CN109971403A - A kind of preparation method of soybean protein based bi-component wood adhesive - Google Patents
A kind of preparation method of soybean protein based bi-component wood adhesive Download PDFInfo
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- CN109971403A CN109971403A CN201910150790.4A CN201910150790A CN109971403A CN 109971403 A CN109971403 A CN 109971403A CN 201910150790 A CN201910150790 A CN 201910150790A CN 109971403 A CN109971403 A CN 109971403A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to a kind of preparation methods of soybean protein based bi-component wood adhesive, belong to field of adhesive technology.After soybean protein is carried out alkali modification by the present invention, carboxymethyl cellulose and acrylic acid are grafted on modified soy-bean protein as adhesive host agent, bound bitumen and carboxyl styrene emulsion, the adhesive prepared has good water resistance and caking property, carboxyl styrene emulsion has very strong water-reduction, higher cohesive force and conjunctiva intensity, carboxyl styrene emulsion can be such that macropore inside adhesive reduces, pore structure refinement, so that the water absorption rate of adhesive is greatly lowered, full water intensity is greatly improved；Present invention grafted propylene acid on modified soy-bean protein, in the solidification of soybean protein based bi-component wood adhesive, one layer of hydrophobic film with hydrophobicity can be generated, outside moisture can be effectively spaced apart, to achieve the purpose that waterproof performance, therefore cohesive force also enhances therewith.
Description
Technical field
The present invention relates to a kind of preparation methods of soybean protein based bi-component wood adhesive, belong to adhesive technology neck
Domain.
Background technique
Glued board (Plywood), a kind of wood-based plate, common glued board have three-ply board, five-ply board and seven plywood etc..With
Other plates are compared, and plywood machinery nature difference is smaller.Glued board can also improve timber utilization rate, be the one kind for saving timber
Effective way.Glued board is a kind of furniture material, while being also aircraft, ship, train, automobile, building and the effects of packing case
Material.
The chemical classification of Wood Adhesive, the adhesive for being widely used in production glued board have urea acid resin adhesive
(UF), cruel urea formaldehyde adhesive (PF), the cruel adhesive of isocyanic acid (MDI) and melamine modified urea acid resin adhesive (MUF)
Deng raw material is mainly derived from fossil resource.In recent years, with the gradually B of petroleum resources is weary and wood adhesive market not
Disconnected to expand, the production cost of the adhesive such as UF, PF, MDI and MUF climbs up and up.And due to containing free in UF, PF and MUF
First ferment group, can be discharged for a long time in the production and use process to the harmful formic acid of environment and human body.So that wood adhesive
Industry starts Jian hair emphatically and studies nontoxic, natural novel environment friendly adhesive.Right adhesive has protein adhesive and carbon water
It is just had begun before two kinds of compound adhesive, thousands of years of the mankind and uses protein and carbohydrate as adhesive, history
It is long.The characteristics of natural adhesive has itself: preparing that simple, easy for construction, cheap, adhesive speed is fast, and majority is
Water solubility, it is nontoxic.It is widely used in daily life and industrial production.Such as industrial art, school supply and stationery, Furniture manufacturing.
But the source of protein and carbohydrate is by very various influences such as weather, area, season and limitation, cohesive force compared with
Low, water resistance is poor, does not adapt to the large-scale industrial production of modernization.Protein adhesive can be divided into according to source difference
Tip object protein adhesive and animal protein glue.Vegetable protein has soybean albumen adhesive etc., and animal protein adhesive has skin
Bone cement, cheese cement stick etc..
Protein adhesive and carbohydrate are generated good due to that can form atmosphere bond structure between timber interface
Dry state bonding strength.But due to the hydrophilic defects of two substances itself, gas key inherently ruptures in the state of wet.It is whole
For upper, the water resistance of protein adhesive is better than carbohydrate.Because protein has divided in assimilation process, hydrophily
Group and oxygen key are combined into complex and the hydrophobic group of protein wood body are made to repel Boulez in extexine.On the contrary, carbon water
Although compound forms good oxygen key combination complex in inner layer in solidification process, there are many hydrophilic radicals for outer layer also foot.Institute
If with both substances make glued board wood adhesive, must by modification.Since carbohydrate divides
It, can not be with hydroxyl (- 0H), the amino (- NH in protein only containing single through base active function groups2), carboxyl (- COOH)
It is compared with phenolic hydroxyl group (- CoHsO), modifying machine can be fewer than protein very much.
U.S. Department of Energy (UnitedStatesDepartmentofEnergy) plan is renewable from plant to the year two thousand twenty
The basic chemical structure material of resource will account for 10%, and the year two thousand fifty will reach 50%.China also increases to renewable in recent years
The dynamics of the research and development of circulating resources.It can be used for preparing the reproducible object of nontoxic, natural novel adhesive a few days ago
Matter mainly has the polysaccharose substances such as protein, lignin, consaturated oil and chitosan, starch.Wherein, albumen
Matter is divided into phytoprotein and animal protein, and source of animal protein is less than 30%, and phytoprotein accounts for 70% or more.Source
Most abundant and cheap protein is soybean protein.Soybean skin, soybean bar, Soybean Leaves, soybean slag etc. also have respective
Use value.Therefore, soybean is that a kind of source is sufficient, renewable natural resources of widely used, product and functional diversities, right
Soybean deeply develop with systematic research, has important practical significance and application prospect.
It will be structural in the interaction and polypeptide chain in soybean protein between macromolecular using physics and chemical method
Connecting key is broken, and is fully extended so that protein helical form has been divided it may first have to the structuralization connecting key between polypeptide chain
With intermolecular interaction is broken changes, be allowed to be formed one be firmly adsorbed on reticular structure do elasticity people divide long-chain interweave and
At gluing soybean protein can be made to be converted into the Wood Adhesive of the excellent traitor of performance.The soybean protein prepared by the above method
Adhesive re-forms chemical crosslinking (disulfide bond etc.) at higher temperature (80-140 DEG C) and certain pressure, can be with shape
At biodegradable, heat cured adhesive layer.More active group is exposed by being crosslinked modification or changing modified soybean protein
Group, interacts with timber interface, the adhesive strength of soybean albumen adhesive and water resistance is made to obtain biggish improvement.Institute
Preparation key with soybean albumen adhesive is how to provide to occur required for cross-linking reaction in the case where adapting to fixed temperature and pressure
Functional group.Make soybean protein that there is enough tacks and carries out a degree of modification.
It is the soy based wood adhesives named as the U.S. is successfully proposed with " Purebong " over nearly 4 or five years,
So that it is stringent that California Air management administration (CARB), which proposes to the highest burst size of methanal ratio Eo more i of glued board,
New demand.The practice and extension of CARB regulation changes the international trade lattice of entire industry of artificial boards (all tool industry of family, floor industry etc.)
Office also makes China become firm " barrier " that wood-based plate exports to developed country.And soybean albumen adhesive industrialized production
Middle material loss is big, and production technology is complicated, requires production equipment high.In consideration of it, to promote agricultural and sideline product to high added value
Biomass high molecular material and the conversion of fossil feedstock substitute have application study and application value；And it is dirty to environment is mitigated
It contaminates pressure and reduction and excessively relies on fossil feedstock, alleviate the imbalance between supply and demand of wood-based plate and Flooring and promote industrial and agriculture
Coordinated development have important practical significance.
Soybean protein makes the viscosity of rubber made from soybean cake be up to 75000mPas or more as a kind of large biological molecule, not only unfavorable
Bonding strength is influenced in wetting, is also difficult to uniformly effectively be sprayed application to the fusing unit of the bigger serfaces such as wood shavings, fiber
On, therefore, rubber made from soybean cake is mainly used in the artificial board enterprise that normal plywood, core-board, integrated timber etc. are convenient for gluing at present
In, particieboard, oriented wood chipboard, etc. in enterprises, be still difficult to realize industrialized production.In order to reduce the viscosity of rubber made from soybean cake, lead to
The solid content of rubber made from soybean cake is often dropped into 10%-15%, to meet its sizing requirement in particieboard and fiberboard preparation.But it is big
Bean gum solid content is low, extends the hot pressing evacuation time of plate, causes production energy consumption to increase, efficiency reduction, is unfavorable for industry
Metaplasia produces.Therefore, under the premise of ensuring particieboard hot pressing efficiency, the viscosity of rubber made from soybean cake is reduced, to meet glue spraying requirement, is become
One technical bottleneck of bean gum particieboard preparation.
The core for improving rubber made from soybean cake particieboard hot pressing efficiency is to be crosslinked rubber made from soybean cake rapidly and sufficiently in hot pressing
Solidification, effectively improve the initial internal bond strength of particieboard, make particieboard can be resisted before release steam pressure without
It is bubbled.
Summary of the invention
The technical problems to be solved by the invention: it is lower for the soybean albumen adhesive cohesive force in existing market, it is resistance to
It is aqueous poor, the problem of not adapting to modernization large-scale industrial production, provide a kind of soybean protein based bi-component timber
The preparation method of adhesive.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) soyabean protein powder and deionized water are mixed, carries out stirring in water bath processing to get mixed solution, in mixed solution
Mixed and modified liquid is added, continues 1~2h of stirring in water bath to get matrix liquid；
(2 take matrix liquid, acrylic acid, carboxymethyl cellulose, N, and N '-methylene-bisacrylamide, ammonium persulfate, urea, 2- dredge base
Urea is added in matrix liquid and carries out gelatinization processing to get dextrin B, is being gelatinized for ethyl alcohol, acetone, dehydrated alcohol, deionized water
2- is added in liquid B and dredges base ethyl alcohol, is stirred to get reaction solution, acrylic acid, carboxymethyl cellulose is added in reaction solution
Element, N, N '-methylene-bisacrylamide and deionized water carry out constant temperature and are stirred to react to get mixed solution A, in mixed solution A
Middle addition ammonium persulfate continues to be stirred to react 4~5h to get mixed solution B, acetone precipitation is added in mixed solution B, centrifugation
It separates up to sediment, is added dehydrated alcohol, Soxhlet extraction 20~for 24 hours to get extracting material, drawer material, which is placed in temperature, is
It dries at 60~80 DEG C to constant weight, is cooled to room temperature to get presoma；
(3) presoma, pitch, carboxyl styrene emulsion, curing agent isocyanates are taken, by presoma, pitch and carboxyl styrene emulsion
Mixing, be stirred to get mixed material, in mixed material be added curing agent isocyanates, continue stirring 5~
10min is to get soybean protein based bi-component wood adhesive.
Stirring in water bath processing step described in step (1) are as follows: in mass ratio 1: 5 mixes soyabean protein powder and deionized water
It closes, is 50~60 DEG C in bath temperature, mixing speed is 20~30min of stirring in water bath under 200~300r/min.
The preparation step of mixed and modified liquid described in step (1) are as follows: in mass ratio 1: 2: 2 by lauryl sodium sulfate, matter
Amount score is 40% sodium hydroxide solution and mass fraction is that 40% calcium hydroxide is uniformly mixed to get mixed and modified liquid.
Mass ratio described in step (1) between mixed and modified liquid and mixed solution is 1: 10.
Matrix liquid, acrylic acid, carboxymethyl cellulose, N described in step (2), N '-methylene-bisacrylamide, persulfuric acid
Ammonium, urea, 2- dredge base ethyl alcohol, acetone, dehydrated alcohol, the ratio between deionized water and are respectively as follows: according to parts by weight, claim respectively
Take 20~30 parts of matrix liquid, 1~10 part of acrylic acid, 1~5 part of carboxymethyl cellulose, 1~3 part of N, N '-methylene bisacrylamide acyl
Amine, 0.5~0.7 part of ammonium persulfate, 1~5 part of urea, 0.1~0.3 part of 2- dredge base ethyl alcohol, 1~3 part of acetone, 5~10 parts it is anhydrous
Ethyl alcohol, 30~50 parts of deionized waters.
Described in step (2) in matrix liquid be added urea carry out gelatinization processing step are as follows: by matrix liquid temperature be 50
At~60 DEG C be gelatinized 5~10min to get dextrin A, urea is added in dextrin, continue in a nitrogen atmosphere gelatinization 10~
20min。
Stir process step described in step (2) are as follows: 2- is added in dextrin B and dredges base ethyl alcohol, low whipping speed 300
1~2h is stirred under~400r/min.
Constant temperature described in step (2) is stirred to react step are as follows: acrylic acid, carboxymethyl cellulose, N are added in reaction solution,
N '-methylene-bisacrylamide and deionized water stir 1~2h at being 60~70 DEG C in temperature.
Presoma described in step (3), pitch, carboxyl styrene emulsion, the ratio between curing agent isocyanates are respectively as follows:
According to parts by weight, 30~50 parts of presomas, 1~5 part of pitch, 1~10 part of carboxyl styrene emulsion, 1~3 part of solidification are weighed respectively
Agent isocyanates.
Stir process step described in step (3) are as follows: mix presoma, pitch and carboxyl styrene emulsion, in stirring speed
Degree is that 1~2h is stirred under 500~600r/min.
The present invention is compared with other methods, and advantageous effects are:
(1) after soybean protein is carried out alkali modification by the present invention, carboxymethyl cellulose and acrylic acid are grafted on modified soy-bean protein
As adhesive host agent, bound bitumen and carboxyl styrene emulsion, the adhesive prepared have good water resistance and caking property,
Carboxyl styrene emulsion has very strong water-reduction, higher cohesive force and conjunctiva intensity, and carboxyl styrene emulsion can make gluing
Macropore is reduced inside agent, pore structure refinement, so that the water absorption rate of adhesive is greatly lowered, full water intensity has obtained greatly mentioning
It is high；
(2) present invention grafted propylene acid on modified soy-bean protein, in the solidification of soybean protein based bi-component wood adhesive, meeting
One layer of hydrophobic film with hydrophobicity is generated, outside moisture can be effectively spaced apart, which reduces moisture to enter soybean protein
Inside based bi-component wood adhesive, to achieve the purpose that waterproof performance, therefore cohesive force also enhances therewith；
(3) carboxymethyl cellulose in the present invention has thickening, the protection of film forming, gluing, water tariff collection, colloid, emulsification and suspends
The effects of；The dark brown complex mixture that pitch is made of the hydrocarbon and its non metallic derivatives of different molecular weight,
It is one kind of high viscosity organic liquid, pitch belongs to hydrophobic material, it is waterproof, is also practically insoluble in water；Carboxy cream
Liquid is to add a small amount of carboxylic acid and other auxiliary agents with butadiene, styrene, the copolymer generated by emulsion polymerization, is a kind of with indigo plant
The milky aqueous dispersion of purple gloss；Combinated styrene content ratio is higher, cohesive force with higher and conjunctiva intensity, it is mechanical and
The advantages that chemical stability is good, and mobility, storage stability are good, and loading is big, residual benzene class monomer is little, belongs to environment-friendly type and produces
Product；Therefore the soybean protein based bi-component wood adhesive of preparation has good water resistance, caking property, and environmentally protective；
(4)-OH ,-COOH ,-NH isopolarity group and the base in soybean protein based bi-component wood adhesive prepared by the present invention
The intermolecular interaction force of material is the main source of soybean protein based bi-component wood adhesive bonding force；It is imbedded in albumen
Polar group inside matter spherical structure only can just be exposed under the action of modifying agent, theoretically protein molecule
Secondary structure more irregularly polar group exposure it is also more, steric hindrance between polar group and substrate molecule is also got over
It is low, also more it is conducive to the splicing of protein molecular and substrate；Mixed base modification liquid can make glycinin depolymerization, polypeptide chain exhibition
It opens, the degree of disorder becomes larger, to increase effective contact area between soybean protein group and substrate molecule, modified albumen
Its original of matter is hidden in internal hydrophobic side and interacts by then towards outer and surfactant hydrophobic position and form micella
Group, to increase the hydrophobicity of adhesive layer and then improve water-resistance, so that soybean protein based bi-component wood-gluing
The cohesive force and water resistance of agent are improved.
Specific embodiment
Lauryl sodium sulfate, mass fraction are 40% sodium hydroxide solution by mass ratio 1: 2: 2 and mass fraction is
40% calcium hydroxide is uniformly mixed to get mixed and modified liquid；In mass ratio 1: 5 mixes soyabean protein powder and deionized water, in water
Bath temperature is 50~60 DEG C, and mixing speed is that 20~30min of stirring in water bath is under 200~300r/min to get mixed solution, by matter
Mixed and modified liquid is added than 1: 10 in mixed solution for amount, continues 1~2h of stirring in water bath to get matrix liquid；According to parts by weight,
20~30 parts of matrix liquid, 1~10 part of acrylic acid, 1~5 part of carboxymethyl cellulose, 1~3 part of N, N '-di-2-ethylhexylphosphine oxide third are weighed respectively
Acrylamide, 0.5~0.7 part of ammonium persulfate, 1~5 part of urea, 0.1~0.3 part of 2- dredge base ethyl alcohol, 1~3 part of acetone, 5~10 parts
Dehydrated alcohol, 30~50 parts of deionized waters, at being 50~60 DEG C in temperature by matrix liquid 5~10min of gelatinization to get dextrin A,
Urea is added in dextrin, continues 10~20min of gelatinization in a nitrogen atmosphere to get dextrin B, is added in dextrin B
2- dredges base ethyl alcohol, and low whipping speed is that 1~2h is stirred under 300~400r/min to get reaction solution, and propylene is added in reaction solution
Acid, carboxymethyl cellulose, N, N '-methylene-bisacrylamide and deionized water, constant temperature stirring is anti-at being 60~70 DEG C in temperature
It answers 1~2h to get mixed solution A, ammonium persulfate is added in mixed solution A, it is molten to get mixing to continue to be stirred to react 4~5h
Acetone precipitation is added in mixed solution B in liquid B, is centrifugated up to sediment, is added dehydrated alcohol, and Soxhlet extraction 20~
For 24 hours to get extracting material, it is to dry at 60~80 DEG C to constant weight that drawer material, which is placed in temperature, is cooled to room temperature to get forerunner
Body；According to parts by weight, 30~50 parts of presomas, 1~5 part of pitch, 1~10 part of carboxyl styrene emulsion, 1~3 part are weighed respectively
Curing agent isocyanates mixes presoma, pitch and carboxyl styrene emulsion, and low whipping speed is to stir under 500~600r/min
1~2h is mixed to get mixed material, curing agent isocyanates is added in mixed material, continues 5~10min of stirring to get soybean
Albumen based bi-component wood adhesive.
Embodiment 1
Pretreatment steel wire and hawser fiber filament are twisted to get high-strength weather-proof type ship hawser.Pre-process the preparation of steel wire
Step are as follows: in steel wire surface even spread methenamine, naturally dry pre-processes steel wire to obtain the final product.Hawser fibre in mass ratio 1: 2: 2
By lauryl sodium sulfate, mass fraction be 40% sodium hydroxide solution and mass fraction is that 40% calcium hydroxide is uniformly mixed, i.e.,
Obtain mixed and modified liquid；In mass ratio 1: 5 mixes soyabean protein powder and deionized water, is 50 DEG C in bath temperature, mixing speed
Be stirring in water bath 20min under 200r/min to get mixed solution, in mass ratio 1: 10 be added in mixed solution it is mixed and modified
Liquid continues stirring in water bath 1h to get matrix liquid；According to parts by weight, 20 parts of matrix liquid, 1 part of acrylic acid, 1 part of carboxylic are weighed respectively
Methylcellulose, 1 part of N, N '-methylene-bisacrylamide, 0.5 part of ammonium persulfate, 1 part of urea, 0.1 part of 2- dredge base ethyl alcohol, 1 part
Acetone, 5 parts of dehydrated alcohols, 30 parts of deionized waters are gelatinized 5min at being 50 DEG C in temperature by matrix liquid to get dextrin A, are pasting
Change in liquid and urea is added, continues to be gelatinized 10min in a nitrogen atmosphere to get dextrin B, 2- is added in dextrin B and dredges base second
Alcohol, low whipping speed be under 300r/min stirring 1h to get reaction solution, be added in reaction solution acrylic acid, carboxymethyl cellulose,
N, N '-methylene-bisacrylamide and deionized water, constant temperature is stirred to react 1h to get mixed solution A at being 60 DEG C in temperature,
Ammonium persulfate is added in mixed solution A, continues to be stirred to react 4h to get mixed solution B, it is heavy that acetone is added in mixed solution B
It forms sediment, is centrifugated up to sediment, dehydrated alcohol is added, drawer material is placed in temperature to get extracting material by Soxhlet extraction 20h
Degree is to dry at 60 DEG C to constant weight, is cooled to room temperature to get presoma；According to parts by weight, 30 parts of presomas, 1 are weighed respectively
Part pitch, 1 part of carboxyl styrene emulsion, 1 part of curing agent isocyanates, presoma, pitch and carboxyl styrene emulsion are mixed, stirred
Mixing speed is that curing agent isocyanates is added in mixed material, continues to stir to get mixed material by stirring 1h under 500r/min
5min is to get soybean protein based bi-component wood adhesive.
Embodiment 2
Lauryl sodium sulfate, mass fraction are 40% sodium hydroxide solution by mass ratio 1: 2: 2 and mass fraction is 40% hydrogen
Calcium oxide is uniformly mixed to get mixed and modified liquid；In mass ratio 1: 5 mixes soyabean protein powder and deionized water, in water-bath temperature
Degree is 55 DEG C, and mixing speed is that stirring in water bath 25min is molten in mixing to get mixed solution, in mass ratio 1: 10 under 250r/min
Mixed and modified liquid is added in liquid, continues stirring in water bath 1.5h to get matrix liquid；According to parts by weight, 25 parts of matrixes are weighed respectively
Liquid, 5 parts of acrylic acid, 3 parts of carboxymethyl celluloses, 2 parts of N, N '-methylene-bisacrylamide, 0.6 part of ammonium persulfate, 3 parts of urea,
0.2 part of 2- dredges base ethyl alcohol, 2 parts of acetone, 7 parts of dehydrated alcohols, 40 parts of deionized waters, is gelatinized at being 55 DEG C in temperature by matrix liquid
Urea is added to get dextrin A in 7min in dextrin, continues to be gelatinized 15min in a nitrogen atmosphere to get dextrin B,
2- is added in dextrin B and dredges base ethyl alcohol, low whipping speed is to stir 1.5h under 350r/min to get reaction solution, in reaction solution
Acrylic acid, carboxymethyl cellulose, N, N '-methylene-bisacrylamide and deionized water is added, constant temperature stirs at being 65 DEG C in temperature
Reaction 1.5h is mixed to get mixed solution A, ammonium persulfate is added in mixed solution A, continues to be stirred to react 4.5h to get mixing
Acetone precipitation is added in mixed solution B in solution B, is centrifugated up to sediment, addition dehydrated alcohol, Soxhlet extraction 22h,
Up to extracting material, it is to dry at 70 DEG C to constant weight that drawer material, which is placed in temperature, is cooled to room temperature to get presoma；By weight
Number meter is measured, 40 parts of presomas, 3 parts of pitches, 5 parts of carboxyl styrene emulsions, 2 parts of curing agent isocyanates are weighed respectively, by forerunner
Body, pitch and carboxyl styrene emulsion mixing, low whipping speed are that 1.5h is stirred under 550r/min to get mixed material, are being mixed
Curing agent isocyanates is added in material, continues to stir 7min to get soybean protein based bi-component wood adhesive.
Embodiment 3
Lauryl sodium sulfate, mass fraction are 40% sodium hydroxide solution by mass ratio 1: 2: 2 and mass fraction is 40% hydrogen
Calcium oxide is uniformly mixed to get mixed and modified liquid；In mass ratio 1: 5 mixes soyabean protein powder and deionized water, in water-bath temperature
Degree is 60 DEG C, and mixing speed is that stirring in water bath 30min is molten in mixing to get mixed solution, in mass ratio 1: 10 under 300r/min
Mixed and modified liquid is added in liquid, continues stirring in water bath 2h to get matrix liquid；According to parts by weight, weigh respectively 30 parts of matrix liquid,
10 parts of acrylic acid, 5 parts of carboxymethyl celluloses, 3 parts of N, N '-methylene-bisacrylamide, 0.7 part of ammonium persulfate, 5 parts of urea, 0.3
Part 2- dredges base ethyl alcohol, 3 parts of acetone, 10 parts of dehydrated alcohols, 50 parts of deionized waters, is gelatinized at being 60 DEG C in temperature by matrix liquid
Urea is added to get dextrin A in 10min in dextrin, continues to be gelatinized 20min in a nitrogen atmosphere to get dextrin B,
2- is added in dextrin B and dredges base ethyl alcohol, low whipping speed is to stir 2h under 400r/min to get reaction solution, is added in reaction solution
Enter acrylic acid, carboxymethyl cellulose, N, N '-methylene-bisacrylamide and deionized water, constant temperature stirs at being 70 DEG C in temperature
2h is reacted to get mixed solution A, ammonium persulfate is added in mixed solution A, continues to be stirred to react 5h to get mixed solution B,
Acetone precipitation is added in mixed solution B, is centrifugated up to sediment, dehydrated alcohol is added, Soxhlet extraction is for 24 hours to get pumping
Extract material, it is to dry at 80 DEG C to constant weight that drawer material, which is placed in temperature, is cooled to room temperature to get presoma；In parts by weight
Meter, weighs 50 parts of presomas, 5 parts of pitches, 10 parts of carboxyl styrene emulsions, 3 parts of curing agent isocyanates respectively, by presoma, drip
Blueness and carboxyl styrene emulsion mixing, low whipping speed are that 2h is stirred under 600r/min to get mixed material, are added in mixed material
Enter curing agent isocyanates, continues to stir 10min to get soybean protein based bi-component wood adhesive.
Soybean protein based bi-component wood adhesive prepared by the present invention is detected, specific testing result such as following table table
1:
The soybean protein based bi-component wood adhesive prepared through the present embodiment 1-3 is a kind of environmental-protection type adhesive, without harmful gas
Body release, pH value 7.3 are in neutrality, and reduce the stimulation to glued material corrosive properties and direct labor.Using of the invention big
Legumin based bi-component wood adhesive suppresses 3 layers of poplar plywood, evaluates the bonding strength and water-fast intensity of adhesive.Poplar
Specification of the Board be 300mm × 300mm × 2mm, resin added every square centimeter be 1.5mg, 140 DEG C of hot pressing temperature, hot pressing pressure
For 2.5MPa, hot pressing time 60s/mm.Then by the glued board of compacting according to GB/T9846-2004 standard testing bonding strength,
By the glued board of compacting according to GB/T9846-2004 standard clipping after, being immersed in temperature is that 5h(examination is impregnated in 63 ± 5 DEG C of water
Sample is all immersed in water and plus lid), it takes out after being stored at room temperature 10min, it is water-fast glued strong in mechanical test aircraft measurements
Degree.
1 soybean protein based bi-component wood adhesive performance characterization of table
Soybean protein based bi-component wood adhesive prepared by the present invention as shown in Table 1, butt bonding strength is 1.31MPa, wet
Base bonding strength is 1.15MPa, greater than the requirement that national standard is greater than 0.7MPa, reaches National Standards for Plywood GB/T9846-2004
In II class adhesive standard, water-tolerant, caking property is strong.
Claims (10)
1. a kind of preparation method of soybean protein based bi-component wood adhesive, it is characterised in that specific preparation step are as follows:
(1) soyabean protein powder and deionized water are mixed, carries out stirring in water bath processing to get mixed solution, in mixed solution
Mixed and modified liquid is added, continues 1~2h of stirring in water bath to get matrix liquid；
(2 take matrix liquid, acrylic acid, carboxymethyl cellulose, N, and N '-methylene-bisacrylamide, ammonium persulfate, urea, 2- dredge base
Urea is added in matrix liquid and carries out gelatinization processing to get dextrin B, is being gelatinized for ethyl alcohol, acetone, dehydrated alcohol, deionized water
2- is added in liquid B and dredges base ethyl alcohol, is stirred to get reaction solution, acrylic acid, carboxymethyl cellulose is added in reaction solution
Element, N, N '-methylene-bisacrylamide and deionized water carry out constant temperature and are stirred to react to get mixed solution A, in mixed solution A
Middle addition ammonium persulfate continues to be stirred to react 4~5h to get mixed solution B, acetone precipitation is added in mixed solution B, centrifugation
It separates up to sediment, is added dehydrated alcohol, Soxhlet extraction 20~for 24 hours to get extracting material, drawer material, which is placed in temperature, is
It dries at 60~80 DEG C to constant weight, is cooled to room temperature to get presoma；
(3) presoma, pitch, carboxyl styrene emulsion, curing agent isocyanates are taken, by presoma, pitch and carboxyl styrene emulsion
Mixing, be stirred to get mixed material, in mixed material be added curing agent isocyanates, continue stirring 5~
10min is to get soybean protein based bi-component wood adhesive.
2. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, it is characterised in that:
Stirring in water bath processing step described in step (1) are as follows: in mass ratio 1: 5 mixes soyabean protein powder and deionized water, in water-bath
Temperature is 50~60 DEG C, and mixing speed is 20~30min of stirring in water bath under 200~300r/min.
3. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, it is characterised in that:
The preparation step of mixed and modified liquid described in step (1) are as follows: lauryl sodium sulfate, mass fraction are by mass ratio 1: 2: 2
40% sodium hydroxide solution and mass fraction are that 40% calcium hydroxide is uniformly mixed to get mixed and modified liquid.
4. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, it is characterised in that:
Mass ratio described in step (1) between mixed and modified liquid and mixed solution is 1: 10.
5. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, it is characterised in that:
Matrix liquid, acrylic acid, carboxymethyl cellulose, N described in step (2), N '-methylene-bisacrylamide, ammonium persulfate, urea,
2- dredges base ethyl alcohol, acetone, dehydrated alcohol, the ratio between deionized water and is respectively as follows: according to parts by weight, weighs 20~30 respectively
Part matrix liquid, 1~10 part of acrylic acid, 1~5 part of carboxymethyl cellulose, 1~3 part of N, N '-methylene-bisacrylamide, 0.5~
0.7 part of ammonium persulfate, 1~5 part of urea, 0.1~0.3 part of 2- dredge base ethyl alcohol, 1~3 part of acetone, 5~10 parts of dehydrated alcohols, 30~
50 parts of deionized waters.
6. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, it is characterised in that:
Urea is added described in step (2) in matrix liquid and carries out gelatinization processing step are as follows: by matrix liquid in the case where temperature is 50~60 DEG C
5~10min is gelatinized to get dextrin A, urea is added in dextrin, continues 10~20min of gelatinization in a nitrogen atmosphere.
7. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, it is characterised in that:
Stir process step described in step (2) are as follows: 2- is added in dextrin B and dredges base ethyl alcohol, low whipping speed is 300~400r/
1~2h is stirred under min.
8. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, it is characterised in that:
Constant temperature described in step (2) is stirred to react step are as follows: acrylic acid, carboxymethyl cellulose, N, N '-methylene are added in reaction solution
Bisacrylamide and deionized water stir 1~2h at being 60~70 DEG C in temperature.
9. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, it is characterised in that:
Presoma described in step (3), pitch, carboxyl styrene emulsion, the ratio between curing agent isocyanates are respectively as follows: by weight
Number meter, weighs 30~50 parts of presomas, 1~5 part of pitch, 1~10 part of carboxyl styrene emulsion, 1~3 part of curing agent isocyanic acid respectively
Ester.
10. a kind of preparation method of soybean protein based bi-component wood adhesive according to claim 1, feature exist
In: stir process step described in step (3) are as follows: mix presoma, pitch and carboxyl styrene emulsion, low whipping speed is
1~2h is stirred under 500~600r/min.
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| CN113321936A (en) * | 2021-06-30 | 2021-08-31 | 西南林业大学 | High-strength biomass membrane material and preparation method thereof |
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