, while adjust curing agent IIB and bean powder
Part by weight be respectively 1：6,1：4,1：3,1：2；Add and continue 10 minutes obtained mixed solutions of stirring as bonding
The adhesive D of timber.After tested, the dry shape bonding strength of gained composite plywood is all higher than 4.0 MPa, through being soaked in 60 DEG C of hot water
That steeps after 3 h wet is all higher than 1.3 MPa by force.
Embodiment 5
Synthetic proteins base timber adhesive E
In 500 mL beakers, by soy meal（20 grams）36 grams of water being slowly added in stirring, slowly instill 20 wt%
NaOH solution, the pH to 10 of big soybean milk liquid is adjusted, after continuing stirring 10 minutes, added in the soy meal mixed solution alkaline to this
40 gram of 10 wt% -4,6 dimethylhexanediamines of aliphatic firming agent tetramethyl-epoxychloropropane（Compound IID）The aqueous solution,
It is respectively 1 to adjust curing agent IID and the part by weight of bean powder simultaneously：6,1：4,1：3,1：2；Add to continue to stir 10 minutes and obtain
Mixed solution as bonding the adhesive E of timber.After tested, the dry shape bonding strength of gained composite plywood is all higher than
4.2 MPa, after soaking 3 h in 60 DEG C of hot water it is wet it is strong be 1.3 MPa.
Embodiment 6
Synthetic proteins base timber adhesive F
In 500 mL beakers, 44 gram of 10 wt% tetramethyl-ethylenediamine-epoxychloropropane（IID）The aqueous solution be added to
In 60 grams of water in stirring, with vigorous stirring, 0.2 gram of NaOH is slowly added into, stirred 10 minutes.Add 5 grams of glycerine and
0.2 gram of Na2B4O7, is stirred, then 15 grams of bean powderes are slowly added into, and is stirred, and is added 5 grams of wheat flours, is added continuation
20 minutes obtained mixed solutions of stirring are as the adhesive F for bonding timber.After tested, the dry shape of gained composite plywood
Bonding strength is 5.1 MPa, after soaking 3 h in 60 DEG C of hot water it is wet it is strong be 1.4 MPa.
Embodiment 7
Synthetic proteins base timber adhesive G
In 500 mL beakers, 40 gram of 10 wt% tetramethyl -1,6- hexamethylene diamine-epoxychloropropane（IIA）The aqueous solution
It is added in 90 grams of water in stirring, with vigorous stirring, is slowly added into 0.2 gram of NaOH, stirs 10 minutes；Add 10 gram 12.5
Wt% polyamide polyamine-epoxychloropropane（PAE）, after stirring 10 minutes, 26 grams of bean powderes are slowly added into, adds and continues to stir
20 minutes obtained mixed solutions are as the adhesive G for bonding timber.After tested, the dry shape of gained composite plywood is glued
Intensity is 5.2 MPa, after soaking 3 h in 60 DEG C of hot water it is wet it is strong be 1.5 MPa.
Embodiment 8
Synthetic proteins base timber adhesive H
In 500 mL beakers, 44 gram of 10 wt% tetramethyl -1,6- hexamethylene diamine-epoxychloropropane（IIA）The aqueous solution
It is added in 100 grams of water in stirring, with vigorous stirring, 0.2 gram of Na2B4O7, stirs, add 6 grams of CMC, stirring is equal
It is even, then 30 grams of bean powderes are slowly added into, add and continue to stir 20 minutes obtained mixed solutions as the glue for bonding timber
Stick H.After tested, the dry shape bonding strength of gained composite plywood is 4.9 MPa, wet after soaking 3 h in 60 DEG C of hot water
Strong is 1.6 MPa.
Embodiment 9
Synthetic proteins base timber adhesive I
In 500 mL beakers, 40 gram of 10 wt% DMP30- epoxychloropropane（IA）The aqueous solution be added to stirring in
In 100 grams of water, with vigorous stirring, 0.2 gram of NaOH is slowly added into, stirred 10 minutes.Add the poly- of 10 gram of 12.5 wt%
Acid amides polyamine-epichlorohydrin（PAE）, after stirring 10 minutes, 26 grams of bean powderes are slowly added into, adds and continues to stir 20 minutes
To mixed solution as bonding the adhesive I of timber.After tested, the dry shape bonding strength of gained composite plywood is
5.5 MPa, after soaking 3 h in 60 DEG C of hot water it is wet it is strong be 1.6 MPa.
Embodiment 10
Synthetic proteins base timber adhesive J
Key step is such as embodiment 9, the difference is that adding the mixture of 26 grams of bean powderes and ox-hide lignin（Dry weight is than 3：
1）To replace 26 grams of bean powderes, add and continue to stir 10 minutes obtained mixed solutions as the adhesive J for bonding timber.Through
Test, the dry shape bonding strength of gained composite plywood is 5.2 MPa, wet strong for 1.5 after soaking 3 h in 60 DEG C of hot water
MPa。
Embodiment 11
Synthetic proteins base timber adhesive K
In 500 mL beakers, 44 gram of 10 wt% compound（IE）The aqueous solution be added to stirring in 60 grams of water in,
It is stirred vigorously down, is slowly added into 0.2 gram of NaOH, stirs 10 minutes.5 grams of glycerine and 0.3 gram of Na2B4O7 are added, stirring is equal
It is even, then 15 grams of bean powderes are slowly added into, stir, add 5 grams of wheat flours, add and continue to stir obtained mixing in 20 minutes
Solution is as the adhesive K for bonding timber.After tested, the dry shape bonding strength of gained composite plywood is 4.8 MPa, warp
Soaked in 60 DEG C of hot water after 3 h it is wet it is strong be 1.3 MPa.
Embodiment 12
Synthetic proteins base timber adhesive L
In 500 mL beakers, 44 gram of 10 wt% compound（IC）The aqueous solution be added to stirring in 100 grams of water in,
It is stirred vigorously down, 0.3 gram of Na2B4O7, stirs, add 5 grams of CMC, stir, then 30 grams of bean powderes is slowly added into,
Add and continue to stir 20 minutes obtained mixed solutions as the adhesive L for bonding timber.After tested, the compound gluing of gained
The dry shape bonding strength of plate is 5.6 MPa, after soaking 3 h in 60 DEG C of hot water it is wet it is strong be 1.8 MPa.
Embodiment 13
Synthetic proteins base timber adhesive M
In 500 mL beakers, by soy meal（20 grams）36 grams of water being slowly added in stirring, slowly instill triethylamine, adjust
The pH to 8 of big soybean milk liquid is saved, after continuing stirring 10 minutes, 40 gram of 10 wt% of addition into the mixed solution of the alkaline soy meal
The aqueous solution of DMP30- epoxychloropropane, add and continue to stir 10 minutes obtained mixed solutions as the glue for bonding timber
Stick M.After tested, the dry shape bonding strength of gained composite plywood is 5 MPa, wet strong after soaking 3 h in 60 DEG C of hot water
For 1.5 MPa.Its turnaround time is 6 hours.
Embodiment 14
Synthetic proteins base timber adhesive N
In 500 mL beakers, the aqueous solution of 40 gram of 10 wt% DMP30- epoxychloropropane is added to 36 grams of water in stirring
In, with vigorous stirring, 0.2 gram of calcium acetate is slowly added into, stirred 10 minutes.20 grams of bean powderes are slowly added into again, add continuation
20 minutes obtained mixed solutions of stirring are as the adhesive N for bonding timber.After tested, the dry shape of gained composite plywood
Bonding strength is 4.6 MPa, after soaking 3 h in 60 DEG C of hot water it is wet it is strong be 1.6 MPa.Its turnaround time is 6 hours.
Embodiment 15
Synthetic proteins base timber adhesive O
In 500 mL beakers, the aqueous solution of 30 gram of 10 wt% DMP30- epoxychloropropane is added to 60 grams of water in stirring
In, with vigorous stirring, 0.2 gram of calcium acetate is slowly added into, adds the mixture of 30 grams of bean powderes and farina（I.e. 24 grams
Bean powder and 6 g potato starch）, add and continue to stir 20 minutes obtained mixed solutions as the adhesive for bonding timber
O.After tested, the dry shape bonding strength of gained composite plywood is 4.8 MPa, and wet after soaking 3 h in 60 DEG C of hot water is by force
1.5 MPa.Its turnaround time is 7 hours.
Embodiment 16
Synthetic proteins base timber adhesive P
In 500 mL beakers, 44 gram of 10 wt% tetramethyl-ethylenediamine-epoxychloropropane（IID）The aqueous solution be added to
In 60 grams of water in stirring, with vigorous stirring, 0.2 gram of calcium acetate is slowly added into, stirred 10 minutes.Again by 15 grams of bean powderes
It is slowly added into, stirs, add 5 g potato starch, adds and continue 20 minutes obtained mixed solutions of stirring as use
In the adhesive P for bonding timber.After tested, the dry shape bonding strength of gained composite plywood is 5.1 MPa, through in 60 DEG C of hot water
Soak after 3 h it is wet it is strong be 1.4 MPa.Its turnaround time is 8 hours.
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound
The property made work can makes many modifications and variations according to the design of the present invention.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be in the protection domain being defined in the patent claims.
Claims (13)
- A kind of 1. albumen base timber adhesive, it is characterised in that：Including vegetable protein, lignin, without aldehyde curing agent, alkali and fill out Material；Based on the gross weight of the albumen base timber adhesive,The content of the vegetable protein is 5-50wt%；The content of the lignin is 0-30wt%；The content of the no aldehyde curing agent is 1-30wt%；The content of the alkali is 0.1-15wt%；The content of the filler is 0-20wt%；The formaldehydeless curing agent includes polynary expoxy propane chain quaternary ammonium salt epoxy resin, polynary expoxy propane chain quaternary amine Epoxy resin is aromatic series or aliphatic quaternary ammonium salt epoxy resin containing 2 or the expoxy propane of more than 2；The aromatic series Quaternary ammonium salt epoxy resin, the structural formula difference of aliphatic quaternary ammonium salt epoxy resin are as follows：（I）,（II）,Wherein, m, n are integer, and n=2-3, m=2-10.
- 2. albumen base timber adhesive according to claim 1, it is characterised in that：The vegetable protein is little Mai paddy Yuan eggs In vain, zeins or peas protein.
- 3. albumen base timber adhesive according to claim 1, it is characterised in that：The lignin is that BRAUNS is wooden Element, cellulase lignin, dioxanes acidolysis lignin, grind wood lignin, Klason lignin, periodic acid lignin, Kraft lignin or lignosulfonates.
- 4. albumen base timber adhesive according to claim 1, it is characterised in that：The formaldehydeless curing agent also includes poly- Acid amides polyamine or polyamide polyamine-epoxychloropropane, carboxymethyl cellulose, glycerine or starch.
- 5. albumen base timber adhesive according to claim 1, it is characterised in that：Polynary expoxy propane chain quaternary amine ring Oxygen tree fat is DMP30- epoxy resin, EMTDA- epoxychloropropane or tetramethyl -1,6- hexamethylene diamines-epoxychloropropane.
- 6. albumen base timber adhesive according to claim 1, it is characterised in that：The alkali is sodium hydroxide, hydroxide Potassium, calcium hydroxide, calcium oxide, Boratex, triethylamine or calcium acetate.
- 7. albumen base timber adhesive according to claim 1, it is characterised in that：The filler be silica, paraffin, Wheat flour, bark powder or shuck powder.
- 8. the albumen base timber adhesive as any one of claim 1-7, it is characterised in that：Described albumen sill material Adhesive also includes farina, based on the gross weight of the albumen base timber adhesive, the content of the farina For 5-15wt%.
- A kind of 9. method for preparing the albumen base timber adhesive as described in claim any one of 1-8, it is characterised in that：Including with Lower step：Step 1）, the mixture of vegetable protein or vegetable protein and lignin is added in inorganic base or solution of Lewis base, Stirring is until vegetable protein and lignin are completely dispersed in the solution；Step 2）, to step 1）In disperse after solution in add formaldehydeless curing agent or add formaldehydeless curing agent and potato Starch, stir；Step 3）, to step 2）Filler is added in solution after stirring, adds and stirs, so as to obtain the albumen base Wood adhesive.
- A kind of 10. application of protein-based wood adhesive as claimed in claim 9, it is characterised in that：Described albumen base Wood adhesive can be used for wood-base fibre and particle panel material and all kinds of composite floor boards, bamboo flooring, consolidated floor glued board；It is described wooden artificial Plate is woodwork plate, bamboo plywood, particieboard（OSB）, flake board, fiberboard, parallel become a useful person（PSL）, interlayer becomes a useful person （LSL）, laminated veneer lumber（LVL）.
- A kind of 11. application method of albumen base timber adhesive as claimed in claim 9, it is characterised in that：By the albumen Base timber adhesive is applied to the veneer surface of wood-base fibre and particle panel material by roller coat, scraper for coating, curtain coating, or sprinkling；Then it is more The individual veneer is accumulated to form the sheet material of required thickness；Resulting sheet is displayed again, cold pressing, that hot pressing obtains composite wood is artificial Plate.
- 12. the application method of albumen base timber adhesive according to claim 11, it is characterised in that：It is described wooden artificial Plate includes glued board, woodwork plate, particieboard, fiberboard, laminated veneer lumber, composite floor board or consolidated floor.
- 13. the application method of albumen base timber adhesive according to claim 11, it is characterised in that：During described hot pressing Between be 0.5-0.8 min/mm, hot pressing temperature is 100 DEG C -190 DEG C, and hot pressing pressure is 9-15 kg/cms.
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| CN201510016168.6A CN104774588B (en) | 2014-01-13 | 2015-01-13 | A kind of albumen base timber adhesive and its preparation method and application and application method |
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| CN201410013631.7A CN103740326A (en) | 2014-01-13 | 2014-01-13 | Protein-based wood adhesive and preparation method thereof |
| CN2014100136317 | 2014-01-13 | ||
| CN201510016168.6A CN104774588B (en) | 2014-01-13 | 2015-01-13 | A kind of albumen base timber adhesive and its preparation method and application and application method |
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| CN104774588B true CN104774588B (en) | 2018-03-13 |
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| CN201410013631.7A Pending CN103740326A (en) | 2014-01-13 | 2014-01-13 | Protein-based wood adhesive and preparation method thereof |
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| WO2024011256A1 (en) * | 2022-07-08 | 2024-01-11 | Trustees Of Tufts College | Renewable and sustainable composite wood compositions and methods of making and using the same |
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| WO2024011256A1 (en) * | 2022-07-08 | 2024-01-11 | Trustees Of Tufts College | Renewable and sustainable composite wood compositions and methods of making and using the same |
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| CN103740326A (en) | 2014-04-23 |
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