CN107641495A - A kind of vegetable protein adhesive and its preparation method and application - Google Patents
A kind of vegetable protein adhesive and its preparation method and application Download PDFInfo
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- CN107641495A CN107641495A CN201710979162.8A CN201710979162A CN107641495A CN 107641495 A CN107641495 A CN 107641495A CN 201710979162 A CN201710979162 A CN 201710979162A CN 107641495 A CN107641495 A CN 107641495A
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- vegetable protein
- glucose
- protein adhesive
- adhesive
- crosslinking agent
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Abstract
The invention provides a kind of vegetable protein adhesive and its preparation method and application.Adhesive provided by the invention does not all include formaldehyde using green material as crosslinking agent in all preparing raw materials, fundamentally can thoroughly solve the problems, such as adhesive Form aldehyde release, more green, environmental protection.It can be seen from the result of embodiment, complete greenization is realized without poisonous and harmful substances, adhesives such as free formaldehyde, free benzene compounds in the vegetable protein adhesive that the present invention obtains, the green core-board of unharmful substance release can be produced.And the viscosity of the vegetable protein adhesive prepared by the present invention is between 4520~9860MPas, hence it is evident that more than the viscosity (3490~3610MPas) of the adhesive prepared by the method for reference examples 1~3.
Description
Technical field
The present invention relates to adhesive technical field, more particularly to a kind of vegetable protein adhesive and preparation method thereof and should
With.
Background technology
Along with the reduction of the forest reserves and the shortage of timber, wood-based plate has become important in human being's production and life
Material, the development that wood-based panel industry is also advanced by leaps and bounds, China's wood-based plate yield in 2016 is more than 3.5 billion cubic meters, surely
Rank first in the world.At present, the adhesive generally used in Wood-based Panel Production is formaldehyde system synthetic resin, with Lauxite and its
Based on modified product.The timber products such as the wood-based plate manufactured using urea-formaldehyde resin adhesive and its furniture, floor can be successive
Ground discharges formaldehyde, pollutes indoor air environment, endangers the health of the people, and formaldehyde pollution turns into the focus that society pays high attention to
Problem.
In recent years, wood-based plate production technology level in China's had obtained large increase, was reducing artificial board formaldehyde burst size side
Many research work have been done in face, such as：By reducing the mol ratio of formaldehyde, adding resorcinol, cyanurotriamide modified and formaldehyde
The modes such as agent for capturing reduce the free formaldehyde content of Lauxite, or the activity easily combined using ammonia, ozone etc. with formaldehyde
Molecule post-processes to wood-based plate, and these measures or method reduce the burst size of methanal of wood-based plate to a certain extent, but not
Can fundamentally solve the problems, such as the formaldehyde pollution of wood-based plate and its timber products.
Because soybean protein molecular weight is big, structure and complicated components, chemical modification or modification to protein molecular are brought
Larger difficulty, soy protein adhesives, which can not be completely secured, in conventional modification has qualified water-fast bonding property.And
Strengthen modified method using crosslinking agent, be remarkably improved the water resistance and bonding strength of soy protein adhesives.However, at present
The complete green of soy protein adhesives is not implemented using non-renewable petrochemical industry derivative as raw material in the crosslinking agent overwhelming majority used
Color and renewableization, and aldehydes and its derivative, isocyanates material and other macromolecules are used as crosslinking agent, meeting
The pollution problem of the volatile harmful material such as free formaldehyde, benzene homologues is brought to soy protein adhesives and its splicing wood-based plate.
The content of the invention
It is an object of the invention to provide a kind of vegetable protein adhesive and its preparation method and application.It is provided by the invention
Adhesive does not all include formaldehyde, fundamentally can thoroughly solve glue using green material as crosslinking agent in all preparing raw materials
Glutinous agent Form aldehyde release problem, more green, environmental protection.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of vegetable protein adhesive, it is prepared by the raw material comprising following mass fraction：
The crosslinking agent is glucose-lignin resin crosslinking agent, urea-dialdehyde starch resin and tannin-furfuryl alcohol resin
In one or more；
The glucose-lignin resin crosslinking agent is the hydrolysate of glucose and the polymerizate of lignin.
Preferably, the glucose-lignin resin crosslinking agent is prepared according to the method comprised the following steps：
D/W is issued into unboiled water solution in the catalysis of acidic catalyst, obtains hydrolysate system；
The pH value for adjusting the hydrolysate system is 10~13, obtains alkaline hydrolysis products system；
The alkaline hydrolysis products system and lignin are subjected to polymerisation, obtain glucose-lignin resin crosslinking
Agent.
Preferably, the mass ratio of glucose and water is (2~5) in the D/W:1.
Preferably, the mass ratio of the glucose, acidic catalyst and lignin is (2~5):(0.01~0.1):(0.1
~0.5).
Preferably, the acidic catalyst is the one or more in hydrochloric acid, sulfuric acid, nitric acid, halogen acids and oxalic acid.
Preferably, the temperature of the polymerisation is 80~85 DEG C.
Preferably, the vegetable protein is defatted soy flour, defatted soybean meal, soybean protein isolate, degreased peanut flour, absorbent cotton
One or more in the seed dregs of rice, degreasing oil-tea-cake meal and degreasing bio-fuel almond powder.
Present invention also offers a kind of preparation method of vegetable protein adhesive described in above-mentioned technical proposal, includes following step
Suddenly：
(1) vegetable protein, water, activator and alkali are subjected to hot mixing, obtain the mixed raw material of heat；
(2) the mixed raw material of the heat and crosslinking agent are subjected to cross-linked polymeric, obtain vegetable protein adhesive.
Preferably, the temperature of hot mixing is 80~90 DEG C in the step (1), and the time is 1~3h；
The temperature of cross-linked polymeric is 65~78 DEG C in the step (2), and the time is 0.1~2h.
Present invention also offers preparation described in vegetable protein adhesive described in above-mentioned technical proposal or above-mentioned technical proposal
Application of the vegetable protein adhesive that method obtains in core-board is prepared.
The invention provides a kind of vegetable protein adhesive and preparation method thereof.Vegetable protein adhesive provided by the invention
Used raw material without the harmful substance such as formaldehyde, benzene compounds, organic amine compound, and alkali lye used in raw material,
Activator is the chemical reagent of usual non-toxic；Preservative used is the typical additives for food antiseptic；Crosslinking used
Agent come from reproducible lignin and glucose hydrolysis product polymer or for urea-dialdehyde starch resin and tannin-
Furfuryl alcohol resin, there is the advantages of nontoxic, green, environmentally safe, so that the complete greenization of plant albumin glue adhesive, therefore
The release of the volatile organic matters such as formaldehyde, organic benzene homologues, ammonia is not present in wood-based plate prepared by vegetable protein adhesive, thoroughly solution
Volatile organic matter pollution problem in the indoor environment that wood-based plate and its woodwork are brought of having determined.
Primary raw material-vegetable protein used in vegetable protein adhesive provided by the invention is former both from agricultural-forestry biomass
The residues caused by processing such as material production edible oil materials, bio-fuel, wide material sources, relative low price, can significantly reduce glue
The production cost of stick, while the comprehensive utilization of resource is realized, effectively increase the added value of agricultural-forestry biomass raw material.
Vegetable protein adhesive preparation method provided by the invention is simple, easy to use, the alternative conventional people containing formaldehyde
Plate adhesive is made, and existing Wood-based Panel Production equipment and production technology need not be modified, therefore equipment throwing need not be increased
Skilled worker is provided and retrains, suitable for industrialized production and application.
The technical scheme of vegetable protein adhesive of the present invention is carried out using first with activator and alkali to vegetable protein
Multiplicity reactivation, by destroying the secondary keys such as the intersegmental hydrogen bond of protein molecular peptide chain, sat linkage and hydrophobic, hydrophilic interaction, make
Albumen globular molecule is fully unfolded, and the hydroxyl inside protein conformation, amino isoreactivity group are fully exposed, and is improved
The reactivity of molecule, the protein molecular then activated lead to lignin-glucose molecular resin containing aldehyde radical, methylol
Aldol, high molecular polymer of the aldimine condensation reaction generation with resistance to water-bound are crossed, while vegetable protein adhesive is used to be glued
When core-board dash board and core plate, lignin-glucose molecular resin can lead to protein molecular network under the conditions of high temperature hot pressing
Cross curing cross-linking reaction formation network and mutually pass structure, further increase the water-fast glue performance of albumen adhesive.Vegetable protein
Crosslinking agent is that origin comes from the polymerization that the lignin of natural resources and glucose are formed by polymerisation used by adhesive
Thing, first glucose resolve into activated monomer HMF 5 hydroxymethyl 2 furaldehyde under hot acid catalytic action, then in alkaline medium environment
Middle HMF 5 hydroxymethyl 2 furaldehyde has water-fast with the phenol ring ortho position active site on lignin molecule by addition, polycondensation reaction generation
The lignin of structure-grape glucoresin.The water proof bonding strength of the core-board prepared by the vegetable protein adhesive of the present invention,
Dipping and stripping performance has reached standard GB/T/T 5849-2006《Core-board》Specified in II class bonding strength requirement and
Dipping and stripping performance requirement.
Embodiment
The invention provides a kind of vegetable protein adhesive, it is prepared by the raw material comprising following mass fraction：
The crosslinking agent is glucose-lignin resin crosslinking agent, urea-dialdehyde starch resin and tannin-furfuryl alcohol resin
In one or more；
The glucose-lignin resin crosslinking agent is the hydrolysate of glucose and the polymerizate of lignin.
In the present invention, the raw material for preparing the vegetable protein adhesive includes 10~40 parts of vegetable proteins, and preferably 25
~35 parts, more preferably 30 parts.In the present invention, the vegetable protein is preferably defatted soy flour, defatted soybean meal, soybean separation protein
In vain, the one or more in degreased peanut flour, degreased cottonseed meal, degreasing oil-tea-cake meal and degreasing bio-fuel almond powder；Institute
The particle diameter for stating vegetable protein is preferably not less than 100 mesh, more preferably 200~500 mesh, most preferably 300~400 mesh.This hair
The bright source to the vegetable protein does not have any particular/special requirement, using commercially available plant well-known to those skilled in the art
Albumen.In the specific embodiment of the invention, the vegetable protein is specifically to have purchased from Shandong three-dimensional grease group share
Limit company or Chinese grain and oil limited company.
In the present invention, the raw material for preparing the vegetable protein adhesive includes 20~60 parts of water, preferably 30~50 parts,
More preferably 35~45 parts.In the present invention, the water uses the adhesive water that those skilled in the art commonly use.
In the present invention, the raw material for preparing the vegetable protein adhesive includes 5~25 parts of crosslinking agents, and preferably 10~20
Part, more preferably 15~18 parts.In the present invention, the crosslinking agent be preferably glucose-lignin resin crosslinking agent, urea-
Dialdehyde starch resin and one kind in tannin-furfuryl alcohol resin, two or three.The present invention is to the urea-dialdehyde starch resin
There is no any particular/special requirement with the source of tannin-furfuryl alcohol resin, formed sediment using urea well-known to those skilled in the art-dialdehyde
The commercially available prod of powder resin and tannin-furfuryl alcohol resin.
In the present invention, the preparation method of the glucose-lignin resin crosslinking agent, preferably comprises following steps：
D/W is issued into unboiled water solution in the catalysis of acidic catalyst, obtains hydrolysate system；
The pH value for adjusting the hydrolysate system is 10~13, obtains alkaline hydrolysis products system；
The alkaline hydrolysis products system and lignin are subjected to polymerisation, obtain glucose-lignin resin crosslinking
Agent.
D/W is issued unboiled water solution by the present invention in the catalysis of acidic catalyst, obtains hydrolysate system.
In the present invention, commercially available glucose that the glucose is well known to those skilled in the art.In the present invention, the acidity is urged
Agent is preferably the one or more in hydrochloric acid, sulfuric acid, nitric acid, halogen acids and oxalic acid.The present invention is to the hydrochloric acid, sulfuric acid, nitre
The concentration of acid, halogen acids and oxalic acid does not have any particular/special requirement, can be any concentration.
In the present invention, the mass ratio of glucose and water is preferably (2~5) in the D/W:1, more preferably
For (3~4):1.In the present invention, the mass ratio of the glucose and acidic catalyst is preferably (2~5):(0.01~0.1),
More preferably (3~4):(0.02~0.08).
In the present invention, the temperature of the acidic catalyst catalysis glucose hydrolysis is preferably 90~98 DEG C, more preferably
92~96 DEG C；Time is preferably 1~3h, more preferably 2h.
Acidic catalyst is preferably added in the D/W by the present invention at 55~65 DEG C, is then heated up again
It is hydrolyzed to 90~98 DEG C.The hydrolysis time of the present invention is calculated since be warming up to 90~98 DEG C.The present invention is to the grape
The source of sugar aqueous solution does not have any particular/special requirement, and the present invention is specifically to obtain glucose is soluble in water.In the water
In solution preocess, glucose hydrolysis are 5 hydroxymethyl furfural by the acidic catalyst.
After obtaining the hydrolysate system, the pH value that the present invention adjusts the hydrolysate system is 10~13, is obtained
Alkaline hydrolysis products system.The pH value that the present invention adjusts the hydrolysate system is 10~13, preferably 10.5~12.5, more
Preferably 11~12.The present invention adds alkali lye to be adjusted to its pH value preferably into the hydrolysate system.In this hair
In bright, the alkali lye is preferably inorganic alkali lye, more preferably hydroxide aqueous solution, most preferably sodium hydroxide solution or hydrogen-oxygen
Change potassium solution.In the present invention, the mass concentration of the alkali lye is preferably 20~40%, and more preferably 25~35%, most preferably
For 30%.In the present invention, the regulation of the pH value is preferably carried out at 80~85 DEG C, more preferably 82~83 DEG C.
After obtaining the alkaline hydrolysis products system, the present invention is gathered the alkaline hydrolysis products system and lignin
Reaction is closed, obtains glucose-lignin resin crosslinking agent.In the present invention, the lignin is enzymolysis xylogen, alkali lignin
With the one or more in sulfonate lignin.The present invention does not have any particular/special requirement to the source of the lignin, uses
Commercially available lignin well-known to those skilled in the art, or extracted from plant material or papermaking wastewater wooden
Element.
In the present invention, the mass ratio of the glucose and lignin is preferably (2~5):(0.1~0.5), more preferably
(3~4):(0.2~0.4).In the present invention, the temperature of the polymerisation is preferably 80~85 DEG C, more preferably 82~83
℃.The present invention does not have particular/special requirement to time of the polymerisation, the preferable viscosity when product system for 100~
Stop reaction, most preferably more preferably 200~600MPas, 250~350MPas during 800MPas (25 DEG C).
The viscosity of the glucose that the present invention obtains-lignin resin crosslinking agent is preferably 100~800MPas, more preferably
For 200~600MPas, most preferably 250~350MPas；PH value is preferably 7~10, and more preferably 8~9；Solids content
Preferably 20~70wt%, more preferably 30~60wt%, most preferably 40~50wt%；Molecular weight is preferably 600~5000,
More preferably 1000~4000, most preferably 2000~3000.
In the present invention, the raw material for preparing the vegetable protein adhesive includes 0.5~5 part of alkali, preferably 1~4 part, more
Preferably 2~3 parts.In the present invention, the alkali is preferably alkali metal hydroxide, alkaline earth metal hydroxide and alkali metal carbon
One or more in hydrochlorate, more preferably sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate and potassium carbonate
In one or more.In the present invention, when the alkali is simultaneously comprising sodium hydroxide, calcium hydroxide, potassium hydroxide, hydroxide
Two kinds in barium, sodium carbonate and potassium carbonate or it is more kinds of when, the addition of various specific alkali is preferably equal.
In the present invention, the alkali can be added and use in solid form, can also be in the form of aqueous slkali
It is added and uses.In the present invention, the mass concentration of the aqueous slkali is preferably 20~40%, more preferably 25~
35%, most preferably 30%.In the present invention, when the alkali is added in the form of aqueous slkali, the amount of alkali is with solution
The gauge of alkali soluble matter.In the present invention, the aqueous slkali is preferably the aqueous solution of alkali.In the present invention, the plant egg is prepared
Water in the raw material of white adhesive preferably comprises the aqueous solvent in aqueous slkali.
In the present invention, the raw material for preparing the vegetable protein adhesive includes 0.5~8 part of activator, and preferably 1~6
Part, more preferably 2~4 parts.In the present invention, the activator be preferably neopelex, lauryl sodium sulfate,
One or more in guanidine hydrochloride and thiocarbamide.The present invention does not have any particular/special requirement to the source of the activator, using this
The commercially available prod of above-mentioned specific activator known to art personnel.
In the present invention, the vegetable protein adhesive is preferably prepared by the raw material for also including 1~5 portion of preservative,
More preferably 2~4 parts, most preferably 3 parts.In the present invention, the preservative is preferably sodium benzoate, potassium sorbate, dehydrogenation
One or more in sodium acetate, calcium propionate, sodium Diacetate, sodium lactate, propylparaben and nisin.
In the present invention, when the preservative is preferably sodium benzoate, potassium sorbate, dehydroactic acid sodium, calcium propionate, sodium Diacetate, lactic acid
During any two kinds of materials in sodium, propylparaben and nisin, the mass ratio of any two kinds of materials is preferred
For (1~9):(1~9), more preferably (3~6):(3~6).The present invention does not have any special to the source of the preservative
It is required that the commercially available prod using above-mentioned specific preservative well-known to those skilled in the art.
Present invention also offers a kind of preparation method of vegetable protein adhesive described in above-mentioned technical proposal, includes following step
Suddenly：
(1) vegetable protein, water, activator and alkali are subjected to hot mixing, obtain the mixed raw material of heat；
(2) the mixed raw material of the heat and crosslinking agent are subjected to cross-linked polymeric, obtain vegetable protein adhesive.
Vegetable protein, water, activator and alkali lye are carried out hot mixing by the present invention, obtain the mixed raw material of heat.In the present invention, institute
The temperature for stating hot mixing in step (1) is preferably 80~90 DEG C, more preferably 82~88 DEG C, most preferably 85~86 DEG C；It is described
The time of hot mixing is preferably 1~3h in step (1), more preferably 2h.
Order by merging of the present invention to the vegetable protein, water, activator and alkali lye does not have any particular/special requirement, each thing
Matter can be mixed in any order.
In the present invention, hot mixing is preferably carried out under agitation in the step (1), and the present invention is to the stirring
Mode and speed do not have any particular/special requirement, and mixed system can stir.
After obtaining the mixed raw material of the heat, the mixed raw material of the heat and crosslinking agent are carried out cross-linked polymeric by the present invention, obtain plant
Albumen adhesive.In the present invention, the temperature of cross-linked polymeric is preferably 65~78 DEG C in the step (2), more preferably 70~
75℃；The time of cross-linked polymeric is preferably 0.1~2h in the step (2), more preferably 0.5~1.5h, most preferably 1h.
In the present invention, cross-linked polymeric is preferably carried out under agitation in the step (2), and the present invention is to the stirring
Mode and speed there is no any particular/special requirement, mixed system can be stirred.
In the present invention, when also including preservative in the raw material for preparing vegetable protein adhesive, the present invention preferably again will
The polymer and preservative that cross-linked polymeric obtains in the step (2) carry out hot mixing, obtain vegetable protein adhesive.In this hair
In bright, the temperature of the hot mixing of the cross-linked polymer product and preservative is preferably 20~40 DEG C, more preferably 25~35 DEG C.
The present invention does not have any particular/special requirement to the time of described and preservative hot mixing, can be well mixed.
Present invention also offers preparation described in vegetable protein adhesive described in above-mentioned technical proposal or above-mentioned technical proposal
Application of the vegetable protein adhesive that method obtains in core-board is prepared.The present invention is to using plant described in application scheme
The method that albumen adhesive prepares core-board does not have any particular/special requirement, can be with well-known to those skilled in the art
It is prepared by meaning method.
Vegetable protein adhesive provided by the invention and its preparation method and application is carried out with reference to embodiment detailed
Explanation, but they can not be interpreted as limiting the scope of the present invention.
Used key instrument refers to table 1 with facility information in all embodiments of the application.
The embodiment instrument of table 1 and equipment details
Used sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate in all embodiments of the application
Xi Long science limited company, purity are purchased from potassium carbonate：Chemistry is pure；Hydrochloric acid, sulfuric acid, nitric acid, halogen acids and oxalic acid,
Purchased from Beijing Yili Fine Chemicals Co., Ltd., purity：Chemistry is pure；Glucose, technical grade are commercially available；DBSA
Sodium, lauryl sodium sulfate, guanidine hydrochloride, thiocarbamide, sodium benzoate, potassium sorbate, dehydroactic acid sodium, calcium propionate, sodium Diacetate, breast
Sour sodium, propylparaben, analysis is pure, is purchased from Chemical Reagent Co., Ltd., Sinopharm Group；Nisin, contain
Amount：More than 98%, this bio tech ltd of Jinan day.
Embodiment 1
A kind of vegetable protein adhesive, counted using the gross mass of the adhesive raw material as 100%, each component and matter in raw material
It is as follows to measure percentage composition：
A kind of preparation method of vegetable protein adhesive, methods described comprise the following steps that：
(1) 300 kilograms of glucose and 100 kg of water are put into reactor, divided with 80r/min rotating speeds mechanical agitation 10
60 DEG C are warming up to after clock, adds 5 kilograms of sulfuric acid, 90 DEG C and insulation reaction 3h is gradually heating to, 80 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution adjusts pH value to add 35 kilograms of enzymolysis xylogens to 12, carry out polymerisation, product to be polymerized applies 4 viscosity
(25 DEG C) reach 200MPas, are cooled to 30 DEG C, discharging, obtain the glucose-lignin resin crosslinking agent.
(2) it is 30% carbonic acid by 200 kilograms of defatted soy flours, 600 kg of water, 80 kilograms of guanidine hydrochlorides and 5 kilograms of mass concentrations
Sodium water solution is put into reactor, after 68r/min rotating speeds mechanical agitation 5 minutes, is gradually heating to 85 DEG C, and insulated and stirred
2h；
(3) mixture that step (2) obtains is cooled to 65 DEG C, adds 100 kilograms of glucose-lignin resin crosslinking
Agent, and insulated and stirred 2h；
(4) mixture that step (3) obtains is cooled to 40 DEG C, adds 15 kilograms of sodium benzoates, stir.
Embodiment 2
A kind of vegetable protein adhesive, counted using the gross mass of the adhesive raw material as 100%, each component and matter in raw material
It is as follows to measure percentage composition：
(1) 300 kilograms of glucose and 100 kg of water are put into reactor, divided with 80r/min rotating speeds mechanical agitation 10
60 DEG C are warming up to after clock, adds 5 kilograms of sulfuric acid, 95 DEG C and insulation reaction 1h is gradually heating to, 85 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution adjusts pH value to add 35 kilograms of alkali lignins to 13, carry out polymerisation, product viscosity (25 DEG C) to be polymerized
Reach 250MPas, be cooled to 30 DEG C, discharging, obtain the crosslinking agent (glucose-lignin resin).
(2) it is 400 kilograms of degreased peanut flours, 450 kg of water, 20 kilograms of neopelexes and 30 kilograms of quality are dense
Spend and put into for 30% potassium hydroxide aqueous solution in reactor, after 68r/min rotating speeds mechanical agitation 5 minutes, gradually heating
To 80 DEG C, and insulated and stirred 1h；
(3) mixture that step (2) obtains is cooled to 70 DEG C, adds 50 kilograms of glucose-lignin resin crosslinking
Agent, and insulated and stirred 1.5h；
(4) mixture that step (3) obtains is cooled to 30 DEG C, adds 5 kilograms of sodium Diacetates, stir.
Embodiment 3
A kind of vegetable protein adhesive, counted using the gross mass of the adhesive raw material as 100%, each component and matter in raw material
It is as follows to measure percentage composition：
(1) 300 kilograms of glucose and 100 kg of water are put into reactor, divided with 80r/min rotating speeds mechanical agitation 10
60 DEG C are warming up to after clock, adds 5 kilograms of sulfuric acid, 98 DEG C and insulation reaction 2h is gradually heating to, 82 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution adjusts pH value to add 35 kilograms of enzymolysis xylogens to 12, carry out polymerisation, product viscosity (25 to be polymerized
DEG C) reach 400MPas, 30 DEG C are cooled to, discharging, obtains the crosslinking agent (glucose-lignin resin).
(2) it is 30% by 100 kilograms of soybean separation protein white powders, 600 kg of water, 5 kilograms of thiocarbamides and 50 kilograms of mass concentrations
Baryta water put into reactor, after 68r/min rotating speeds mechanical agitation 5 minutes, be gradually heating to 90 DEG C, and
Insulated and stirred 3h；
(3) mixture that step (2) obtains is cooled to 78 DEG C, adds 200 kilograms of glucose-lignin resin crosslinking
Agent, and insulated and stirred 1h；
(4) mixture that step (3) obtains is cooled to 25 DEG C, adds 45 kilograms of propylparabens, stirring is equal
It is even.
Embodiment 4
A kind of vegetable protein adhesive, counted using the gross mass of the adhesive raw material as 100%, each component and matter in raw material
It is as follows to measure percentage composition：
(1) 300 kilograms of glucose and 100 kg of water are put into reactor, divided with 80r/min rotating speeds mechanical agitation 10
60 DEG C are warming up to after clock, adds 5 kilograms of sulfuric acid, is gradually heating to 94 DEG C and insulation reaction 2.5h, is then cooled to 85 DEG C, is used
30% sodium hydrate aqueous solution adjusts pH value to add 35 kilograms of enzymolysis xylogens to 13, carry out polymerisation, product viscosity to be polymerized
(25 DEG C) reach 350MPas, are cooled to 30 DEG C, discharging, obtain the crosslinking agent (glucose-lignin resin).
(2) by 270 kilograms of oil-tea-cake meals, 380 kg of water, 15 kilograms of lauryl sodium sulfate, 25 kilograms of mass concentrations
The wet chemical that sodium hydrate aqueous solution and 25 kilograms of mass concentrations for 30% are 30% is put into reactor, with
68r/min rotating speeds mechanical agitation is gradually heating to 85 DEG C, and insulated and stirred 1.5h after 5 minutes；
(3) mixture that step (2) obtains is cooled to 65 DEG C, adds 250 kilograms of glucose-lignin resin crosslinking
Agent, and insulated and stirred 0.5h；
(4) mixture that step (3) obtains is cooled to 30 DEG C, adds 10 kilograms of dehydroactic acid sodiums and 25 kilograms of benzoic acid
Sodium, stir.
Embodiment 5
A kind of vegetable protein adhesive, counted using the gross mass of the adhesive raw material as 100%, each component and matter in raw material
It is as follows to measure percentage composition：
(1) 300 kilograms of glucose and 100 kg of water are put into reactor, divided with 80r/min rotating speeds mechanical agitation 10
60 DEG C are warming up to after clock, adds 5 kilograms of sulfuric acid, 92 DEG C and insulation reaction 3h is gradually heating to, 83 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution adjusts pH value to add 35 kilograms of enzymolysis xylogens to 11.5, carry out polymerisation, product viscosity to be polymerized
(25 DEG C) reach 100MPas, are cooled to 30 DEG C, discharging, obtain the crosslinking agent (glucose-lignin resin).
(2) hydrogen for being 30% by 300 kilograms of defatted soybean meals, 450 kg of water, 50 kilograms of guanidine hydrochlorides and 30 kilograms of mass concentrations
Aqueous solution of sodium oxide is put into reactor, after 68r/min rotating speeds mechanical agitation 5 minutes, is gradually heating to 85 DEG C, and be incubated
Stir 2.5h；
(3) mixture that step (2) obtains is cooled to 75 DEG C, adds 145 kilograms of glucose-lignin resin crosslinking
Agent, and insulated and stirred 1h；
(4) mixture that step (3) obtains is cooled to 40 DEG C, adds 25 kilograms of sodium lactates, stir.
Embodiment 6
A kind of vegetable protein adhesive, counted using the gross mass of the adhesive raw material as 100%, each component and matter in raw material
It is as follows to measure percentage composition：
(1) 300 kilograms of glucose and 100 kg of water are put into reactor, divided with 80r/min rotating speeds mechanical agitation 10
60 DEG C are warming up to after clock, adds 5 kilograms of sulfuric acid, is gradually heating to 95 DEG C and insulation reaction 2.5h, is then cooled to 83 DEG C, is used
30% sodium hydrate aqueous solution adjusts pH value to add 35 kilograms of enzymolysis xylogens to 12, carry out polymerisation, product viscosity to be polymerized
(25 DEG C) reach 260MPas, are cooled to 30 DEG C, discharging, obtain the crosslinking agent (glucose-lignin resin).
(2) by 200 kilograms of degreasing bio-fuel almond powders, 550 kg of water, 55 kilograms of guanidine hydrochlorides, 15 kilograms of mass concentrations
The calcium hydroxide aqueous solution that sodium hydrate aqueous solution and 15 kilograms of mass concentrations for 30% are 30% is put into reactor, with
68r/min rotating speeds mechanical agitation is gradually heating to 85 DEG C, and insulated and stirred 3h after 5 minutes；
(3) mixture that step (2) obtains is cooled to 65 DEG C, adds 150 kilograms of glucose-lignin resin crosslinking
Agent, and insulated and stirred 0.5h；
(4) mixture that step (3) obtains is cooled to 35 DEG C, adds 15 kilograms of sodium benzoates, stir.
Embodiment 7
A kind of vegetable protein adhesive, counted using the gross mass of the adhesive raw material as 100%, each component and matter in raw material
It is as follows to measure percentage composition：
(1) 300 kilograms of glucose and 100 kg of water are put into reactor, divided with 80r/min rotating speeds mechanical agitation 10
60 DEG C are warming up to after clock, adds 5 kilograms of sulfuric acid, 93 DEG C and insulation reaction 2h is gradually heating to, 82 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution adjusts pH value to add 35 kilograms of enzymolysis xylogens to 10, carry out polymerisation, product viscosity (25 to be polymerized
DEG C) reach 310MPas, 30 DEG C are cooled to, discharging, obtains the crosslinking agent (glucose-lignin resin).
(2) by 230 kilograms of degreased cottonseed meals, 400 kg of water, 20 kilograms of lauryl sodium sulfate, 40 kilograms of thiocarbamides and 40
The calcium hydroxide aqueous solution that kilogram mass concentration is 30% is put into reactor, and 5 points are stirred with 68r/min rotating speeds mechanical agitation
Zhong Hou, it is gradually heating to 80 DEG C, and insulated and stirred 3h；
(3) mixture that step (2) obtains is cooled to 78 DEG C, adds 220 kilograms of glucose-lignin resin crosslinking
Agent, and insulated and stirred 2h；
(4) mixture that step (3) obtains is cooled to 30 DEG C, adds 50 kilograms of nisins, stir.
Embodiment 8
(1) hydrogen for being 30% by 250 kilograms of defatted soy flours, 600 kg of water, 10 kilograms of guanidine hydrochlorides, 20 kilograms of mass concentrations
The aqueous sodium carbonate that aqueous solution of sodium oxide and 20 kilograms of mass concentrations are 30% is put into reactor, with 68r/min rotating speeds
After mechanical agitation 5 minutes, 90 DEG C, and insulated and stirred 2.5h are gradually heating to；
(2) mixture that step (1) obtains is cooled to 70 DEG C, adds 80 kilograms of urea-dialdehyde starch resin cross-linking agent,
And insulated and stirred 2h；
(3) mixture that step (2) obtains is cooled to 40 DEG C, adds 15 kilograms of sodium benzoates, 5 kilograms of para hydroxybenzene first
Propyl propionate, stir.
Embodiment 9
(1) it is 30% by 200 kilograms of soybean protein isolates, 550 kg of water, 80 kilograms of thiocarbamides and 40 kilograms of mass concentrations
Sodium hydrate aqueous solution is put into reactor, after being stirred 5 minutes with 68r/min rotating speeds mechanical agitation, is progressively warming up to 85 DEG C,
And insulated and stirred 1.5h；
(2) mixture that step (1) obtains is cooled to 73 DEG C, adds 100 kilograms of tannin-furfuryl alcohol resin crosslinking agent, and
Insulated and stirred 2h；
(3) mixture that step (2) obtains is cooled to 35 DEG C, adds 30 kilograms of potassium sorbates, stir.
Reference examples 1
Vegetable protein adhesive is prepared according to method same as Example 1.Except that directly substituted with glucose
The crosslinking agent prepares vegetable protein adhesive.
Reference examples 2
Vegetable protein adhesive is prepared according to method same as Example 1.Except that directly substituted with lignin
The crosslinking agent prepares vegetable protein adhesive.
Reference examples 3
Vegetable protein adhesive is prepared according to method same as Example 1, except that the crosslinking agent preparation side
In method, glucose is not hydrolyzed into 5 hydroxymethyl furfural under sulfuric acid catalysis effect, but D/W is directly adjusted to
For pH value to 12, then addition enzymolysis xylogen, which directly carries out polymerisation, (can not occur polymerisation, viscosity does not reach yet
100MPa·s)。
Embodiment 10
In order to verify the performance of vegetable protein adhesive of the present invention and its application effect on core-board product
With product it is green, to human body non-hazardous the advantages of, and carried out a series of experiments, particular content is as follows：
Solids content, pH value, storage are carried out to the adhesive prepared using above-described embodiment 1~9 and reference examples 1~3 respectively
The performance tests such as phase, viscosity, free formaldehyde, benzene compounds (benzene,toluene,xylene) and total volatile organism are deposited, are passed through
Core-board is prepared to carry out its bonding strength, dipping and stripping performance, burst size of methanal, TOVC release rate
Detection, application effect of the evaluation vegetable protein adhesive on core-board product.Wherein, solids content, pH value, storage period,
The test of viscosity, free formaldehyde is according to GB/T 14074-2006《Wood adhesive and its resin method of inspection》Specified in phase
Detection method is answered to carry out, the detection of benzene compounds (benzene,toluene,xylene) content and total volatile organism content is according to GB
18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Specified in corresponding detection method, testing result
As shown in table 2.
The performance parameter for the adhesive that the embodiment 1~9 of table 2 and reference examples 1~3 obtain
As can be seen from Table 2, because the raw material of albumen adhesive is mainly derived from the vegetable protein, lignin, Portugal of regeneration
The biomass such as grape sugar, using in the vegetable protein adhesive prepared by the method for the embodiment of the present invention 1~9 and the method for reference examples 1~3
Without poisonous and harmful substances such as free formaldehyde, free benzene compounds, make the complete greenization of adhesive.
Using the viscosity of the vegetable protein adhesive prepared by the method for the embodiment of the present invention 1~9 in 4520~9860MPa
Between s, hence it is evident that more than the viscosity (3490~3610MPas) of the adhesive prepared by the method for reference examples 1~3.It is because right
As usual in 1~3 method be not used synthesis crosslinking agent, and glucose, lignin and not sulfuric acid catalysis effect under be hydrolyzed into
5 hydroxymethyl furfural and lignin formed polymer be not the polymer with resistance to water-bound, and with legumin molecule
Activity of cross-linking reaction is far away from glucose-lignin resin, thus the vegetable protein adhesive viscosity prepared is relatively low, does not form tool
There is the network size molecule of resistance to water-bound.
The storage period of albumen adhesive prepared by the method for the embodiment of the present invention 1~9, more than 20 days, meet albumen
Adhesive need to be in more than 15 days requirements to storage period as core-board adhesive.Using routine diaion as
, it is necessary to impregnation be carried out to adhesive to improve the tack of adhesive, generally in resin when preparing core-board with adhesive
Add the flour of weight resin 30~40%.And the albumen adhesive prepared by the method for the embodiment of the present invention 1~9 is with higher
Viscosity, it is additionally added flour just has good tack, reduce further albumen adhesive as thin wood
The use cost of work plate glue.
Core plate is China fir batten (900 millimeters of length, 400 millimeters of width, the milli of thickness 10 used by preparing core-board
Rice) pass through the sheet material that coating albumen adhesive gluing forms.Used dash board is 5 years fast-growing Eucalyptus veneer (millis of length 2440
Rice, 1220 millimeters of width, 2.2 millimeters of thickness), moisture content is 10~20%.The preparation technology of core-board：First by fir core plate
Carry out polishing processing using sander, then choose Eucalyptus veneer, and Eucalyptus veneer is coated protein adhesive, then by Eucalyptus
Veneer is adhered on core plate upper and lower surface, finally carries out repairing treatment to whole sheet material using putty, the sheet material repaired is sent
Enter and hot pressing is carried out in hot press, hot pressing technique is：(1) it is glued：The two-sided applying glue of core, resin added are 330~380g/m2；
(2) aging and time：Closure ageing, 30~90min；(3) hot compression parameterses：Pressure 1.1-1.3MPa, temperature be 120~
125 DEG C, the time is 13-15 minutes.Finally the sheet material after hot pressing is sent into sander and carries out polishing processing, produces vegetable protein
The Formaldehydeless fine wooden board of glue laminated.
According to GB/T 5849-2006《Core-board》Specified in II class bonding strength, the method for testing of dipping and stripping and
The vegetable protein adhesive and 3 reference examples methods that burst size of methanal measure method of testing 9 kinds of embodiment methods of detection obtain obtain
Bonding strength, dipping and stripping performance and the burst size of methanal of the core-board prepared by adhesive obtained, as a result as shown in table 3.
According to HJ571-2010《Environmental labelling product technical requirements --- wood-based plate and its product》Specified in general volatile organic
The method of testing detection of compound
The TOVC release rate of core-board product, as a result as shown in table 3.
The performance parameter of the core-board for the adhesive gluing that the embodiment 1~9 of table 3 and reference examples 1~3 obtain
As shown in table 3, the joiner prepared using the vegetable protein adhesive prepared by the method for the embodiment of the present invention 1~9
Plate is respectively provided with higher bonding strength, meets standard GB/T/T 5849-2006《Core-board》Specified in indoor II class
Bonding strength (being not less than 0.70MPa) requires, and is respectively provided with qualified dipping and stripping performance, wherein the side of embodiment 1,2,3,8,9
Adhesive prepared by method has higher bonding strength, and uses the thin wood of the Resin adhesive preparation prepared by reference examples method
The bonding strength of work plate is below 0.70MPa, does not reach II class bonding strength national standard.
The core-board manufactured using the vegetable protein adhesive prepared by the method for the embodiment of the present invention 1~9 has extremely low micro-
The Form aldehyde release of amount, this is due to caused by timber itself can discharge formaldehyde, and TOVC release rate
Numerical value is extremely low, close to Form aldehyde release value, illustrates the core-board of preparation in addition to the ultra-low volume formaldehyde that timber itself discharges,
Without other poisonous, harmful organic matter releases, show using the vegetable protein gluing prepared by the method for the embodiment of the present invention 1~9
Agent can produce the green core-board product of unharmful substance release.
As seen from the above embodiment, the invention provides a kind of vegetable protein adhesive and its preparation method and application.Root
Understood according to the result of embodiment, without free formaldehyde, free benzene compounds in the vegetable protein adhesive prepared by the present invention
Deng poisonous and harmful substances, adhesive realizes complete greenization, can produce the green joiner of unharmful substance release
Plate.And the viscosity of the vegetable protein adhesive prepared by the present invention is between 4520~9860MPas, hence it is evident that more than reference examples 1
The viscosity (3490~3610MPas) of adhesive prepared by~3 methods.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of vegetable protein adhesive, is prepared by the raw material comprising following mass fraction：
The crosslinking agent is in glucose-lignin resin crosslinking agent, urea-dialdehyde starch resin and tannin-furfuryl alcohol resin
It is one or more of；
The glucose-lignin resin crosslinking agent is the hydrolysate of glucose and the polymerizate of lignin.
2. vegetable protein adhesive according to claim 1, it is characterised in that the glucose-lignin resin crosslinking
Agent is prepared according to the method comprised the following steps：
D/W is issued into unboiled water solution in the catalysis of acidic catalyst, obtains hydrolysate system；
The pH value for adjusting the hydrolysate system is 10~13, obtains alkaline hydrolysis products system；
The alkaline hydrolysis products system and lignin are subjected to polymerisation, obtain glucose-lignin resin crosslinking agent.
3. vegetable protein adhesive according to claim 2, it is characterised in that in the D/W glucose and
The mass ratio of water is (2~5):1.
4. vegetable protein adhesive according to claim 3, it is characterised in that the glucose, acidic catalyst and wood
The mass ratio of quality is (2~5):(0.01~0.1):(0.1~0.5).
5. the vegetable protein adhesive according to claim 2 or 4, it is characterised in that the acidic catalyst is hydrochloric acid, sulphur
One or more in acid, nitric acid, halogen acids and oxalic acid.
6. vegetable protein adhesive according to claim 2, it is characterised in that the temperature of the polymerisation is 80~85
℃。
7. vegetable protein adhesive according to claim 1, it is characterised in that the vegetable protein is defatted soy flour, taken off
Fat dregs of beans, soybean protein isolate, degreased peanut flour, degreased cottonseed meal, degreasing oil-tea-cake meal and degreasing bio-fuel almond powder
In one or more.
8. the preparation method of vegetable protein adhesive, is comprised the following steps described in claim 1~7 any one：
(1) vegetable protein, water, activator and alkali are subjected to hot mixing, obtain the mixed raw material of heat；
(2) the mixed raw material of the heat and crosslinking agent are subjected to cross-linked polymeric, obtain vegetable protein adhesive.
9. preparation method according to claim 8, it is characterised in that in the step (1) temperature of hot mixing be 80~
90 DEG C, the time is 1~3h；
The temperature of cross-linked polymeric is 65~78 DEG C in the step (2), and the time is 0.1~2h.
10. vegetable protein adhesive described in claim 1~7 any one or the preparation method of claim 8 or 9 obtain
Application of the vegetable protein adhesive in core-board is prepared.
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| CN108531128A (en) * | 2018-02-27 | 2018-09-14 | 山东顺创新材料科技有限公司 | A kind of no aldehyde lignin adhesive and preparation method thereof |
| CN111363482A (en) * | 2019-05-20 | 2020-07-03 | 湖南宏润科技发展有限公司 | High-strength water-resistant plant protein adhesive and preparation method thereof |
| CN115179385A (en) * | 2022-06-23 | 2022-10-14 | 北京林业大学 | Preparation method of aldehyde-free artificial board for oil tea fruit shell base room |
| CN115820161A (en) * | 2022-12-12 | 2023-03-21 | 南京林业大学 | Pure natural high-performance environment-friendly adhesive for plywood and preparation method and application thereof |
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| CN102617819A (en) * | 2012-04-23 | 2012-08-01 | 浙江农林大学 | Production method for dialdehyde starch adhesive |
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| CN115179385A (en) * | 2022-06-23 | 2022-10-14 | 北京林业大学 | Preparation method of aldehyde-free artificial board for oil tea fruit shell base room |
| CN115820161A (en) * | 2022-12-12 | 2023-03-21 | 南京林业大学 | Pure natural high-performance environment-friendly adhesive for plywood and preparation method and application thereof |
| CN115820161B (en) * | 2022-12-12 | 2023-05-16 | 南京林业大学 | Purely natural high-performance environment-friendly adhesive for plywood and preparation method and application thereof |
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| CN107641495B (en) | 2019-07-12 |
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