CN101412899A - Completely degradable plant protein wood adhesive and preparation thereof - Google Patents
Completely degradable plant protein wood adhesive and preparation thereof Download PDFInfo
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Abstract
The invention relates to a full biodegradable plant protein wood adhesive and a preparation method thereof, and belongs to the technical field of adhesive. The adhesive is prepared from the following components in weight portion: 100 portions of water, 5 to 20 portions of plant protein powder, 0 to 15 portions of acidity regulator, 0.05 to 20 portions of modifying agent, 0.05 to 10 portions of assistant, 0.1 to 10 portions of preservative, and 0 to 10 portions of stuffing. The preparation method comprises the following steps in turn: adding the water into a container, and dissolving the acidity regulator under a stirring state; adding the plant protein powder into the container under the stirring state; at the same time, complementing the acidity regulator according to change situations of pH values; heating a reaction system to a temperature needed by modification reaction, adding the modifying agent and the assistant into the container under the stirring state, and keeping the temperature to make the mixture reacted for 15 to 240 minutes at a temperature of between 5 and 60 DEG C; and in the last 2 to 5 minutes of the temperature keeping reaction, adding the preservative into the solution, and stirring the mixture evenly; and adding the stuffing into the reaction system, stirring evenly the mixture, and finally obtaining the wood adhesive. The adhesive has the advantages that the adhesive is easy to process, good in adhering property, and degradable.
Description
Technical field
The invention belongs to the adhesive technology field, particularly a kind of completely degradable plant protein wood adhesive and preparation method thereof.
Background technology
Wood adhesive is generally macromolecular compound, according to its different raw material sources, can be divided into natural polymer tackiness agent and synthetic macromolecule tackiness agent.The natural polymer tackiness agent has very long history in China, and half leaf also once used at US and European in a large number before eighties of last century.Because it is a raw material with the crude substance mainly, exist a large amount of hydrophilic radicals such as hydroxyl in the molecule, its water resistance, resistance toheat and bonding strength are all not really desirable, have limited it in industrial widespread use.Since the sixties in last century, along with the expansion of wood-based panel industry scale, the demand of tackiness agent is also growing, thereby has promoted the development of synthetic macromolecule tackiness agent.This class tackiness agent has that the veneer wettability is good, easy to use, the bonding strength advantages of higher, has dominated the timber industry tackiness agent rapidly.At present, the tackiness agent of wood-based panel industry use is based on urea-formaldehyde resin adhesive, Phenol aldehyde resin and ultrapas glutol.According to incompletely statistics, by 2007, the urea-formaldehyde resin adhesive that the artificial board industry of China consumes surpassed 4,000,000 tons.
Yet the synthetic macromolecule tackiness agent also exists the defective that can not be ignored when generally using.This class tackiness agent is discharged the toxic substance contaminate environment in production and use, in use discharge obnoxious flavoures such as formaldehyde with its bonding sheet material, also can influence environmental quality when depleted sheet material is degraded under field conditions (factors).Along with the enhancing of expanding economy and people's environmental consciousness, the drawback of adhesive made of synthetic resin more and more causes human great attention.Numerous and confused new laws and regulations, the burst size of methanal in the restriction wood-based plate worked out of developed country and area such as Japan, the U.S. and European Union.Under this situation, from the nineties in last century so far, started natural polymer Study on making adhesives upsurge in the world again.
Vegetable-protein has abundant reserves as the protein of cheapness at occurring in nature, possesses reproducible characteristics, and contains in the molecule in a large number and can participate in the Activity of Chemical Reaction group.The tackiness agent of producing with its modification has cheap, and production technique is simple, and is easy to use, to the person poultry harmless, can biological degradation, and can not cause advantages such as public hazards to environment, be that the ideal that substitutes three-aldehyde glue is selected.The research that utilizes vegetable-protein to make wood adhesive at present mainly still concentrates on the modification aspect to soybean protein, and is fewer for the proteic research of other plant.The present invention has proposed pointed method of modifying on the basis that vegetable seed, peanut, wheat protein molecular structure and characteristic are fully studied, thereby provides new approach for the comprehensive utilization of grain and oil crops.
Summary of the invention
It is the completely degradable plant protein wood adhesive and preparation method thereof of main raw material with the plant protein powder that the object of the invention is to provide a kind of.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: completely degradable plant protein wood adhesive, formulated by the composition of following parts by weight:
100 parts in water,
5～20 parts of plant protein powders,
0～15 part of acidity regulator,
0.05～20 part of properties-correcting agent,
0.05～10 part of auxiliary agent,
0.1～10 part of sanitas,
0～10 part of filler.
Described plant protein powder is one or more the mixture in defatted soyflour, degreased peanut flour, gluten powder, the degreasing rapeseed meal; Described acidity regulator is one or more the mixture in citric acid, Trisodium Citrate, yellow soda ash, sodium bicarbonate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, boric acid, Repone K, hydrochloric acid, sulfuric acid, sodium hydroxide, the potassium hydroxide; Described properties-correcting agent is one or more the mixture in phosphorus oxychloride, diacetyl oxide, succinyl oxide, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium bisulfite, S-WAT, mercaptoethanol, Thiovanic acid, sulfo-threitol, urea, the Guanidinium hydrochloride; Described auxiliary agent is one or more the mixture in tetracol phenixin, normal hexane, tributyl phosphate, mono-glycerides, Resorcinol, Resorcinol, pyrocatechol, glycerine, sorbyl alcohol, ethylene glycol, glycol ether, seaweed gel, guar gum, the sodium polyacrylate; Described sanitas is one or more the mixture in potassium sorbate, phytic acid, dehydroacetic acid (DHA), butyl p-hydroxybenzoate, dimethyl fumarate, sodium Diacetate, Sodium Benzoate, Sodium Propionate, the calcium propionate; Described filler is one or more the mixture in flour, diatomite, kaolin, wilkinite, light calcium carbonate, silicon-dioxide, potter's clay, wollastonite, the Mierocrystalline cellulose.
The protein content of described plant protein powder must not be lower than 50%wt (weight content, down together).
The preparation method of completely degradable plant protein wood adhesive comprises the following steps: successively
(1), in container, add the water of 100 weight parts, under whipped state, add 0～10 part acidity regulator dissolving;
(2), under whipped state, in container, add the plant protein powder of 5～20 weight parts, simultaneously according to the changing conditions of pH value, additional acidity regulator;
(3), that reaction system is warming up to modified-reaction is temperature required, adds 0.05～20 part properties-correcting agent and 0.05～10 part auxiliary agent under the whipped state in container, 5 ℃～60 ℃ insulation reaction 15～240 minutes;
(4), last 2～5 minutes of insulation reaction, in solution, add the sanitas of 0.1～10 weight part, stir;
(5), the filler that adds 0～10 weight part in reaction system stirs, wood adhesive.
Described acidity regulator is one or more the mixture in citric acid, Trisodium Citrate, yellow soda ash, sodium bicarbonate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, boric acid, Repone K, hydrochloric acid, sulfuric acid, sodium hydroxide, the potassium hydroxide; Described plant protein powder is one or more the mixture in defatted soyflour, degreased peanut flour, gluten powder, the degreasing rapeseed meal; Described properties-correcting agent is one or more mixtures in phosphorus oxychloride, diacetyl oxide, succinyl oxide, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium bisulfite, S-WAT, mercaptoethanol, Thiovanic acid, sulfo-threitol, urea, the Guanidinium hydrochloride; Described auxiliary agent is one or more the mixture in tetracol phenixin, normal hexane, tributyl phosphate, mono-glycerides, Resorcinol, Resorcinol, pyrocatechol, glycerine, sorbyl alcohol, ethylene glycol, glycol ether, seaweed gel, guar gum, the sodium polyacrylate; Described sanitas is one or more the mixture in potassium sorbate, phytic acid, dehydroacetic acid (DHA), butyl p-hydroxybenzoate, dimethyl fumarate, sodium Diacetate, Sodium Benzoate, Sodium Propionate, the calcium propionate; Described filler is one or more the mixture in flour, diatomite, kaolin, wilkinite, light calcium carbonate, silicon-dioxide, potter's clay, wollastonite, the Mierocrystalline cellulose.
The protein content of described plant protein powder must not be lower than 50%wt.
Temperature of reaction in the step (3); the temperature of reaction of acylation modification is 40 ℃～60 ℃; the temperature of reaction of esterification modification is 20 ℃～45 ℃, and temperature of reaction surfactant-modified and the reduction modification is 20 ℃～60 ℃, and the temperature of reaction of urea modification is 15 ℃～50 ℃.
Technological process of the present invention is: the albumen dispersion emulsion that plant protein powder and water is made into 5%～20%wt, elevated temperature simultaneously adds behind the properties-correcting agent modification 0.25～4h under specific pH and temperature environment again, adds sanitas and filler at last, be cooled to normal temperature then, discharging.Only need simple impregnation to use before the applying glue.
Utilize in the production plywood process of the present invention, in gluing and assembly step, the veneer of long core direction carried out two-sided applying glue after, drying makes water ratio reduce to 13～17%, is spliced into complete central layer-dried offset plate; Again the complete central layer of the horizontally-spliced one-tenth of veneer of short core direction, to forming the plate base with the dried offset plate assembly that superposes in length and breadth after its two-sided applying glue; Between hot pressing and finish process, increase the health step, between the plate base, place the stacking of parting bead piling and leave standstill more than the 48h.The same prior art of other steps.
It is raw material that the present invention adopts greases such as defatted soyflour, degreased peanut flour, gluten powder, degreasing rapeseed meal and starch industry byproduct, and wherein vegetable-protein is carried out chemical modification, forms specific molecular structure, satisfies the requirement of bonding timber; Adopt acidylate, esterification, urea modification, reduction modification, method such as surfactant-modified, prepare the plant albumin glue adhesive of the better water resistance of several tools; Used chemical is nontoxic or low toxicity during modification, advantages such as the tackiness agent of making has stable in properties, set time is short, bonding strength is high, biodegradable, be applicable to the production of glued board series products, alternative present widely used urea-formaldehyde resin adhesive.Technological operation of the present invention is easy, and non-environmental-pollution is easy to form suitability for industrialized production.
By the glued board gummed intensity of the tackiness agent production of the inventive method processing reach 1.95MPa (GB/T9846-2004 for 〉=0.70MPa), burst size of methanal only 0.1mg/L (GB/T9846-2004 is≤0.5mg/L).
Embodiment
Embodiment 1: completely degradable plant protein wood adhesive prescription (parts by weight) is:
Gluten powder 9
Water 100
Citric acid 0.77
Sodium phosphate dibasic 2.21
Phosphorus oxychloride 0.5
Tetracol phenixin 2.5
Glycerine 0.5
Potassium sorbate 0.1.
Preparation process is: citric acid and Sodium phosphate dibasic are dissolved in the buffered soln that is mixed with pH6.0 in the 20-30 ℃ of water, add gluten powder while stirring, making it to be uniformly dispersed becomes milk sap.Phosphorus oxychloride is dissolved in advance the solution that is made into 20% (v/v) in the tetracol phenixin.Under whipped state, phosphorus oxychloride solution is slowly dripped in reaction system, dropwised in 10 minutes.Keep mixing speed constant, insulation reaction 60 minutes.Reaction finishes preceding 5 minutes, adds glycerine and potassium sorbate.After reaction finishes, be finished product.
Embodiment 2: completely degradable plant protein wood adhesive prescription (parts by weight) is:
Defatted soyflour 10
Water 100
Diacetyl oxide 1
Sodium polyacrylate 0.1
Dehydroacetic acid (DHA) 0.25
Sodium bentonite 5
Preparation process is: get load weighted defatted soyflour and slowly add in the water that is preheated to 50 ℃, feed time was controlled at 5～10 minutes, adopted 150 rev/mins rotating speed to stir in adition process.After stirring becomes the homogeneous emulsion, divide diacetyl oxide 5 times and add in the reaction system, adding in 10 minutes finishes.Stirring velocity is reduced to 75r/min, insulation reaction 90 minutes.When reaction proceeds to 80 minutes, add sodium polyacrylate and dehydroacetic acid (DHA).Reaction is cooled to 20 ℃～30 ℃ after finishing, and adds sodium bentonite, continues stirring and is finished product in 5 minutes.
Embodiment 3: completely degradable plant protein wood adhesive prescription (parts by weight) is:
Degreasing rapeseed meal 10
Water 100
Yellow soda ash 11.5
Sodium bicarbonate 0.5
Sodium lauryl sulphate 0.5
Mercaptoethanol 0.2
Butyl p-hydroxybenzoate 0.2
Octanol 0.2
Kaolin 5.
Preparation process is: yellow soda ash and sodium bicarbonate are mixed with the aqueous solution of 0.1mol/L concentration respectively, and the two mixed with 4:6 becomes buffered soln.Buffered soln is preheated to 55 ℃, adds the degreasing rapeseed meal while stirring, mixing speed 100r/min, reinforced finishing in 5 minutes.Keep mixing speed constant, add sodium lauryl sulphate and mercaptoethanol successively, insulation reaction 60 minutes.Add octanol in the reaction process, eliminate the foam that reaction produces.Reaction finishes preceding 5 minutes, adds the sanitas butyl p-hydroxybenzoate.After reaction finishes, add kaolin, continue to stir 5 minutes, be finished product while lowering the temperature.
Embodiment 4: completely degradable plant protein wood adhesive prescription (parts by weight) is:
Degreased peanut flour 9
Water 100
Boric acid 0.38
Repone K 0.46
Sodium hydroxide 0.1
Urea 9
Guar gum 0.3
Glycol ether 1
Dimethyl fumarate 0.5
Light calcium carbonate 4.
Preparation process is: boric acid, Repone K and potassium hydroxide are made into pH9.0 buffered soln in proportion.Under 20～30 ℃ of conditions, in buffered soln, slowly add degreased peanut flour, mixing speed 90r/min, 5～10 minutes reinforced finishing.Keep mixing speed constant, add urea, insulation reaction 60 minutes.When reacting 55 minutes, add glycol ether, guar gum, dimethyl fumarate and light calcium carbonate, continue to stir 10 minutes, be finished product.
Claims (7)
1, completely degradable plant protein wood adhesive is characterized in that, and is formulated by the composition of following parts by weight:
100 parts in water,
5～20 parts of plant protein powders,
0～15 part of acidity regulator,
0.05～20 part of properties-correcting agent,
0.05～10 part of auxiliary agent,
0.1～10 part of sanitas,
0～10 part of filler.
2, completely degradable plant protein wood adhesive as claimed in claim 1 is characterized in that, described plant protein powder is one or more the mixture in defatted soyflour, degreased peanut flour, gluten powder, the degreasing rapeseed meal; Described acidity regulator is one or more the mixture in citric acid, Trisodium Citrate, yellow soda ash, sodium bicarbonate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, boric acid, Repone K, hydrochloric acid, sulfuric acid, sodium hydroxide, the potassium hydroxide; Described properties-correcting agent is one or more the mixture in phosphorus oxychloride, diacetyl oxide, succinyl oxide, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium bisulfite, S-WAT, mercaptoethanol, Thiovanic acid, sulfo-threitol, urea, the Guanidinium hydrochloride; Described auxiliary agent is one or more the mixture in tetracol phenixin, normal hexane, tributyl phosphate, mono-glycerides, Resorcinol, Resorcinol, pyrocatechol, glycerine, sorbyl alcohol, ethylene glycol, glycol ether, seaweed gel, guar gum, the sodium polyacrylate; Described sanitas is one or more the mixture in potassium sorbate, phytic acid, dehydroacetic acid (DHA), butyl p-hydroxybenzoate, dimethyl fumarate, sodium Diacetate, Sodium Benzoate, Sodium Propionate, the calcium propionate; Described filler is one or more the mixture in flour, diatomite, kaolin, wilkinite, light calcium carbonate, silicon-dioxide, potter's clay, wollastonite, the Mierocrystalline cellulose.
3, completely degradable plant protein wood adhesive as claimed in claim 2 is characterized in that, the protein content of described plant protein powder must not be lower than 50%wt.
4, the preparation method of completely degradable plant protein wood adhesive is characterized in that, comprises the following steps: successively
(1), in container, add the water of 100 weight parts, under whipped state, add 0～10 part acidity regulator dissolving;
(2), under whipped state, in container, add the plant protein powder of 5～20 weight parts, simultaneously according to the changing conditions of pH value, additional acidity regulator;
(3), that reaction system is warming up to modified-reaction is temperature required, adds 0.05～20 part properties-correcting agent and 0.05～10 part auxiliary agent under the whipped state in container, 5 ℃～60 ℃ insulation reaction 15～240 minutes;
(4), last 2～5 minutes of insulation reaction, in solution, add the sanitas of 0.1～10 weight part, stir;
(5), the filler that adds 0～10 weight part in reaction system stirs, wood adhesive.
5, the preparation method of completely degradable plant protein wood adhesive as claimed in claim 4, it is characterized in that described acidity regulator is one or more the mixture in citric acid, Trisodium Citrate, yellow soda ash, sodium bicarbonate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, boric acid, Repone K, hydrochloric acid, sulfuric acid, sodium hydroxide, the potassium hydroxide; Described plant protein powder is one or more the mixture in defatted soyflour, degreased peanut flour, gluten powder, the degreasing rapeseed meal; Described properties-correcting agent is one or more mixtures in phosphorus oxychloride, diacetyl oxide, succinyl oxide, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium bisulfite, S-WAT, mercaptoethanol, Thiovanic acid, sulfo-threitol, urea, the Guanidinium hydrochloride; Described auxiliary agent is one or more the mixture in tetracol phenixin, normal hexane, tributyl phosphate, mono-glycerides, Resorcinol, Resorcinol, pyrocatechol, glycerine, sorbyl alcohol, ethylene glycol, glycol ether, seaweed gel, guar gum, the sodium polyacrylate; Described sanitas is one or more the mixture in potassium sorbate, phytic acid, dehydroacetic acid (DHA), butyl p-hydroxybenzoate, dimethyl fumarate, sodium Diacetate, Sodium Benzoate, Sodium Propionate, the calcium propionate; Described filler is one or more the mixture in flour, diatomite, kaolin, wilkinite, light calcium carbonate, silicon-dioxide, potter's clay, wollastonite, the Mierocrystalline cellulose.
6, the preparation method of completely degradable plant protein wood adhesive as claimed in claim 5 is characterized in that, the protein content of described plant protein powder must not be lower than 50%wt.
7, the preparation method of completely degradable plant protein wood adhesive as claimed in claim 5; it is characterized in that; temperature of reaction in the step (3); the temperature of reaction of acylation modification is 40 ℃～60 ℃; the temperature of reaction of esterification modification is 20 ℃～45 ℃; temperature of reaction surfactant-modified and the reduction modification is 20 ℃～60 ℃, and the temperature of reaction of urea modification is 15 ℃～50 ℃.
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