CN103740326A - Protein-based wood adhesive and preparation method thereof - Google Patents
Protein-based wood adhesive and preparation method thereof Download PDFInfo
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- CN103740326A CN103740326A CN201410013631.7A CN201410013631A CN103740326A CN 103740326 A CN103740326 A CN 103740326A CN 201410013631 A CN201410013631 A CN 201410013631A CN 103740326 A CN103740326 A CN 103740326A
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Abstract
The invention relates to a protein-based wood adhesive and a preparation method thereof, and particularly relates to a protein-based wood adhesive prepared from vegetable protein and non-toxic epoxy resin and a preparation method thereof. The protein-based wood adhesive is prepared from natural vegetable protein, a formaldehyde-free epoxy resin curing agent, a filler and the like. The protein-based wood adhesive disclosed by the invention is a non-toxic and environment-friendly adhesive, and no formaldehyde or a toxic organic substance is released in production, transportation and application processes or use of the product. Meanwhile, the adhesive is high in bonding strength, and good in water tolerance, the strength of the adhesive after being boiled by boiling water can be comparable to the performance of phenol glue, and the use standard of secondary glue is completely achieved. The protein-based wood adhesive provided by the invention is simple in preparation technology, the hot-press time is much smaller than that of a formaldehyde-type adhesive, and an energy source is greatly saved.
Description
Technical field
The present invention relates to a kind of wood adhesive and preparation method thereof, relate in particular to a kind of protein-based wood adhesive of being made by vegetable-protein and nontoxic epoxy resin and preparation method thereof.
Background technology
As everyone knows, wood industry need to be used a large amount of tackiness agent to process for product.In industry at present, the most frequently used wood adhesive 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 relative merits separately.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 higher its scope of application of price decision are comparatively limited, are 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 has all been used aldehyde compound, the finished product of therefore being made by it, and these products all can produce volatile organic compounds (VOC) in production, transportation, use procedure.In recent years, for the VOC distributing, particularly formaldehyde, the impact of HUMAN HEALTH is received to increasing concern, 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 furniture and floor that particularly urea-formaldehyde glue is produced, sustainable release formaldehyde 5-15.Meanwhile, traditional three-aldehyde glue consumes a large amount of petroleum productss in process of production, and reserves must be also limited.Therefore, in order fundamentally to address these problems, just must develop a kind of asepsis environment-protecting adhesive products, its production process be from former expect product with and use the material and the process that do not relate to any poisonous and not environmental protection.
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 be limited to technology at that time, the intensity of this class tackiness agent is low, and water resistance is poor.In five sixties, along with the development of petrochemical complex, protein-base adhesive is substituted by three-aldehyde glue rapidly.
In the last few years, increasingly deep along with environmental consciousness, people are also more and more higher to the requirement of environmental protection.U.S. California Air Resources Board(CARB in 2007) tackiness agent using in timber products has been had to strict environment protection control standard, and this standard all came into effect in the whole America in 2013.Therefore, protein-based glue has entered into people's sight line again, and many R&D institutions have carried out relevant R&D work.The wherein technical relatively more outstanding natural bean gum product that has Dr. Li research group, for example US 7,722,712 B2 etc.; The bonding strength of the product of its report and water tolerance have all exceeded urea-formaldehyde glue, now large-scale commercial production.But, because this glue paste is used polymeric amide polyamine-epoxy chloropropane (Polyamidoamine-Epichlorohydrin, PAE) as solidifying agent, greatly increased the cost of product, make the price of final timber finished product on market higher.Therefore seeking various alternative solidifying agent becomes the another research direction of protein-based glue.
Because epoxy resin is to contain two or more epoxide groups in molecule
organic high molecular compound, therefore epoxy resin can with soybean protein in the functional group such as a lot of functional groups such as hydroxyl, amino, sulfydryl, carboxyl react, these features make epoxy resin become a kind of potential solidifying agent.But, because traditional epoxy resin exists price higher, the factors such as long reaction time, therefore few people are applied in sheet material processing 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 has epoxy resin to be applied to the possibility of sheet material processing industry.
Summary of the invention
The object of the present invention is to provide a kind of protein-based wood adhesive and preparation method thereof, utilize vegetable-protein and cheap quaternary ammonium salt epoxy resin to prepare free of contamination epoxy resin protein-based wood adhesive, the product cost that has reduced protein-based wood adhesive, in addition, preparation method is simple.
The technical solution adopted in the present invention:
A kind of protein-based wood adhesive, is characterized in that: comprise vegetable-protein, xylogen, formaldehydeless solidifying agent, mineral alkali and filler; Based on the gross weight of described protein-based wood adhesive,
The content of described vegetable-protein is 5 wt%-50 wt %;
The content of described xylogen is 0-30 wt %;
The content of described formaldehydeless solidifying agent is 1 wt%-30 wt %;
The content of described mineral alkali is 0.1 wt %-15 wt %;
The content of described filler is 0-20 wt %;
Preferred, based on the gross weight of described protein-based wood adhesive, the content of vegetable-protein is 25%-45%; The content of xylogen is 0%-20%; The content of formaldehydeless solidifying agent is 3%-25%; The content of mineral alkali is 0.2%-12%; The content of filler is 0-20 wt %.
Described formaldehydeless solidifying agent comprises polynary propylene oxide chain quaternary ammonium salt epoxy resin, as the quaternary ammonium salt epoxy resin take DMP30-epoxy chloropropane (DMP30-Epichlorohydrin) as representative.Polynary propylene oxide chain quaternary amine epoxy resin is aromatic series or the aliphatic quaternary ammonium salt epoxy resin that contains 2 or 2 above propylene oxide; Wherein, aromatic series quaternary ammonium salt epoxy resin is the phenol ring that contains 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 that contains 2 or 2 above propylene oxide side chains;
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 the quaternary ammonium salt epoxy resin of the multiple propylene oxide side chains of tool that contains straight or branched, its structure as shown in molecular formula (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 formaldehydeless solidifying agent 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.Wherein, described other compounds are aliphatic polyhydroxy compound, multi-carboxy compound or polyamines based compound.
Preferably, aliphatic polyamine based compound is the aliphatic polymer that contains more than 2 or 2 amido, the reaction product of for example polymeric amide polyamine well known in the prior art (molecular formula IIIA) 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:
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）。
Described 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.
As above of living in, when formaldehydeless solidifying agent is polynary propylene oxide chain quaternary amine epoxy resin, the content of described formaldehydeless solidifying agent is 1 wt%-30 wt % of tackiness agent weight.When formaldehydeless solidifying agent is 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 contains a propylene oxide structure, and the polymerization single polymerization monomer of propylene oxide of the present invention is take aromatic nucleus or short carbon chain as molecule core, and from core, derives multiple propylene oxide chains.This structure has increased substantially polymerization efficiency, and the polymerization degree is multiplied, thereby can reduce the usage quantity of polymerization single polymerization monomer, reduces costs.Meanwhile, because each polymerization single polymerization monomer all contains multiple propylene oxide chains, therefore after polymerization, more easily form complicated netted paradigmatic structure, and then improve performance.Specifically take DMP30-epoxy chloropropane as example, the DMP30-epoxy chloropropane of per molecule contains three propylene oxide units, therefore after polyreaction, can and form complicated tridimensional network 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 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, formaldehydeless solidifying agent of the present invention is water miscible bifunctional 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.And this based epoxy resin is cheap, short with lignocellulose and soyflour reaction times, 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 of little Mai paddy Yuan albumen, zein or legume protein; Preferably, be legume protein; More preferably, be soybean protein.Current three kinds of modal soy protein products are respectively soyflour, soybean protein enriched material, and soybean protein isolate (SPI).Maximum difference between these products is the content of protein.Typically, soyflour comprises the protein of approximately 45 wt%, and soybean protein enriched material comprises that, at least about the protein of 65 wt% (dry weight), SPI comprises at least about the protein of 85 wt% (dry weight).In the present invention, soybean protein is preferably SPI or soyflour; More preferably soyflour.
Described xylogen is BRAUNS xylogen, cellulase xylogen, dioxan acidolysis xylogen, grinds wood lignin, Klason xylogen, Periodic acid xylogen, kraft paper xylogen or sulfonated lignin.The features such as to have cost low due to kraft paper xylogen, and performance is good, in the situation of equal usage quantity, are used the high 5%-10% of product performance of comparable other xylogen of use of performance of the product that kraft paper xylogen obtains.The in the situation that of equal cost, its product performance can improve more than 10%; The preferred kraft paper xylogen of xylogen of the present invention.
Described mineral alkali is oxide compound or the oxyhydroxide of IA family, or the oxide compound of IIA family, oxyhydroxide or borate; Preferably, mineral alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or Sodium Tetraborate one wherein.
Described filler is silicon-dioxide, paraffin, whole meal flour, tree bark powder or nutshell powder.
A preparation method for protein-based wood adhesive, is characterized in that: comprise the following steps:
Step 1), the mixture of vegetable-protein or vegetable-protein and xylogen is joined in inorganic alkali solution, stir until albumen and xylogen are dispersed in solution completely;
Step 2), in the solution after disperseing in step 1), add formaldehydeless solidifying agent, stir;
Step 3), to step 2) add filler in solution after stirring, add and stir, thereby obtain described protein-based wood adhesive.
A using method for protein-based wood adhesive as above, passes through roller coat, scraper for coating, curtain coating by described protein-based wood adhesive, or sprays the veneer surface that is applied to wood-base fibre and particle panel material; Then multiple described veneers pile up to form the sheet material of desired thickness; Again resulting sheet is displayed, colded 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 becomes a useful person, interlayer is become a useful person, laminated veneer lumber, all kinds of composite floor board, bamboo floor or consolidated floor.
The assembly time of described sheet material is 1-3 hour under room temperature; The 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 ℃-200 ℃, is preferably 100 ℃-190 ℃.According to dry shape bonding strength > 4 MPa of the composite wood wood-based plate of using method gained of the present invention, and, in 60 ℃ of hot water, soak more than wet after 3 h can reach 1.2 MPa by force, reach 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 are qualified glued board; And the dry shape bonding strength of glued board illustrates that the adhesive capacity of this glue paste is fine while being 4-5 MPa.
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, being applied to before bonding timber, in the very short time, other compositions of solidifying agent and binding agent are mixed, thereby the binding agent forming had the open hour up to approximately one week before bonding timber.
Beneficial effect of the present invention:
The synthetic method of polynary propylene oxide chain quaternary amine epoxy resin of the present invention is simple, raw material cheapness, good water solubility; And can significantly reduce the temperature that it reacts with protein-based, shorten the time of reacting with protein-based.Therefore the protein-based wood adhesive that, the present invention prepares take it as solidifying agent with low cost; And 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 be compared with phenolic glue; And the advantages such as operating procedure is simple, energy-conservation.
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 to produce, transportation, and application process does not still all have the release of formaldehyde or toxic organic compound in finished product is used.And the bonding strength of protein-based wood adhesive of the present invention is high, water-tolerant; After testing, use dry shape bonding strength > 4 MPa 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, has greatly saved the energy (being listed as follows).
| ? | Urea-formaldehyde resin adhesive | Phenol aldehyde resin | Melamine resin adehsive | The protein-based wood adhesive of claim |
| Whether release formaldehyde | Be | Be | Be | No |
| Whether main raw material is from renewable resources | No | No | No | Be |
| Hot pressing time (take 18 mm glued boards as example) | 25-30 minute | 40-50 minute | 30-35 minute | 9-14 minute |
| Production cost | Low | High | High | Low |
| Bonding strength | Generally | Good | Good | Good |
Embodiment
In the present invention, when the synthetic tackiness agent of embodiment is used for boning timber as wood adhesive, described timber is take glued board as example, can pass through roller coat, scraper for coating, curtain coating, or sprays the surface that is applied to plywood single board; Then multiple veneers pile up to form the sheet material of desired thickness; Finally resulting sheet is displayed, colded pressing, hot pressing obtains composite plywood.Wherein, the detection method of synthetic composite plywood is to carry out according to the wet method detection method stipulating in wood-based plate and face artificial board physicochemical property testing method.Resulting sheet assembly time is lower 1 hour of room temperature, and the 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 ℃-150 ℃, and hot pressing pressure is 9-12 kg/cm.
Embodiment 1
Synthetic (the Compound I A) of quaternary ammonium salt epoxy resin
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 solution is chilled to 0 ℃, slowly splash into epoxy chloropropane (174.8 g, 1.89 mol), during dropping, control temperature and be less than 25 ℃.After dripping off, at this temperature, stir 2 h, then temperature is risen to 30 ℃ of stirring 1 h, obtain aromatic curing agent DMP30-epoxy chloropropane IA.
Embodiment 2
Synthetic (the Compound I B) of quaternary ammonium salt epoxy resin
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 solution is chilled to 0 ℃, slowly splash into epoxy chloropropane (124.7 g, 1.22 mol), during dropping, control temperature and be less than 25 ℃.After dripping off, at this temperature, stir 2 h, then temperature is risen to 30 ℃ of stirring 1 h, obtain aromatic curing agent 3,5-bis--(dimethylamino methyl) phenol-epoxy chloropropane IB.
Embodiment 3
Synthetic (the Compound I C) of quaternary ammonium salt epoxy resin
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 solution is chilled to 0 ℃, slowly splash into epoxy chloropropane (124.7 g, 1.22 mol), during dropping, control temperature and be less than 25 ℃.After dripping off, at this temperature, stir 2 h, then temperature is risen to 30 ℃ of stirring 1 h, obtain aromatic curing agent 2,4-bis--(dimethylamino methyl) phenol-epoxy chloropropane IC.
Embodiment 4
Synthetic (the Compound I IA) of quaternary ammonium salt epoxy resin
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 solution is chilled to 0 ℃, slowly splash into epoxy chloropropane (110.6 g, 1.2mol), during dropping, control temperature and be less than 25 ℃.After dripping off, at this temperature, stir 2 h, then temperature is risen to 30 ℃ of stirring 1 h, obtain aliphatic firming agent tetramethyl--1,6-hexanediamine-epoxy chloropropane IIA.
Embodiment 5
Synthetic (the Compound I IB) of quaternary ammonium salt epoxy resin
（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 solution is chilled to 0 ℃, slowly splash into epoxy chloropropane (129 g, 1.4 mol), during dropping, control temperature and be less than 25 ℃.After dripping off, at this temperature, stir 2 h, then temperature is risen to 30 ℃ of stirring 1 h, obtain aliphatic firming agent tetramethyl--quadrol-epoxy chloropropane (EMTDA-epoxy chloropropane) IIB.
Embodiment 6
Synthetic (the Compound I IC) of quaternary ammonium salt epoxy resin
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) to add solution is chilled to 0 ℃, slowly splash into epoxy chloropropane (110.6 g, 1.2mol), during dropping, control temperature and be less than 25 ℃.After dripping off, at this temperature, stir 2 h, then temperature is risen to 30 ℃ of stirring 1 h, obtain aliphatic firming agent tetramethyl--positive decamethylene diamine-epoxy chloropropane IIC.
Embodiment 7
Synthetic (the Compound I ID) of quaternary ammonium salt epoxy resin
（IID）
In the there-necked flask of 2000 mL, add 922.4 g water, more slowly add tetramethyl--4,6 dimethyl hexanediamine (120 g, 0.6 mol) add solution is chilled to 0 ℃, slowly splash into epoxy chloropropane (110.6 g, 1.2mol), during dropping, control temperature and be less than 25 ℃.After dripping off, at this temperature, stir 2 h, then temperature is risen to 30 ℃ of stirring 1 h, obtain aliphatic firming agent tetramethyl--4,6 dimethyl hexanediamine-epoxy chloropropane IID.
Embodiment 8
Synthetic (the Compound I IE) of quaternary ammonium salt epoxy resin
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 solution is chilled to 0 ℃, slowly splashes into epoxy chloropropane (110.6 g, 1.2mol), controls temperature and be less than 25 ℃ during dropping.After dripping off, at this temperature, stir 2 h, then temperature is risen to 30 ℃ of stirring 1 h, obtain aliphatic firming agent tetramethyl--3-propyl succinimide amine-epoxy chloropropane IIE.
Embodiment 9
Synthetic adhesive A
In 500 mL beakers, soyflour (SF) (20 grams) is slowly added to 36 grams of water in stirring, slowly splash into 20 wt%NaOH solution, regulate the pH to 10 of soybean slurries, continue to stir after 10 minutes, to the aqueous solution that adds the DMP30-epoxy chloropropane (IA) of 40 gram of 10 wt% in the mixing solutions of this alkalescence SF, add and continue to stir the mixing solutions obtaining for 10 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.5 MPa.
Embodiment 10
Synthetic 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, under vigorous stirring, slowly adds 0.2 gram of CaO, stirs 10 minutes.Again 20 grams of bean powderes are slowly added, add and continue to stir the mixing solutions obtaining for 20 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.6 MPa.
Embodiment 11
Synthetic 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, under vigorous stirring, slowly add 0.2 gram of NaOH, add again the mixture (i.e. 24 grams of bean powderes and 6 grams of MgO) of 30 grams of bean powderes and MgO, add and continue to stir the mixing solutions obtaining for 20 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.5 MPa.
Embodiment 12
Synthetic adhesive D
In 500 mL beakers, soyflour (SF) (20 grams) is slowly added to 36 grams of water in stirring, slowly splash into 20 wt%NaOH solution, regulate the pH to 10 of soybean slurries, continue to stir after 10 minutes, to the aqueous solution that adds the aliphatic firming agent (EMTDA-epoxy chloropropane IIB) of 40 gram of 10 wt% in the mixing solutions of this alkalescence SF, 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 to stir the mixing solutions obtaining for 10 minutes 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, soaks wet 1.3 MPa that are all greater than by force after 3 h in 60 ℃ of hot water.
Embodiment 13
Synthetic adhesive E
In 500 mL beakers, soyflour (SF) (20 grams) is slowly added to 36 grams of water in stirring, slowly splash into 20 wt% NaOH solution, regulate the pH to 10 of soybean slurries, continue to stir after 10 minutes, to aliphatic firming agent tetramethyl--4 that add 40 gram of 10 wt% in the mixing solutions of this alkalescence SF, the aqueous solution of 6 dimethyl hexanediamine-epoxy chloropropane (Compound I ID) 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 to stir the mixing solutions obtaining for 10 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.3 MPa.
Embodiment 14
Synthetic adhesive F
In 500 mL beakers, the aqueous solution of tetramethyl--quadrol-epoxy chloropropane (IID) of 44 gram of 10 wt% is added in 60 grams of water in stirring, under vigorous stirring, slowly adds the NaOH of 0.2 gram, stirs 10 minutes.Add again 5 grams of glycerine and 0.2 gram of Na
2b
4o
7, stir, then 15 grams of bean powderes are slowly added, stir, then add 5 grams of wheat-flours, add and continue to stir the mixing solutions obtaining for 20 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.4 MPa.
Embodiment 15
Synthetic adhesive G
In 500 mL beakers, tetramethyl--1 of 40 gram of 10 wt%, the aqueous solution of 6-hexanediamine-epoxy chloropropane (IIA) is added in 90 grams of water in stirring, under vigorous stirring, slowly adds 0.2 gram of NaOH, stirs 10 minutes; Add again polymeric amide polyamine-epoxy chloropropane (PAE) of 10 gram of 12.5 wt%, stir after 10 minutes, 26 grams of bean powderes are slowly added, add and continue to stir the mixing solutions obtaining for 20 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.5 MPa.
Embodiment 16
Synthetic adhesive H
In 500 mL beakers, 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, under vigorous stirring, 0.2 gram of Na
2b
4o
7, stir, then add 6 grams of CMC, stir, then 30 grams of bean powderes are slowly added, add and continue to stir the mixing solutions obtaining for 20 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.6 MPa.
Embodiment 17
Synthetic 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, under vigorous stirring, slowly adds the NaOH of 0.2 gram, stirs 10 minutes.Add again polymeric amide polyamine-epoxy chloropropane (PAE) of 10 gram of 12.5 wt%, stir after 10 minutes, 26 grams of bean powderes are slowly added, add and continue to stir the mixing solutions obtaining for 20 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.6 MPa.
Embodiment 18
Synthetic adhesive J
Key step is as embodiment 9, and different is to add the mixture (dry weight is than 3:1) of 26 grams of bean powderes and ox-hide xylogen to replace 26 grams of bean powderes, adds and continues to stir the mixing solutions obtaining for 10 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.5 MPa.
Embodiment 19
Synthetic 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, under vigorous stirring, slowly adds the NaOH of 0.2 gram, stirs 10 minutes.Add again 5 grams of glycerine and 0.3 gram of Na
2b
4o
7, stir, then 15 grams of bean powderes are slowly added, stir, then add 5 grams of wheat-flours, add and continue to stir the mixing solutions obtaining for 20 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.3 MPa.
Embodiment 20
Synthetic 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, under vigorous stirring, and 0.3 gram of Na
2b
4o
7, stir, then add 5 grams of CMC, stir, then 30 grams of bean powderes are slowly added, add and continue to stir the mixing solutions obtaining for 20 minutes 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 in 60 ℃ of hot water, soaking wetting after 3 h is by force 1.8 MPa.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area just can design according to the present invention be made many modifications and variations without creative work.Therefore, all technician in the art, all should be in 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 (11)
1. a protein-based wood adhesive, is characterized in that: comprise vegetable-protein, xylogen, formaldehydeless solidifying agent, mineral alkali and filler; Based on the gross weight of described protein-based wood adhesive,
The content of described vegetable-protein is 5 wt%-50 wt %;
The content of described xylogen is 0-30 wt %;
The content of described formaldehydeless solidifying agent is 1 wt%-30 wt %;
The content of described mineral alkali is 0.1 wt %-15 wt %;
The content of described filler is 0-20 wt %;
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 that contains 2 or 2 above propylene oxide; The structural formula of described aromatic series quaternary ammonium salt epoxy resin, aliphatic quaternary ammonium salt epoxy resin is as follows respectively:
Wherein, m, n is 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, grinds wood lignin, Klason xylogen, Periodic acid xylogen, kraft paper xylogen 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-epoxy chloropropane; Aliphatics multi-carboxy compound is the starch after carboxymethyl cellulose or improvement; 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 mineral alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or Sodium Tetraborate.
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. a preparation method for protein-based wood adhesive, is characterized in that: comprise the following steps:
Step 1), the mixture of vegetable-protein or vegetable-protein and xylogen is joined in inorganic alkali solution, stir until albumen and xylogen are dispersed in solution completely;
Step 2), in the solution after disperseing in step 1), add formaldehydeless solidifying agent, stir;
Step 3), to step 2) add filler in solution after stirring, add and stir, thereby obtain described protein-based wood adhesive.
9. a using method for the protein-based wood adhesive as described in claim 1-7, is characterized in that: described protein-based wood adhesive is passed through to roller coat, scraper for coating, curtain coating, or spray the veneer surface that is applied to wood-base fibre and particle panel material; Then multiple described veneers pile up to form the sheet material of desired thickness; Again resulting sheet is displayed, colded pressing, hot pressing obtains composite wood wood-based plate.
10. the using method of protein-based wood adhesive according to claim 9, 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 becomes a useful person, interlayer is become a useful person, laminated veneer lumber, all kinds of composite floor board, bamboo floor or consolidated floor.
The using method of 11. protein-based wood adhesives according to claim 9, is characterized in that: described hot pressing time is 0.5-0.8 min/mm, and hot pressing temperature is 100 ℃-190 ℃, and hot pressing pressure is 9-15 kg/cm.
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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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| CN104774588A (en) | 2015-07-15 |
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Application publication date: 20140423 |