CN104774588A - Protein-based wood adhesive, and preparation method and application and use method thereof - Google Patents

Protein-based wood adhesive, and preparation method and application and use method thereof Download PDF

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CN104774588A
CN104774588A CN201510016168.6A CN201510016168A CN104774588A CN 104774588 A CN104774588 A CN 104774588A CN 201510016168 A CN201510016168 A CN 201510016168A CN 104774588 A CN104774588 A CN 104774588A
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protein
wood adhesive
based wood
adhesive
xylogen
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CN104774588B (en
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阎肖华
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Henan Wanguang Construction Co ltd
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Abstract

The invention relates to a wood adhesive and a preparation method thereof, and especially relates to a protein-based wood adhesive prepared from vegetable proteins and nontoxic epoxy resin, and a preparation method and an application and use method thereof. The protein-based wood adhesive is prepared from natural vegetable proteins, a formaldehyde-free epoxy resin curing agent and a filler, is a nontoxic environmentally-friendly adhesive, and does not release formaldehyde or toxic organic matters in the application process or the use process of a finished product; and the adhesive has high adhesion strength and good water resistance, the strength of the adhesive boiled in boiling water has same performances with phenolic adhesives, and the adhesive completely reaches use standards of 2 level adhesives. The preparation method of the protein-based wood adhesive is simple; and the hot pressing time of the protein-based wood adhesive is much lower than that of formaldehyde-type adhesives, so energy is greatly saved.

Description

A kind of protein-based wood adhesive and its preparation method and application and using method
Technical field
The present invention relates to a kind of wood adhesive and preparation method thereof, particularly relate to a kind of protein-based wood adhesive be made up of vegetable-protein and non-toxic epoxy and its preparation method and application and using method.
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 used soybean protein and other additive to make wood adhesive at that time.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.U.S. California Air Resources Board(CARB in 2007) there is 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 US 7,722,712 B2 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 (Dolbey R. etc. Recent developments in epoxy resins. Rapra Rev. 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 provide a kind of with low cost, prepare simple and free of contamination novel protein base timber adhesive and its preparation method and application and using method, especially a kind of protein-based wood adhesive be made up of vegetable-protein and non-toxic epoxy and preparation method thereof is provided, protein-based wood adhesive utilizes vegetable-protein, and prepare free of contamination epoxy resin protein-based wood adhesive using the quaternary ammonium salt epoxy resin of cheapness as solidifying agent, in addition, the preparation method of protein-based wood adhesive is not only simple to operate, and reduce the product cost of protein-based wood adhesive.
The technical solution adopted in the present invention:
A kind of protein-based wood adhesive, comprise vegetable-protein, xylogen, without aldehyde solidifying agent, alkali and filler; Based on the gross weight of described protein-based wood adhesive,
The content of described vegetable-protein is 5-50wt%;
The content of described xylogen is 0-30wt%;
The described content without aldehyde solidifying agent is 1-30wt%;
The content of described alkali is 0.1-15wt%;
The content of described filler is 0-20wt%.
Preferably, based on the gross weight of described protein-based wood adhesive, the content of vegetable-protein is 10%-45 wt%.
More preferably, based on the gross weight of described protein-based wood adhesive, the content of vegetable-protein is 25-45 wt%; The content of xylogen is 0-20wt%; Content without aldehyde solidifying agent is 3-25wt%; The content of alkali is 0.2-12wt%; The content of filler is 0-20wt%.
Described formaldehydeless solidifying agent comprises polynary propylene oxide chain quaternary ammonium salt epoxy resin, such as, with the quaternary ammonium salt epoxy resin that DMP30-epoxy chloropropane (DMP30-Epichlorohydrin) is representative; Polynary propylene oxide chain quaternary amine epoxy resin refers to aromatic series containing the propylene oxide of more than 2 or 2 or aliphatic quaternary ammonium salt epoxy resin; Wherein, aromatic series quaternary ammonium salt epoxy resin is the phenol ring containing 2-3 propylene oxide substitution in side chain, and general structure is as shown in molecular formula (I); Or the aromatic ester quaternary ammonium resin containing the propylene oxide side chain of more than 2 or 2;
（I）；
Wherein, n is integer, and n=2-3.Preferably, aromatic series quaternary ammonium salt epoxy resin is commercially available DMP30-epoxy chloropropane, and its structural formula is as shown in molecular formula (IA):
（IA）。
Aliphatic quaternary ammonium salt epoxy resin is the carbon chain lengths of 2-10 carbon containing straight or branched and the quaternary ammonium salt epoxy resin of the multiple propylene oxide side chain of tool, its structure as shown in molecular formula (II),
（II）；
Wherein, m is integer, and m=2-10.
Preferably, aliphatic quaternary ammonium salt epoxy resin is EMTDA-epoxy chloropropane or tetramethyl--1,6-hexanediamine-epoxy chloropropane etc.
Described is the mixture of polynary propylene oxide chain quaternary amine epoxy resin or this polynary propylene oxide chain quaternary amine epoxy resin and other compounds without aldehyde solidifying agent, as the mixture of aliphatic polyhydroxy compound, multi-carboxy compound or polyamines based compound.
Preferably, aliphatic polyamine based compound is the aliphatic polymer containing more than 2 or 2 amidos, the reaction product of polymeric amide polyamine (molecular formula IIIA) as be known in the art or itself and epoxy haloalkane, as polyamide polyamine epichlorhydrin (PAE) (molecular formula IIIB) compound etc.
The expression formula of polymeric amide polyamine is as follows:
（IIIA）；
Wherein, R 1and R 2for the methylene radical of 2-10, be preferably hexanodioic acid and diethylenetriamine multipolymer.
The expression formula of polyamide polyamine epichlorhydrin is as follows:
（IIIB）。
Aliphatics multi-carboxy compound is CMC(carboxymethyl cellulose) or improvement after starch etc.Preferably, aliphatic polyhydroxy compound is glycerine or starch etc.More preferably, aliphatic polyhydroxy compound is glycerine.
When described be polynary propylene oxide chain quaternary amine epoxy resin without aldehyde solidifying agent time, the described content without aldehyde solidifying agent is the 1-30 wt% of adhesive weight; When without aldehyde solidifying agent being the mixture of polynary propylene oxide chain quaternary amine epoxy resin and other compounds, the weight ratio of polynary propylene oxide chain quaternary amine epoxy resin and other compounds is 1.5-8:1.
The polymerization single polymerization monomer of traditional epoxy resin generally only containing a propylene oxide structure, and the polymerization single polymerization monomer of propylene oxide of the present invention with aromatic nucleus or short carbon chain for molecule core, and from core, derive multiple propylene oxide chain.This structure has increased substantially polymerization efficiency, and the polymerization degree is multiplied, thus can reduce the usage quantity of polymerization single polymerization monomer, reduces costs.Meanwhile, because each polymerization single polymerization monomer is all containing multiple propylene oxide chain, therefore more easily form complicated reticulated polymeric structures after polymerisation, and then improve performance.Specifically for DMP30-epoxy chloropropane, the DMP30-epoxy chloropropane of per molecule contains three propylene oxide units, therefore after polymerization, complicated tridimensional network can be formed at three different directions chainings, so the theoretical performance after its unit molal quantity monomer polymerization is 3 times of traditional single epichlorohydrin resin, actual performance test is then 2.1 times of traditional single epichlorohydrin resin.And under the condition of same cost, performance can improve 80%.In addition because each molecule contains 3 quaternary amine structures, therefore it water-solublely improves greatly, be the 1.5-2 of general propylene oxide doubly.In sum, polynary propylene oxide chain quaternary amine epoxy resin of the present invention has following characteristics:
1, soluble in water;
2, can react with protein molecular and solidifying agent molecule itself;
3, the binding property reaction site of wood fiber base material can be provided.
Therefore, of the present invention is water miscible bifunctional solidifying agent without aldehyde solidifying agent.In other words, the first part of the available reaction site on bifunctional solidifying agent molecule can react with other bifunctional solidifying agent molecular reactions or with functional group's (particularly carboxylic acid and amino) of protein.The second section of the available reaction site on bifunctional solidifying agent molecule can be connected to form covalent linkage and/or hydrogen bond with wood fibre substrate.Further, this based epoxy resin is cheap, with lignocellulose and the soyflour reaction times short, temperature of reaction is low, and efficiency is high, can be widely applied in multiple wood-processing industry.
Described vegetable-protein is one or more in little Mai paddy Yuan albumen, zein and legume protein; Preferably, be legume protein; More preferably, be soybean protein; Described soybean protein is preferably SPI or soyflour; Be more preferably soyflour.
Soybean protein is the Exemplary protein used in tackiness agent example disclosed in this invention, and protein-based wood adhesive disclosed in this invention can use any type of soy protein products.Current three kinds of modal soy protein products are soyflour, soybean protein enriched material respectively, and soybean protein isolate (SPI).Maximum difference between these products is the content of protein.Typically, soyflour comprises the protein of about 45 wt%, and soybean protein enriched material comprises the protein (dry weight) at least about 65 wt%, and SPI comprises the protein (dry weight) at least about 85 wt%.
Described xylogen generally refers to the novolac polymer race giving vegetable material strength and stiffness.Described xylogen comprise analyze xylogen preparation as BRAUNS xylogen, cellulase xylogen, dioxan acidolysis xylogen, grind wood lignin, Klason xylogen or Periodic acid xylogen, and industrial lignin preparation is as kraft lignin or sulfonated lignin.Due to kraft lignin, to have cost low, the features such as performance is good, and when equal usage quantity, the performance comparable of the product using kraft lignin to obtain uses the product performance height 5%-10% of other xylogen.When equal cost, its product performance can improve more than 10%.Therefore, in the present invention, xylogen is preferably kraft lignin.
Described alkali is mineral alkali or Lewis base.Described mineral alkali is oxide compound or the oxyhydroxide of IA race, or the oxide compound of IIA race, oxyhydroxide or borate; Preferably, mineral alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or Sodium Tetraborate.Described Lewis base is preferably triethylamine or lime acetate.
Described filler is silicon-dioxide, paraffin, whole meal flour, tree bark powder, nutshell powder or its analogue.
In the present invention, the turnover time of protein-based wood adhesive is generally 1-2 hour, just can be cross-linked afterwards and solidify, but the turnover time generally needed in industrial mass production process is 6-8 hour.Therefore, in order to the turnover time increasing substantially tackiness agent of the present invention, protein-based wood adhesive of the present invention also comprises yam starch, reaches by adding yam starch the object extending the turnover time; Keep the performance of tackiness agent and other characteristics not to change simultaneously.Preferably, this protein-based wood adhesive replaces traditional mineral alkali with Lewis base, and adds yam starch.
Preferably, a kind of protein-based wood adhesive comprise vegetable-protein, xylogen, without aldehyde solidifying agent, yam starch, mineral alkali and filler; Based on the gross weight of described protein-based wood adhesive,
The content of vegetable-protein is 5-50wt%;
The content of yam starch is 5-15wt%;
The content of xylogen is 0-30wt%;
Content without aldehyde solidifying agent is 1-30wt%;
The content of mineral alkali is 0.1-15wt%;
The content of filler is 0-20wt%.
Preferably, a kind of protein-based wood adhesive comprise vegetable-protein, xylogen, without aldehyde solidifying agent, yam starch, Lewis base and filler; Based on the gross weight of described protein-based wood adhesive;
The content of vegetable-protein is 5-50wt%;
The content of yam starch is 5-15wt%;
The content of xylogen is 0-30wt%;
Content without aldehyde solidifying 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 lime acetate.
More preferably, based on the gross weight of described protein-based wood adhesive; The content of vegetable-protein is 5-40 wt%; The content of yam starch is 5-15 wt%; The content of xylogen is 0-20 wt%; Content without aldehyde solidifying 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 lime acetate.
Described yam starch is edible or starch product after the drying of feed rank; The turnover time of tackiness agent can be extended to 6-8 hour by 1-2 before hour by adding yam starch, thus make this type of tackiness agent adapt to the industrial needs significantly produced.
Prepare a method for above-mentioned protein-based wood adhesive, comprise the steps:
In step 1), the mineral alkali that the mixture of vegetable-protein or vegetable-protein and xylogen is joined or solution of Lewis base, stir until albumen and xylogen disperse in the solution completely;
Step 2), to step 1) dispersion after solution in add formaldehydeless solidifying agent or add formaldehydeless solidifying agent and yam starch, stir;
Step 3), to step 2) stir after solution in add filler, add and stir, thus obtain protein-based wood adhesive.
In above-mentioned preparation method, also first mineral alkali can be added to during preparation protein-based wood adhesive and stir without in aldehyde curing agent solution, then add the mixture of vegetable-protein or vegetable-protein and xylogen, after stirring, add filler again.
A kind of application of above-mentioned protein-based wood adhesive, described protein-based 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 protein-based wood adhesive in bonding timber, by described protein-based 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 0.5-0.8 min/mm, and hot pressing temperature is 100 DEG C-190 DEG C, and hot pressing pressure is 9-15 kg/cm.
Protein-based 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 0.5-0.8 min/mm, and hot pressing temperature can change between 90 DEG C-200 DEG C, is preferably 100 DEG C-190 DEG C.Dry shape bonding strength > 4 MPa of gained composite wood wood-based plate, in general, wetting after soaking 3 h in 60 DEG C of hot water can reach 1.2 more than MPa 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, dry shape bonding strength > 2 MPa 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 4-5 MPa.
A kind of protein-based wood adhesive in concrete use, because the quaternary ammonium salt epoxy curing agent in described protein-based wood adhesive has the longer open hour.Therefore, before being applied to bonding timber, other compositions in the very short time by solidifying agent and binding agent mix, thus the binding agent formed had the open hour up to about one week before bonding timber.
In the present invention, the synthetic method of polynary propylene oxide chain quaternary amine epoxy resin is simple, cheaper starting materials, good water solubility; And significantly can reduce the temperature that itself and protein-based are reacted, shorten the time of reacting with protein-based.Therefore, the protein-based wood adhesive for preparing for solidifying agent 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, protein-based wood adhesive of the present invention is a kind of wood adhesive product with applications well prospect.
Protein-based wood adhesive of the present invention is by natural plant protein and not formulated containing the epoxy curing agent of formaldehyde and filler etc.; Protein-based 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 protein-based 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 protein-based wood adhesive of the present invention is simple, and hot pressing time is far smaller than three-aldehyde glue, greatly saves the energy.The wherein environmental protection of product, being compared as follows shown in list of technique and performance characteristics.
Wherein, hot pressing time calculates for 18mm glued board.The main raw material of urea-formaldehyde resin adhesive refers to urea aldehyde and formaldehyde, and the main raw material in Phenol aldehyde resin refers to phenolic aldehyde and formaldehyde, and the main raw material in melamine resin adehsive refers to protein powder in trimeric cyanamide and formaldehyde and the present invention and solidifying agent.
Be described further below with reference to the technique effect of embodiment to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.
Embodiment
A kind of protein-based wood adhesive, this protein-based wood adhesive comprise vegetable-protein, xylogen, without aldehyde solidifying agent, mineral alkali and filler.Wherein, based on the gross weight of described protein-based wood adhesive;
The content of vegetable-protein is 5-50wt%;
The content of xylogen is 0-30wt%;
Content without aldehyde solidifying agent is 1-30wt%;
The content of mineral alkali is 0.1-15wt%;
The content of filler is 0-20wt%.
In a preferred embodiment of the invention, based on the gross weight of described protein-based wood adhesive, the content of vegetable-protein is 10%-45wt%.
More preferably, based on the gross weight of described protein-based wood adhesive, the content of vegetable-protein is 25-45 wt%; The content of xylogen is 0-20wt%; Content without aldehyde solidifying agent is 3-25wt%; The content of mineral alkali is 0.2-12wt%; The content of filler is 0-20wt%.
In the specific embodiment of the present invention, describedly comprise polynary propylene oxide chain quaternary ammonium salt epoxy resin, such as, with the quaternary ammonium salt epoxy resin that DMP30-epoxy chloropropane (DMP30-Epichlorohydrin) is representative without aldehyde solidifying agent.
In the present invention, polynary propylene oxide chain quaternary amine epoxy resin refers to aromatic series containing the propylene oxide of more than 2 or 2 or aliphatic quaternary ammonium salt epoxy resin.Wherein, aromatic series quaternary ammonium salt epoxy resin is the phenol ring containing 2-3 propylene oxide substitution in side chain, and general structure is as shown in molecular formula (I); Or the aromatic ester quaternary ammonium resin containing the propylene oxide side chain of more than 2 or 2;
（I）；
Wherein, n is integer, and n=2-3.Preferably, aromatic series quaternary ammonium salt epoxy resin is commercially available DMP30-epoxy chloropropane, and its structural formula is as shown in molecular formula (IA):
（IA）。
Aliphatic quaternary ammonium salt epoxy resin is the carbon chain lengths of 2-10 carbon containing straight or branched and the quaternary ammonium salt epoxy resin of the multiple propylene oxide side chain of tool, its structure as shown in molecular formula (II),
（II）；
Wherein, m is integer, and m=2-10.Preferably, aliphatic quaternary ammonium salt epoxy resin is EMTDA-epoxy chloropropane or tetramethyl--1,6-hexanediamine-epoxy chloropropane etc.
In the specific embodiment of the present invention, described is the mixture of polynary propylene oxide chain quaternary amine epoxy resin or this polynary propylene oxide chain quaternary amine epoxy resin and other compounds (as aliphatic polyhydroxy compound, multi-carboxy compound or polyamines based compound) without aldehyde solidifying agent.
Preferably, aliphatic polyamine based compound is the aliphatic polymer containing more than 2 or 2 amidos, the reaction product of such as polymeric amide polyamine (molecular formula IIIA) well known in the prior art or itself and epoxy haloalkane, as polyamide polyamine epichlorhydrin (PAE) (molecular formula IIIB) compound etc.
The expression formula of polymeric amide polyamine is as follows:
（IIIA）；
Wherein, R 1and R 2for the methylene radical of 2-10, be preferably hexanodioic acid and diethylenetriamine multipolymer.
The expression formula of polyamide polyamine epichlorhydrin is as follows:
（IIIB）。
In another preferred implementation of the present invention, aliphatics multi-carboxy compound is CMC(carboxymethyl cellulose) or improvement after starch etc.Aliphatic polyhydroxy compound is glycerine or starch etc.More preferably, aliphatic polyhydroxy compound is glycerine.
In the specific embodiment of the present invention, when being polynary propylene oxide chain quaternary amine epoxy resin without aldehyde solidifying agent, the described content without aldehyde solidifying agent is 1-30 wt % of adhesive weight.When without aldehyde solidifying agent being the mixture of polynary propylene oxide chain quaternary amine epoxy resin and other compounds, the weight ratio of polynary propylene oxide chain quaternary amine epoxy resin and other compounds is 1.5-8:1.
The polymerization single polymerization monomer of traditional epoxy resin generally only containing a propylene oxide structure, and the polymerization single polymerization monomer of propylene oxide of the present invention with aromatic nucleus or short carbon chain for molecule core, and from core, derive multiple propylene oxide chain.This structure has increased substantially polymerization efficiency, and the polymerization degree is multiplied, thus can reduce the usage quantity of polymerization single polymerization monomer, reduces costs.Meanwhile, because each polymerization single polymerization monomer is all containing multiple propylene oxide chain, therefore more easily form complicated reticulated polymeric structures after polymerisation, and then improve performance.Specifically for DMP30-epoxy chloropropane, the DMP30-epoxy chloropropane of per molecule contains three propylene oxide units, therefore after polymerization, complicated tridimensional network can be formed at three different directions chainings, so the theoretical performance after its unit molal quantity monomer polymerization is 3 times of traditional single epichlorohydrin resin, actual performance test is then 2.1 times of traditional single epichlorohydrin resin.And under the condition of same cost, performance can improve 80%.In addition because each molecule contains 3 quaternary amine structures, therefore it water-solublely improves greatly, be the 1.5-2 of general propylene oxide doubly.In sum, polynary propylene oxide chain quaternary amine epoxy resin of the present invention has following characteristics:
1, soluble in water;
2, can react with protein molecular and solidifying agent molecule itself;
3, the binding property reaction site of wood fiber base material can be provided.
Therefore, of the present invention is water miscible bifunctional solidifying agent without aldehyde solidifying agent.In other words, the first part of the available reaction site on bifunctional solidifying agent molecule can react with other bifunctional solidifying agent molecular reactions or with functional group's (particularly carboxylic acid and amino) of protein.The second section of the available reaction site on bifunctional solidifying agent molecule can be connected to form covalent linkage and/or hydrogen bond with wood fibre substrate.Further, this based epoxy resin is cheap, with lignocellulose and the soyflour reaction times short, temperature of reaction is low, and efficiency is high, can be widely applied in multiple wood-processing industry.
In the specific embodiment of the present invention, vegetable-protein is one or more in little Mai paddy Yuan albumen, zein and legume protein.Preferably, be legume protein; More preferably, be soybean protein.
Soybean protein is the Exemplary protein used in tackiness agent example disclosed in this invention, and protein-based wood adhesive disclosed in this invention can use any type of soy protein products.Current three kinds of modal soy protein products are soyflour, soybean protein enriched material respectively, and soybean protein isolate (SPI).Maximum difference between these products is the content of protein.Typically, soyflour comprises the protein of about 45 wt%, and soybean protein enriched material comprises the protein (dry weight) at least about 65 wt%, and SPI comprises the protein (dry weight) at least about 85 wt%.
In some embodiment of the present invention, soybean protein is preferably SPI or soyflour; Be more preferably soyflour.
In the present invention, described xylogen generally refers to the novolac polymer race giving vegetable material strength and stiffness.Described xylogen can comprise analyze xylogen preparation as BRAUNS xylogen, cellulase xylogen, dioxan acidolysis xylogen, grind wood lignin, Klason xylogen or Periodic acid xylogen etc., and industrial lignin preparation is as kraft lignin or sulfonated lignin etc.Due to kraft lignin, to have cost low, the features such as performance is good, and when equal usage quantity, the performance comparable of the product using kraft lignin to obtain uses the product performance height 5%-10% of other xylogen.When equal cost, its product performance can improve more than 10%.Therefore, in the specific embodiment of the present invention, xylogen is preferably kraft lignin.
In the present invention, described mineral alkali is oxide compound or the oxyhydroxide of IA race, or the oxide compound of IIA race, oxyhydroxide or borate.Preferably, mineral alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or Sodium Tetraborate.
In protein-based wood adhesive of the present invention, filler is silicon-dioxide, paraffin, whole meal flour, tree bark powder, nutshell powder or its analogue.
Because the synthetic method of polynary propylene oxide chain quaternary amine epoxy resin of the present invention is simple, cheaper starting materials, good water solubility; And significantly can reduce the temperature that itself and protein-based are reacted, shorten the time of reacting with protein-based.Therefore, the protein-based wood adhesive for preparing for solidifying agent 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, protein-based wood adhesive of the present invention is a kind of wood adhesive product with applications well prospect.
In the present invention, the turnover time of protein-based wood adhesive is generally 1-2 hour, just can be cross-linked afterwards and solidify.But the general turnover time needed is 6-8 hour in industrial mass production process.Therefore, in order to the turnover time increasing substantially tackiness agent of the present invention, present invention also offers the preparation and application of another kind of protein-based wood adhesive.This protein-based wood adhesive reaches by adding yam starch the object extending the turnover time; Keep the performance of tackiness agent and other characteristics not to change simultaneously.Preferably, this protein-based wood adhesive replaces traditional mineral alkali with Lewis base, and adds yam starch.
In the specific embodiment of the present invention, protein-based wood adhesive comprise vegetable-protein, xylogen, without aldehyde solidifying agent, yam starch, mineral alkali and filler.Wherein, based on the gross weight of described protein-based wood adhesive;
The content of vegetable-protein is 5-50wt%;
The content of yam starch is 5-15wt%;
The content of xylogen is 0-30wt%;
Content without aldehyde solidifying agent is 1-30wt%;
The content of mineral alkali is 0.1-15wt%;
The content of filler is 0-20wt%.
In a preferred embodiment of the invention, protein-based wood adhesive comprise vegetable-protein, xylogen, without aldehyde solidifying agent, yam starch, Lewis base and filler.Wherein, based on the gross weight of described protein-based wood adhesive;
The content of vegetable-protein is 5-50wt%;
The content of yam starch is 5-15wt%;
The content of xylogen is 0-30wt%;
Content without aldehyde solidifying 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 lime acetate.
In a preferred embodiment of the invention, based on the gross weight of described protein-based wood adhesive; The content of vegetable-protein is 5-40 wt%; The content of yam starch is 5-15 wt%; The content of xylogen is 0-20 wt%; Content without aldehyde solidifying agent is 3-25wt%; The content of Lewis base is 0.2-12wt%; The content of filler is 0-20wt%.
The yam starch used in the present invention is edible or starch product after the drying of feed rank.The turnover time of tackiness agent can be extended to 6-8 hour by 1-2 before hour by adding yam starch, thus make this type of tackiness agent adapt to the industrial needs significantly produced.
On the other hand, present invention also offers a kind of method preparing above-mentioned this kind of nontoxic protein base timber adhesive, comprise the steps:
In step 1), the mineral alkali that the mixture of vegetable-protein or vegetable-protein and xylogen is joined or solution of Lewis base, stir until albumen and xylogen disperse in the solution completely;
Step 2), to step 1) dispersion after solution in add formaldehydeless solidifying agent or add formaldehydeless solidifying agent and yam starch, stir;
Step 3), to step 2) stir after solution in add filler, add and stir, thus obtain protein-based wood adhesive.
In the preparation process in accordance with the present invention, also first mineral alkali can be added to during preparation protein-based wood adhesive and stir without in aldehyde curing agent solution, then add the mixture of vegetable-protein or vegetable-protein and xylogen, after stirring, add filler on demand again.
On the other hand, present invention also offers a kind of application of above-mentioned protein-based wood adhesive.
Protein-based wood adhesive of the present invention 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 protein-based wood adhesive in bonding timber, by described protein-based 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.
Above-mentioned 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.
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 kg/cm.
In the present invention, by protein-based wood adhesive of the present invention when being used for bonding production glued board, can roller coat, scraper for coating, curtain coating be passed through, or spray 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.
In the specific embodiment of the present invention, the assembly time of 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 0.5-0.8 min/mm, and hot pressing temperature can change between 90 DEG C-200 DEG C, is preferably 100 DEG C-190 DEG C.Dry shape bonding strength > 4 MPa of gained composite wood wood-based plate, in general, wetting after soaking 3 h in 60 DEG C of hot water can reach 1.2 more than MPa 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, dry shape bonding strength > 2 MPa 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 4-5 MPa.
On the other hand, present invention also offers the using method of a kind of above-mentioned protein-based wood adhesive in bonding timber.In concrete using method, because the quaternary ammonium salt epoxy curing agent in described protein-based wood adhesive has the longer open hour.Therefore, before being applied to bonding timber, other compositions in the very short time by solidifying agent and binding agent mix, thus the binding agent formed had the open hour up to about one week before bonding timber.
In the present invention, the tackiness agent of embodiment synthesis as wood adhesive for bond timber time, described timber is for glued board, can pass through roller coat, scraper for coating, curtain coating, or sprinkling is applied to the surface of plywood single board; Then multiple veneer is piled up with the sheet material forming desired thickness; Finally resulting sheet is displayed, cold pressing, hot pressing obtains composite plywood.Wherein, the detection method of the composite plywood of synthesis is carried out according to the wet method detection method specified in wood-based plate and face artificial board physicochemical property testing method.Resulting sheet assembly time is lower 1 hour of room temperature, and pressure of colding pressing is 6-10 kg/cm (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 kg/cm.
Quaternary ammonium salt epoxy resin and synthesis thereof:
1, Compound I A
（IA）
In the there-necked flask of 2000 mL, add 1404.4 g water, more slowly add 2,4,6-tri--(dimethylamino methyl) phenol (DMP30,167.5 g, 661 mmol, 95%).Add and solution is chilled to 0 DEG C, slowly instill epoxy chloropropane (174.8 g, 1.89 mol), during dropping, control temperature is less than 25 DEG C.Stir 2 h at this temperature after dripping off, then temperature is risen to 30 DEG C of stirring 1 h, obtain aromatic curing agent DMP30-epoxy chloropropane IA.
2, Compound I B
（IB）
In the there-necked flask of 2000 mL, add 1048.8 g water, more slowly add 3,5-bis--(dimethylamino methyl) phenol (137.5 g, 661 mmol).Add and solution is chilled to 0 DEG C, slowly instill epoxy chloropropane (124.7 g, 1.22 mol), during dropping, control temperature is less than 25 DEG C.Stir 2 h at this temperature after dripping off, then temperature is risen to 30 DEG C of stirring 1 h, obtain aromatic curing agent 3,5-bis--(dimethylamino methyl) phenol-epoxy chloropropane IB.
3, Compound I C
（IC）
In the there-necked flask of 2000 mL, add 1048.8 g water, more slowly add 2,4-bis--(dimethylamino methyl) phenol (137.5 g, 661 mmol).Add and solution is chilled to 0 DEG C, slowly instill epoxy chloropropane (124.7 g, 1.22 mol), during dropping, control temperature is less than 25 DEG C.Stir 2 h at this temperature after dripping off, then temperature is risen to 30 DEG C of stirring 1 h, obtain aromatic curing agent 2,4-bis--(dimethylamino methyl) phenol-epoxy chloropropane IC.
4, Compound II per A
（IIA）
In the there-necked flask of 2000 mL, add 856 g water, more slowly add N, N, N ', N '-tetramethyl--1,6-hexanediamine (103.4 g, 0.6 mol) adds and solution is chilled to 0 DEG C, slowly instill epoxy chloropropane (110.6 g, 1.2mol), during dropping, control temperature is less than 25 DEG C.Stir 2 h at this temperature after dripping off, then temperature is risen to 30 DEG C of stirring 1 h, obtain aliphatic firming agent tetramethyl--1,6-hexanediamine-epoxy chloropropane IIA.
5, Compound II per B
（IIB）
In the there-necked flask of 2000 mL, add 628.8 g water, more slowly add N, N, N ', N '-Tetramethyl Ethylene Diamine (EMTDA, 28.2 g, 0.7 mol).Add and solution is chilled to 0 DEG C, slowly instill epoxy chloropropane (129 g, 1.4 mol), during dropping, control temperature is less than 25 DEG C.Stir 2 h at this temperature after dripping off, then temperature is risen to 30 DEG C of stirring 1 h, obtain aliphatic firming agent tetramethyl--quadrol-epoxy chloropropane (EMTDA-epoxy chloropropane) IIB.
6, Compound II per C
（IIC）
In the there-necked flask of 2000 mL, add 989.6 g water, more slowly add tetramethyl--positive certain herbaceous plants with big flowers diamines (136.8 g, 0.6 mol) and add and solution is chilled to 0 DEG C, slowly instill epoxy chloropropane (110.6 g, 1.2mol), during dropping, control temperature is less than 25 DEG C.Stir 2 h at this temperature after dripping off, then temperature is risen to 30 DEG C of stirring 1 h, obtain aliphatic firming agent tetramethyl--positive decamethylene diamine-epoxy chloropropane IIC.
7, Compound II per D
（IID）
In the there-necked flask of 2000 mL, add 922.4 g water, more slowly add tetramethyl--4,6 dimethylhexanediamine (120 g, 0.6 mol) add solution is chilled to 0 DEG C, slowly instill epoxy chloropropane (110.6 g, 1.2mol), during dropping, control temperature is less than 25 DEG C.Stir 2 h at this temperature after dripping off, then temperature is risen to 30 DEG C of stirring 1 h, obtain aliphatic firming agent tetramethyl--4,6 dimethylhexanediamine-epoxy chloropropane IID.
8, Compound II per E
（IIE）
In the there-necked flask of 2000 mL, add 848.8 g water, tetramethyl--3-propyl succinimide amine (111.6 g, 0.6 mol) adds and solution is chilled to 0 DEG C, and slowly instill epoxy chloropropane (110.6 g, 1.2mol), during dropping, control temperature is less than 25 DEG C.Stir 2 h at this temperature after dripping off, then temperature is risen to 30 DEG C of stirring 1 h, obtain aliphatic firming agent tetramethyl--3-propyl succinimide amine-epoxy chloropropane IIE.
Embodiment 1
Synthetic proteins base timber adhesive A
In 500 mL beakers, soyflour (20 grams) is slowly added 36 grams of water in stirring, slowly instill 20 wt%NaOH solution, regulate the pH to 10 of soybean slurries, continue stirring after 10 minutes, in this alkaline soyflour mixing solutions, add the aqueous solution of the DMP30-epoxy chloropropane (IA) of 40 gram of 10 wt%, add and continue the mixing solutions that obtains for 10 minutes of stirring as the tackiness agent A for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 5 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.5 MPa.
Embodiment 2
Synthetic proteins base timber adhesive B
In 500 mL beakers, the aqueous solution of the DMP30-epoxy chloropropane (IA) of 40 gram of 10 wt% is added in 36 grams of water in stirring, with vigorous stirring, slowly adds 0.2 gram of CaO, stirs 10 minutes.Again 20 grams of bean powderes are slowly added, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent B for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 4.6 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.6 MPa.
Embodiment 3
Synthetic proteins base timber adhesive C
In 500 mL beakers, the aqueous solution of the DMP30-epoxy chloropropane (IA) of 30 gram of 10 wt% is added in 60 grams of water in stirring, with vigorous stirring, slowly add 0.2 gram of NaOH, add the mixture (i.e. 24 grams of bean powderes and 6 grams of MgO) of 30 grams of bean powderes and MgO again, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent C for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 4.8 MPa, and wetting 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, soyflour (20 grams) is slowly added 36 grams of water in stirring, slowly instill 20 wt%NaOH solution, regulate the pH to 10 of soybean slurries, continue stirring after 10 minutes, in the mixing solutions of this alkaline soyflour, add the aqueous solution of the aliphatic firming agent (EMTDA-epoxy chloropropane IIB) of 40 gram of 10 wt%, regulate the part by weight of solidifying agent IIB and bean powder to be respectively 1:6 simultaneously, 1:4,1:3,1:2; Add and continue the mixing solutions that obtains for 10 minutes of stirring as the tackiness agent D for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is all greater than 4.0 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is all greater than 1.3 MPa by force.
Embodiment 5
Synthetic proteins base timber adhesive E
In 500 mL beakers, soyflour (20 grams) is slowly added 36 grams of water in stirring, slowly instill 20 wt% NaOH solution, regulate the pH to 10 of soybean slurries, continue stirring after 10 minutes, the aliphatic firming agent tetramethyl--4 of 40 gram of 10 wt% is added in the soyflour mixing solutions of this alkalescence, the aqueous solution of 6 dimethylhexanediamine-epoxy chloropropane (Compound II per D), regulates the part by weight of solidifying agent IID and bean powder to be respectively 1:6,1:4 simultaneously, 1:3,1:2; Add and continue the mixing solutions that obtains for 10 minutes of stirring as the tackiness agent E for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is all greater than 4.2 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.3 MPa.
Embodiment 6
Synthetic proteins base timber adhesive F
In 500 mL beakers, the aqueous solution of the tetramethyl--quadrol-epoxy chloropropane (IID) of 44 gram of 10 wt% is added in 60 grams of water in stirring, with vigorous stirring, slowly adds the NaOH of 0.2 gram, stirs 10 minutes.Add 5 grams of glycerine and 0.2 gram of Na2B4O7 again, stir, then 15 grams of bean powderes are slowly added, stir, then add 5 grams of wheat-flours, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent F for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 5.1 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.4 MPa.
Embodiment 7
Synthetic proteins base timber adhesive G
In 500 mL beakers, the aqueous solution of tetramethyl--1, the 6-hexanediamine-epoxy chloropropane (IIA) of 40 gram of 10 wt% is added in 90 grams of water in stirring, with vigorous stirring, slowly adds 0.2 gram of NaOH, stirs 10 minutes; Add the polymeric amide polyamine-epichlorohydrin (PAE) of 10 gram of 12.5 wt% again, stir after 10 minutes, 26 grams of bean powderes are slowly added, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent G for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 5.2 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.5 MPa.
Embodiment 8
Synthetic proteins base timber adhesive H
In 500 mL beakers, the tetramethyl--1 of 44 gram of 10 wt%, the aqueous solution of 6-hexanediamine-epoxy chloropropane (IIA) is added in 100 grams of water in stirring, with vigorous stirring, 0.2 gram of Na2B4O7, stirs, add 6 grams of CMC again, stir, then 30 grams of bean powderes are slowly added, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent H for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 4.9 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.6 MPa.
Embodiment 9
Synthetic proteins base timber adhesive I
In 500 mL beakers, the aqueous solution of the DMP30-epoxy chloropropane (IA) of 40 gram of 10 wt% is added in 100 grams of water in stirring, with vigorous stirring, slowly adds the NaOH of 0.2 gram, stirs 10 minutes.Add the polymeric amide polyamine-epichlorohydrin (PAE) of 10 gram of 12.5 wt% again, stir after 10 minutes, 26 grams of bean powderes are slowly added, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent I for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 5.5 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.6 MPa.
Embodiment 10
Synthetic proteins base timber adhesive J
Key step, as embodiment 9, replaces 26 grams of bean powderes unlike the mixture (dry weight is than 3:1) adding 26 grams of bean powderes and ox-hide xylogen, adds and continues the mixing solutions that obtains for 10 minutes of stirring as the tackiness agent J for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 5.2 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.5 MPa.
Embodiment 11
Synthetic proteins base timber adhesive K
In 500 mL beakers, the aqueous solution of the compound (IE) of 44 gram of 10 wt% is added in 60 grams of water in stirring, with vigorous stirring, slowly adds the NaOH of 0.2 gram, stirs 10 minutes.Add 5 grams of glycerine and 0.3 gram of Na2B4O7 again, stir, then 15 grams of bean powderes are slowly added, stir, then add 5 grams of wheat-flours, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent K for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 4.8 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.3 MPa.
Embodiment 12
Synthetic proteins base timber adhesive L
In 500 mL beakers, the aqueous solution of the compound (IC) of 44 gram of 10 wt% is added in 100 grams of water in stirring, with vigorous stirring, 0.3 gram of Na2B4O7, stir, then add 5 grams of CMC, stir, again 30 grams of bean powderes are slowly added, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent L for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 5.6 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.8 MPa.
Embodiment 13
Synthetic proteins base timber adhesive M
In 500 mL beakers, soyflour (20 grams) is slowly added 36 grams of water in stirring, slowly instill triethylamine, regulate the pH to 8 of soybean slurries, continue stirring after 10 minutes, in the mixing solutions of this alkaline soyflour, add the aqueous solution of the DMP30-epoxy chloropropane of 40 gram of 10 wt%, add and continue the mixing solutions that obtains for 10 minutes of stirring as the tackiness agent M for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 5 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.5 MPa.Its turnover time is 6 hours.
Embodiment 14
Synthetic proteins base timber adhesive N
In 500 mL beakers, the aqueous solution of the DMP30-epoxy chloropropane of 40 gram of 10 wt% is added in 36 grams of water in stirring, with vigorous stirring, slowly adds 0.2 gram of lime acetate, stirs 10 minutes.Again 20 grams of bean powderes are slowly added, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent N for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 4.6 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.6 MPa.Its turnover time is 6 hours.
Embodiment 15
Synthetic proteins base timber adhesive O
In 500 mL beakers, the aqueous solution of the DMP30-epoxy chloropropane of 30 gram of 10 wt% is added in 60 grams of water in stirring, with vigorous stirring, slowly add 0.2 gram of lime acetate, add the mixture (i.e. 24 grams of bean powderes and 6 g potato starch) of 30 grams of bean powderes and yam starch again, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent O for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 4.8 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.5 MPa.Its turnover time is 7 hours.
Embodiment 16
Synthetic proteins base timber adhesive P
In 500 mL beakers, the aqueous solution of the tetramethyl--quadrol-epoxy chloropropane (IID) of 44 gram of 10 wt% is added in 60 grams of water in stirring, with vigorous stirring, slowly adds the lime acetate of 0.2 gram, stirs 10 minutes.Again 15 grams of bean powderes are slowly added, stir, then add 5 g potato starch, add and continue the mixing solutions that obtains for 20 minutes of stirring as the tackiness agent P for the timber that bonds.After tested, the dry shape bonding strength of gained composite plywood is 5.1 MPa, and wetting after soaking 3 h in 60 DEG C of hot water is by force 1.4 MPa.Its turnover time is 8 hours.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.

Claims (13)

1. a protein-based wood adhesive, is characterized in that: comprise vegetable-protein, xylogen, without aldehyde solidifying agent, alkali and filler; Based on the gross weight of described protein-based wood adhesive,
The content of described vegetable-protein is 5-50wt%;
The content of described xylogen is 0-30wt%;
The described content without aldehyde solidifying agent is 1-30wt%;
The content of described alkali is 0.1-15wt%;
The content of described filler is 0-20wt%;
Described formaldehydeless solidifying agent comprises polynary propylene oxide chain quaternary ammonium salt epoxy resin, and polynary propylene oxide chain quaternary amine epoxy resin is aromatic series or the aliphatic quaternary ammonium salt epoxy resin of the propylene oxide containing more than 2 or 2; The structural formula of described aromatic series quaternary ammonium salt epoxy resin, aliphatic quaternary ammonium salt epoxy resin is as follows respectively:
（I）， （II），
Wherein, m, n are integer, and n=2-3, m=2-10.
2. protein-based wood adhesive according to claim 1, is characterized in that: described vegetable-protein is little Mai paddy Yuan albumen, zein or legume protein.
3. protein-based wood adhesive according to claim 1, is characterized in that: described xylogen is BRAUNS xylogen, cellulase xylogen, dioxan acidolysis xylogen, grind wood lignin, Klason xylogen, Periodic acid xylogen, kraft lignin or sulfonated lignin.
4. protein-based wood adhesive according to claim 1, is characterized in that: described formaldehydeless solidifying agent also comprises aliphatic polyhydroxy compound, multi-carboxy compound or polyamines based compound; Wherein, polyamines based compound is polymeric amide polyamine or polymeric amide polyamine-epichlorohydrin; Aliphatics multi-carboxy compound is carboxymethyl cellulose or the starch after improveing; Polyol is glycerine or starch.
5. protein-based wood adhesive according to claim 1, is characterized in that: polynary propylene oxide chain quaternary amine epoxy resin is DMP30-epoxy resin, EMTDA-epoxy chloropropane or tetramethyl--1,6-hexanediamine-epoxy chloropropane.
6. protein-based wood adhesive according to claim 1, is characterized in that: described alkali is mineral alkali or Lewis base; Described mineral alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or Sodium Tetraborate; Described Lewis base is triethylamine or lime acetate.
7. protein-based wood adhesive according to claim 1, is characterized in that: described filler is silicon-dioxide, paraffin, whole meal flour, tree bark powder or nutshell powder.
8. the protein-based wood adhesive according to any one of claim 1-7, it is characterized in that: described protein-based wood adhesive also comprises yam starch, based on the gross weight of described protein-based wood adhesive, the content of described yam starch is 5-15wt%.
9. prepare a method for protein-based wood adhesive as described in any one of claim 1-8, it is characterized in that: comprise the following steps:
Step 1), the mixture of vegetable-protein or vegetable-protein and xylogen is joined in mineral alkali or solution of Lewis base, stir until vegetable-protein and xylogen disperse in the solution completely;
Step 2), in step 1) dispersion after solution in add formaldehydeless solidifying agent or add formaldehydeless solidifying agent and yam starch, stir;
Step 3), to step 2) stir after solution in add filler, add and stir, thus obtain described protein-based wood adhesive.
10. an application for protein-based wood adhesive as claimed in claim 9, is characterized in that: described protein-based wood adhesive can be used for wood-base fibre and particle panel material and all kinds of composite floor board, bamboo flooring, consolidated floor glued board; Described wood-base fibre and particle panel material is woodwork plate, bamboo plywood, shaving board (OSB), flake board, fiberboard, parallel become a useful person (PSL), interlayer are become a useful person (LSL), laminated veneer lumber (LVL).
The using method of 11. 1 kinds of protein-based wood adhesives as claimed in claim 9, is characterized in that: by described protein-based 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.
The using method of 12. protein-based wood adhesives according to claim 11, is characterized in that: 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.
The using method of 13. protein-based wood adhesives according to claim 11, is characterized in that: 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 kg/cm.
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