CN107641495B - 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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- CN107641495B CN107641495B CN201710979162.8A CN201710979162A CN107641495B CN 107641495 B CN107641495 B CN 107641495B CN 201710979162 A CN201710979162 A CN 201710979162A CN 107641495 B CN107641495 B CN 107641495B
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Abstract
The present invention provides a kind of vegetable protein adhesives and its preparation method and application.For adhesive provided by the invention using green material as crosslinking agent, all prepare all does not include formaldehyde in raw material, fundamentally can thoroughly solve the problems, such as adhesive Form aldehyde release, more green, environmental protection.Result according to the embodiment is it is found that without poisonous and harmful substances such as free formaldehyde, free benzene compounds in the vegetable protein adhesive that the present invention obtains, the complete greenization of adhesive realization can produce the environmentally protective core-board of unharmful substance release.And the viscosity of vegetable protein adhesive prepared by the present invention is between 4520~9860MPas, hence it is evident that greater than the viscosity (3490~3610MPas) of adhesive prepared by 1~3 method of reference examples.
Description
Technical field
The present invention relates to adhesive technology field more particularly to a kind of vegetable protein adhesive and preparation method thereof and answer
With.
Background technique
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
It ranks first in the world.Currently, 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 releases formaldehyde, pollutes indoor air environment, endangers the health of the people, and formaldehyde pollution has become the hot spot of society's highest attention
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: molar ratio, addition resorcinol, cyanurotriamide modified and formaldehyde by reducing formaldehyde
The modes such as agent for capturing reduce the free formaldehyde content of Lauxite, or the activity using ammonia, ozone etc. easily in conjunction with formaldehyde
Molecule post-processes wood-based plate, these measures or method reduce the burst size of methanal of wood-based plate to a certain extent, but not
It can fundamentally solve the problems, such as the formaldehyde pollution of wood-based plate and its timber products.
Since 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
Using the modified method of crosslinking agent enhancing, it is 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 use aldehydes and its derivative, isocyanates substance and other macromolecules for crosslinking agent, meeting
The pollution problem of the volatile hazardous substances such as free formaldehyde, benzene homologues is brought to soy protein adhesives and its splicing wood-based plate.
Summary of the invention
The purpose of the present invention is to provide a kind of vegetable protein adhesives and its preparation method and application.It is provided by the invention
For adhesive using green material as crosslinking agent, all prepare all does not include formaldehyde in raw material, fundamentally can thoroughly solve glue
Glutinous agent Form aldehyde release problem, more green, environmental protection.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of vegetable protein adhesives, are 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
One or more of；
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:
Glucose solution 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 polymerization reaction, obtain glucose-lignin resin crosslinking
Agent.
Preferably, the mass ratio of glucose and water is (2~5) in the glucose solution: 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 one or more of hydrochloric acid, sulfuric acid, nitric acid, halogen acids and oxalic acid.
Preferably, the temperature of the polymerization reaction 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 of the seed dregs of rice, degreasing oil-tea-cake meal and degreasing bio-fuel almond powder.
The present invention also provides a kind of preparation methods of vegetable protein adhesive described in above-mentioned technical proposal, include following step
It is rapid:
(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.
The present invention also provides prepare described in vegetable protein adhesive described in above-mentioned technical proposal or above-mentioned technical proposal
The vegetable protein adhesive that method obtains is preparing the application in core-board.
The present invention provides a kind of vegetable protein adhesives and preparation method thereof.Vegetable protein adhesive provided by the invention
Used raw material without the harmful substances such as formaldehyde, benzene compounds, organic amine compound, and 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 from reproducible lignin and glucose hydrolysis product polymer or be urea-dialdehyde starch resin and tannin-
Furfuryl alcohol resin has the advantages that nontoxic, green, no pollution to the environment, to make the complete greenization of plant albumin glue adhesive, therefore
There is no the releases of the volatile organic matters such as formaldehyde, organic benzene homologues, ammonia for the wood-based plate of vegetable protein adhesive preparation, thoroughly solve
Volatile organic matter pollution problem in wood-based plate and its woodwork bring indoor environment of having determined.
Primary raw material-vegetable protein used in vegetable protein adhesive provided by the invention is both from agricultural-forestry biomass original
The residue that the processing such as material production edible oil materials, bio-fuel generate, from a wealth of 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 does not need to increase equipment throwing
Skilled worker is provided and retrained, industrialized production and application are suitable for.
The technical solution of vegetable protein adhesive of the present invention carries out vegetable protein using first with activator and alkali
Multiplicity reactivation is made by secondary keys and the hydrophobic, hydrophilic interaction such as hydrogen bond, sat linkage destroyed between protein molecular peptide segment
Albumen globular molecule is sufficiently unfolded, and hydroxyl, the amino isoreactivity group inside protein conformation are sufficiently exposed, and is improved
The reactivity of molecule, the protein molecular then activated and lignin-glucose molecular resin containing aldehyde radical, methylol are logical
Aldol, high molecular polymer of the aldimine condensation reaction generation with resistance to water-bound are crossed, while vegetable protein adhesive is for being glued
When core-board dash board and core plate, lignin-glucose molecular resin can be logical with protein molecular network under the conditions of high temperature hot pressing
It crosses curing cross-linking reaction formation network and mutually passes structure, further improve the water-fast glue performance of albumen adhesive.Vegetable protein
Crosslinking agent used by adhesive is that origin is derived from the lignin of natural resources and glucose passes through polymerization made of polymerization reaction
Object, 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 is generated by addition, polycondensation reaction with water-fast with the phenol ring ortho position active site on lignin molecule
The lignin of structure-grape glucoresin.The water proof bonding strength of the core-board prepared by vegetable protein adhesive of the invention,
Dipping and stripping performance reached II class bonding strength specified in standard GB/T/T 5849-2006 " core-board " require and
Dipping and stripping performance requirement.
Specific embodiment
The present invention provides a kind of vegetable protein adhesives, are 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
One or more of；
The glucose-lignin resin crosslinking agent is the hydrolysate of glucose and the polymerizate of lignin.
In the present invention, prepare the vegetable protein adhesive raw material include 10~40 parts of vegetable proteins, 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
One or more of white, degreased peanut flour, degreased cottonseed meal, degreasing oil-tea-cake meal and degreasing bio-fuel almond powder；Institute
The partial size 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 liability company.
In the present invention, prepare the vegetable protein adhesive raw material include 20~60 parts of water, preferably 30~50 parts,
More preferably 35~45 parts.In the present invention, the water is using adhesive water commonly used by those skilled in the art.
In the present invention, prepare the vegetable protein adhesive raw material include 5~25 parts of crosslinking agents, preferably 10~20
Part, more preferably 15~18 parts.In the present invention, the crosslinking agent is preferably glucose-lignin resin crosslinking agent, urea-
One of dialdehyde starch resin and 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 tannin-furfuryl alcohol resin source, is formed sediment using urea well-known to those skilled in the art-dialdehyde
Powder resin and tannin-furfuryl alcohol resin commercial product.
In the present invention, the glucose-lignin resin crosslinking agent preparation method, preferably comprises following steps:
Glucose solution 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 polymerization reaction, obtain glucose-lignin resin crosslinking
Agent.
Glucose solution is issued unboiled water solution in the catalysis of acidic catalyst by the present invention, 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 one or more of 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 glucose solution: 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 glucose solution at 55~65 DEG C by the present invention, is then heated up again
It is hydrolyzed to 90~98 DEG C.Hydrolysis time of the 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 is 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.Lye is added preferably into the hydrolysate system to be adjusted to its pH value in the present invention.In this hair
In bright, the lye is preferably inorganic 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 lye is preferably 20~40%, and more preferably 25~35%, most preferably
It is 30%.In the present invention, the adjusting of the pH value preferably carries out at 80~85 DEG C, and more preferably 82~83 DEG C.
After obtaining the alkaline hydrolysis products system, the present invention gathers the alkaline hydrolysis products system and lignin
Reaction is closed, glucose-lignin resin crosslinking agent is obtained.In the present invention, the lignin is enzymolysis xylogen, alkali lignin
One or more of with 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 polymerization reaction is preferably 80~85 DEG C, more preferably 82~83
℃.The present invention does not have particular/special requirement to the time of the polymerization reaction, it is preferred when the viscosity of product system is 100~
Stop reaction, more preferably 200~600MPas, most preferably 250~350MPas when 800MPas (25 DEG C).
The glucose that the present invention obtains-lignin resin crosslinking agent viscosity is preferably 100~800MPas, more preferably
For 200~600MPas, most preferably 250~350MPas；PH value is preferably 7~10, and more preferably 8~9；Solid 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, prepare the vegetable protein adhesive raw material include 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 of hydrochlorate, more preferably sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate and potassium carbonate
One or more of.In the present invention, when the alkali includes simultaneously sodium hydroxide, calcium hydroxide, potassium hydroxide, hydroxide
Two kinds in barium, sodium carbonate and potassium carbonate or it is more kinds of when, the additive amount 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 in solution
The meter 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, prepare the vegetable protein adhesive raw material include 0.5~8 part of activator, preferably 1~6
Part, more preferably 2~4 parts.In the present invention, the activator be preferably neopelex, lauryl sodium sulfate,
One or more of guanidine hydrochloride and thiocarbamide.The present invention does not have any particular/special requirement to the source of the activator, using this
The commercial product of above-mentioned specific activator known to the technical staff of field.
In the present invention, the vegetable protein adhesive is preferably prepared by the raw material also comprising 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 of 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
When any two kinds of substances in sodium, propylparaben and nisin, the mass ratio of any two kinds of substances is preferred
For (1~9): (1~9), more preferably (3~6): (3~6).It is any special that the present invention does not have the source of the preservative
It is required that using the commercial product of above-mentioned specific preservative well-known to those skilled in the art.
The present invention also provides a kind of preparation methods of vegetable protein adhesive described in above-mentioned technical proposal, include following step
It is rapid:
(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 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.
The present invention does not have any particular/special requirement, each object to the order by merging of the vegetable protein, water, activator and lye
Matter can be mixed in any order.
In the present invention, hot mixing preferably carries out under agitation in the step (1), and the present invention is to the stirring
Mode and rate do not have any particular/special requirement, can stir evenly mixed system.
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 preferably carries out under agitation in the step (2), and the present invention is to the stirring
Mode and rate there is no any particular/special requirement, mixed system can be stirred evenly.
In the present invention, when including also 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, and 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 uniformly mixed.
The present invention also provides prepare described in vegetable protein adhesive described in above-mentioned technical proposal or above-mentioned technical proposal
The vegetable protein adhesive that method obtains is preparing the application in core-board.The present invention is 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 below with reference to embodiment detailed
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
See Table 1 for details with facility information for used key instrument in all embodiments of the application.
1 embodiment instrument of table and equipment details
Used sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate in all embodiments of the application
Be purchased from western Gansu Province science limited liability company with potassium carbonate, purity: 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；Dodecyl benzene sulfonic acid
Sodium, lauryl sodium sulfate, guanidine hydrochloride, thiocarbamide, sodium benzoate, potassium sorbate, dehydroactic acid sodium, calcium propionate, sodium Diacetate, cream
Sour sodium, propylparaben, analysis is pure, is purchased from Sinopharm Chemical Reagent Co., Ltd.；Nisin contains
Amount: greater than 98%, this Biotechnology Co., Ltd of Jinan day.
Embodiment 1
A kind of vegetable protein adhesive is each component and matter in raw material in terms of 100% by the gross mass of the adhesive raw material
It is as follows to measure percentage composition:
A kind of preparation method of vegetable protein adhesive, specific step is as follows for the method:
(1) 300 kilograms of glucose and 100 kg of water are put into reaction kettle, is divided with 80r/min revolving speed mechanical stirring 10
It is warming up to 60 DEG C after clock, 5 kilograms of sulfuric acid are added, is gradually heated to 90 DEG C and insulation reaction 3h, 80 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution tune pH value is added 35 kilograms of enzymolysis xylogens, carries out polymerization reaction, product to be polymerized applies 4 viscosity to 12
(25 DEG C) reach 200MPas, are cooled to 30 DEG C, and discharging obtains the glucose-lignin resin crosslinking agent.
It (2) 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 reaction kettle, after five minutes with 68r/min revolving speed mechanical stirring, is gradually heated to 85 DEG C, and insulated and stirred
2h；
(3) mixture that step (2) obtains is cooled to 65 DEG C, 100 kilograms of glucose-lignin resin crosslinking is added
Agent, and insulated and stirred 2h；
(4) mixture that step (3) obtains is cooled to 40 DEG C, 15 kilograms of sodium benzoates is added, stir evenly.
Embodiment 2
A kind of vegetable protein adhesive is each component and matter in raw material in terms of 100% by the gross mass of the adhesive raw material
It is as follows to measure percentage composition:
(1) 300 kilograms of glucose and 100 kg of water are put into reaction kettle, is divided with 80r/min revolving speed mechanical stirring 10
It is warming up to 60 DEG C after clock, 5 kilograms of sulfuric acid are added, is gradually heated to 95 DEG C and insulation reaction 1h, 85 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution tune pH value is added 35 kilograms of alkali lignins, carries out polymerization reaction, product viscosity (25 DEG C) to be polymerized to 13
Reach 250MPas, be cooled to 30 DEG C, discharging obtains the crosslinking agent (glucose-lignin resin).
(2) 400 kilograms of degreased peanut flours, 450 kg of water, 20 kilograms of neopelexes and 30 kilograms of quality are dense
Degree is put into reaction kettle for 30% potassium hydroxide aqueous solution, after five minutes with 68r/min revolving speed mechanical stirring, is gradually warmed up
To 80 DEG C, and insulated and stirred 1h；
(3) mixture that step (2) obtains is cooled to 70 DEG C, 50 kilograms of glucose-lignin resin crosslinking is added
Agent, and insulated and stirred 1.5h；
(4) mixture that step (3) obtains is cooled to 30 DEG C, 5 kilograms of sodium Diacetates is added, stir evenly.
Embodiment 3
A kind of vegetable protein adhesive is each component and matter in raw material in terms of 100% by the gross mass of the adhesive raw material
It is as follows to measure percentage composition:
(1) 300 kilograms of glucose and 100 kg of water are put into reaction kettle, is divided with 80r/min revolving speed mechanical stirring 10
It is warming up to 60 DEG C after clock, 5 kilograms of sulfuric acid are added, is gradually heated to 98 DEG C and insulation reaction 2h, 82 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution tune pH value is added 35 kilograms of enzymolysis xylogens, carries out polymerization reaction, product viscosity (25 to be polymerized to 12
DEG C) reach 400MPas, 30 DEG C are cooled to, discharging obtains the crosslinking agent (glucose-lignin resin).
It (2) 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 reaction kettle, after five minutes with 68r/min revolving speed mechanical stirring, be gradually heated to 90 DEG C, and
Insulated and stirred 3h；
(3) mixture that step (2) obtains is cooled to 78 DEG C, 200 kilograms of glucose-lignin resin crosslinking is added
Agent, and insulated and stirred 1h；
(4) mixture that step (3) obtains is cooled to 25 DEG C, 45 kilograms of propylparabens is added, stirring is equal
It is even.
Embodiment 4
A kind of vegetable protein adhesive is each component and matter in raw material in terms of 100% by the gross mass of the adhesive raw material
It is as follows to measure percentage composition:
(1) 300 kilograms of glucose and 100 kg of water are put into reaction kettle, is divided with 80r/min revolving speed mechanical stirring 10
It is warming up to 60 DEG C after clock, 5 kilograms of sulfuric acid are added, is gradually heated to 94 DEG C and insulation reaction 2.5h, is then cooled to 85 DEG C, uses
30% sodium hydrate aqueous solution tune pH value is added 35 kilograms of enzymolysis xylogens, carries out polymerization reaction, product viscosity to be polymerized to 13
(25 DEG C) reach 350MPas, are cooled to 30 DEG C, and discharging obtains 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 for being 30% for 30% sodium hydrate aqueous solution and 25 kilograms of mass concentrations is put into reaction kettle, with
68r/min revolving speed mechanical stirring after five minutes, is gradually heated to 85 DEG C, and insulated and stirred 1.5h；
(3) mixture that step (2) obtains is cooled to 65 DEG C, 250 kilograms of glucose-lignin resin crosslinking is added
Agent, and insulated and stirred 0.5h；
(4) mixture that step (3) obtains is cooled to 30 DEG C, 10 kilograms of dehydroactic acid sodiums and 25 kilograms of benzoic acid is added
Sodium stirs evenly.
Embodiment 5
A kind of vegetable protein adhesive is each component and matter in raw material in terms of 100% by the gross mass of the adhesive raw material
It is as follows to measure percentage composition:
(1) 300 kilograms of glucose and 100 kg of water are put into reaction kettle, is divided with 80r/min revolving speed mechanical stirring 10
It is warming up to 60 DEG C after clock, 5 kilograms of sulfuric acid are added, is gradually heated to 92 DEG C and insulation reaction 3h, 83 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution tune pH value is added 35 kilograms of enzymolysis xylogens, carries out polymerization reaction, product viscosity to be polymerized to 11.5
(25 DEG C) reach 100MPas, are cooled to 30 DEG C, and discharging obtains 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 reaction kettle, after five minutes with 68r/min revolving speed mechanical stirring, is gradually heated to 85 DEG C, and keep the temperature
Stir 2.5h；
(3) mixture that step (2) obtains is cooled to 75 DEG C, 145 kilograms of glucose-lignin resin crosslinking is added
Agent, and insulated and stirred 1h；
(4) mixture that step (3) obtains is cooled to 40 DEG C, 25 kilograms of sodium lactates is added, stir evenly.
Embodiment 6
A kind of vegetable protein adhesive is each component and matter in raw material in terms of 100% by the gross mass of the adhesive raw material
It is as follows to measure percentage composition:
(1) 300 kilograms of glucose and 100 kg of water are put into reaction kettle, is divided with 80r/min revolving speed mechanical stirring 10
It is warming up to 60 DEG C after clock, 5 kilograms of sulfuric acid are added, is gradually heated to 95 DEG C and insulation reaction 2.5h, is then cooled to 83 DEG C, uses
30% sodium hydrate aqueous solution tune pH value is added 35 kilograms of enzymolysis xylogens, carries out polymerization reaction, product viscosity to be polymerized to 12
(25 DEG C) reach 260MPas, are cooled to 30 DEG C, and discharging obtains 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 for being 30% for 30% sodium hydrate aqueous solution and 15 kilograms of mass concentrations is put into reaction kettle, with
68r/min revolving speed mechanical stirring after five minutes, is gradually heated to 85 DEG C, and insulated and stirred 3h；
(3) mixture that step (2) obtains is cooled to 65 DEG C, 150 kilograms of glucose-lignin resin crosslinking is added
Agent, and insulated and stirred 0.5h；
(4) mixture that step (3) obtains is cooled to 35 DEG C, 15 kilograms of sodium benzoates is added, stir evenly.
Embodiment 7
A kind of vegetable protein adhesive is each component and matter in raw material in terms of 100% by the gross mass of the adhesive raw material
It is as follows to measure percentage composition:
(1) 300 kilograms of glucose and 100 kg of water are put into reaction kettle, is divided with 80r/min revolving speed mechanical stirring 10
It is warming up to 60 DEG C after clock, 5 kilograms of sulfuric acid are added, is gradually heated to 93 DEG C and insulation reaction 2h, 82 DEG C is then cooled to, with 30%
Sodium hydrate aqueous solution tune pH value is added 35 kilograms of enzymolysis xylogens, carries out polymerization reaction, product viscosity (25 to be polymerized to 10
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 reaction kettle, stirs 5 points with 68r/min revolving speed mechanical stirring
Zhong Hou is gradually heated to 80 DEG C, and insulated and stirred 3h；
(3) mixture that step (2) obtains is cooled to 78 DEG C, 220 kilograms of glucose-lignin resin crosslinking is added
Agent, and insulated and stirred 2h；
(4) mixture that step (3) obtains is cooled to 30 DEG C, 50 kilograms of nisins is added, stir evenly.
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 reaction kettle, with 68r/min revolving speed
Mechanical stirring after five minutes, is gradually heated to 90 DEG C, and insulated and stirred 2.5h；
(2) mixture that step (1) obtains is cooled to 70 DEG C, 80 kilograms of urea-dialdehyde starch resin cross-linking agent is added,
And insulated and stirred 2h；
(3) mixture that step (2) obtains is cooled to 40 DEG C, 15 kilograms of sodium benzoates, 5 kilograms of para hydroxybenzene first is added
Propyl propionate stirs evenly.
Embodiment 9
It (1) 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 reaction kettle, after five minutes with the stirring of 68r/min revolving speed mechanical stirring, is gradually warming up to 85 DEG C,
And insulated and stirred 1.5h；
(2) mixture that step (1) obtains is cooled to 73 DEG C, 100 kilograms of tannin-furfuryl alcohol resin crosslinking agent is added, and
Insulated and stirred 2h；
(3) mixture that step (2) obtains is cooled to 35 DEG C, 30 kilograms of potassium sorbates is added, stir evenly.
Reference examples 1
Vegetable protein adhesive is prepared in the same manner as shown in Example 1.The difference is that directly being substituted with glucose
The crosslinking agent prepares vegetable protein adhesive.
Reference examples 2
Vegetable protein adhesive is prepared in the same manner as shown in Example 1.The difference is that directly being substituted with lignin
The crosslinking agent prepares vegetable protein adhesive.
Reference examples 3
Vegetable protein adhesive is prepared in the same manner as shown in 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 glucose solution is directly adjusted to
For pH value to 12, then addition enzymolysis xylogen, which directly carries out polymerization reaction, (can not occur polymerization reaction, viscosity is also not achieved
100MPa·s)。
Embodiment 10
Performance in order to verify vegetable protein adhesive of the present invention and its application effect on core-board product
With the advantage environmentally protective, non-hazardous to human body of product, and carry out a series of experiments, particular content is as follows:
Solid 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, total volatile organic compounds release rate
Application effect of the vegetable protein adhesive on core-board product is evaluated in detection.Wherein, solid content, pH value, storage period,
The test of viscosity, free formaldehyde is according to phase specified in GB/T 14074-2006 " wood adhesive and its resin method of inspection "
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
Corresponding detection method specified in 18583-2008 " limits of harmful substances in indoor decorating and refurnishing materials adhesive ", testing result
As shown in table 2.
The performance parameter for the adhesive that 2 Examples 1 to 9 of table and reference examples 1~3 obtain
As can be seen from Table 2, since the raw material of albumen adhesive is mainly derived from regenerated vegetable protein, lignin, Portugal
The biomass such as grape sugar, using in vegetable protein adhesive prepared by 1~3 method of 1~9 method of the embodiment of the present invention and reference examples
Without poisonous and harmful substances such as free formaldehyde, free benzene compounds, make the complete greenization of adhesive.
Using the viscosity of vegetable protein adhesive prepared by 1~9 method of the embodiment of the present invention in 4520~9860MPa
Between s, hence it is evident that greater than the viscosity (3490~3610MPas) of adhesive prepared by 1~3 method of reference examples.This 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 lower, not formed tool
There is the network size molecule of resistance to water-bound.
The storage period of albumen adhesive prepared by 1~9 method of the embodiment of the present invention meets albumen at 20 days or more
Adhesive need to be in requirement in 15 days or more to storage period as core-board adhesive.Use conventional diaion as
When preparing core-board with adhesive, need to carry out adhesive impregnation to improve the tack of adhesive, usually in resin
The flour of weight resin 30~40% is added.And albumen adhesive prepared by 1~9 method of the embodiment of the present invention is with higher
Viscosity makes it not need additionally to add flour just and have good tack, further reduced albumen adhesive as thin wood
The use cost of work plate glue.
Preparing core plate used by core-board is that (900 millimeters of length, 400 millimeters of width, thickness 10 is in the least for China fir batten
Rice) by plate made of coating albumen adhesive gluing.Used dash board is 5 years fast-growing Eucalyptus veneer (2440 millis of length
Rice, 1220 millimeters of width, 2.2 millimeters of thickness), moisture content is 10~20%.The preparation process of core-board: first by fir core plate
It carries out polishing processing using sander, Eucalyptus veneer is then chosen, 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 entire plate using putty, the plate repaired is sent
Enter and carry out hot pressing in hot press, hot pressing technique is: (1) being glued: the two-sided sizing of core material, resin added are 330~380g/m2；
(2) aging and time: closure ageing, 30~90min；(3) hot compression parameters: pressure 1.1-1.3MPa, temperature be 120~
125 DEG C, the time is 13-15 minutes.Finally the plate after hot pressing is sent into sander and polish processing to get vegetable protein
The Formaldehydeless fine wooden board of glue laminated.
According to II class bonding strength, the test method of dipping and stripping specified in GB/T 5849-2006 " core-board " and
Burst size of methanal measurement test method detects the vegetable protein adhesive that 9 kinds of embodiment methods obtain and 3 reference examples methods obtain
Bonding strength, dipping and stripping performance and the burst size of methanal of core-board prepared by the adhesive obtained, the results are shown in Table 3.
According to general volatile organic specified in HJ571-2010 " environmental labelling product technical requirements --- wood-based plate and its product "
Close the test method detection of object
The total volatile organic compounds release rate of core-board product, the results are shown in Table 3.
The performance parameter of the core-board for the adhesive gluing that 3 Examples 1 to 9 of table and reference examples 1~3 obtain
As shown in table 3, the joiner prepared using vegetable protein adhesive prepared by 1~9 method of the embodiment of the present invention
Plate all has higher bonding strength, meets indoor II class specified in standard GB/T/T 5849-2006 " core-board "
Bonding strength (being not less than 0.70MPa) requires, and all has qualified dipping and stripping performance, wherein 1,2,3,8,9 side of embodiment
The adhesive bonding strength with higher of method preparation, and use the thin wood of the preparation of Resin adhesive prepared by reference examples method
The bonding strength of work plate is below 0.70MPa, and II class bonding strength national standard is not achieved.
Had using the core-board that vegetable protein adhesive prepared by 1~9 method of the embodiment of the present invention manufactures extremely low micro-
The Form aldehyde release of amount, this is because caused by timber itself can release formaldehyde, and total volatile organic compounds release rate
Numerical value is extremely low, close to Form aldehyde release magnitude, illustrate the core-board of preparation other than the ultra-low volume formaldehyde that timber itself discharges,
No other toxic, harmful organic matter releases, show using vegetable protein gluing prepared by 1~9 method of the embodiment of the present invention
Agent can produce the environmentally protective core-board product of unharmful substance release.
As seen from the above embodiment, the present invention provides a kind of vegetable protein adhesives and its preparation method and application.Root
According to the result of embodiment it is found that without free formaldehyde, free benzene compounds in vegetable protein adhesive prepared by the present invention
Equal poisonous and harmful substances, adhesive realize complete greenization, can produce the environmentally protective joiner of unharmful substance release
Plate.And the viscosity of vegetable protein adhesive prepared by the present invention is between 4520~9860MPas, hence it is evident that is greater than reference examples 1
The viscosity (3490~3610MPas) of adhesive prepared by~3 methods.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of vegetable protein adhesive, is prepared by the raw material comprising following mass fraction:
The crosslinking agent is glucose-lignin resin crosslinking agent, in 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；
The glucose-lignin resin crosslinking agent is prepared according to the method comprised the following steps:
Glucose solution 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 polymerization reaction, obtain glucose-lignin resin crosslinking agent.
2. vegetable protein adhesive according to claim 1, which is characterized in that in the glucose solution glucose and
The mass ratio of water is (2~5): 1.
3. vegetable protein adhesive according to claim 2, which is characterized in that the glucose, acidic catalyst and wood
The mass ratio of quality is (2~5): (0.01~0.1): (0.1~0.5).
4. vegetable protein adhesive according to claim 1 or 3, which is characterized in that the acidic catalyst is sulfuric acid, nitre
One or more of acid, halogen acids and oxalic acid.
5. vegetable protein adhesive according to claim 1, which is characterized in that the temperature of the polymerization reaction is 80~85
℃。
6. vegetable protein adhesive according to claim 1, which is characterized in that the vegetable protein is defatted soy flour, takes off
One or more of rouge dregs of beans, soybean protein isolate, degreased peanut flour, degreased cottonseed meal and degreasing oil-tea-cake meal.
7. the preparation method of vegetable protein adhesive described in claim 1~6 any one, comprises the following steps:
(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.
8. preparation method according to claim 7, which is characterized 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.
9. vegetable protein adhesive described in claim 1~6 any one or the preparation method of claim 7 or 8 obtain
Vegetable protein adhesive preparing the application in core-board.
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| CN108531128B (en) * | 2018-02-27 | 2020-11-06 | 山东顺创新材料科技有限公司 | Aldehyde-free lignin adhesive and preparation method thereof |
| CN110408329A (en) * | 2019-05-20 | 2019-11-05 | 湖南宏润科技发展有限公司 | A kind of high-strength water-resistance plant albumin glue 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 |
| 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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| CN101039884A (en) * | 2004-10-15 | 2007-09-19 | 亚什兰许可和知识产权有限公司 | Binder composition comprising condensed tannin and furfuryl alcohol and its uses |
| WO2007149589A2 (en) * | 2006-06-23 | 2007-12-27 | Ashland Licensing And Intellectual Property Llc | Two-part bio-based furfuryl adhesive composition for engineered wood |
| CN102617819A (en) * | 2012-04-23 | 2012-08-01 | 浙江农林大学 | Production method for dialdehyde starch adhesive |
| CN104962227A (en) * | 2015-06-30 | 2015-10-07 | 西南林业大学 | Full-biomass timber adhesive and preparation method as well as application thereof |
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| CN101039884A (en) * | 2004-10-15 | 2007-09-19 | 亚什兰许可和知识产权有限公司 | Binder composition comprising condensed tannin and furfuryl alcohol and its uses |
| WO2007149589A2 (en) * | 2006-06-23 | 2007-12-27 | Ashland Licensing And Intellectual Property Llc | Two-part bio-based furfuryl adhesive composition for engineered wood |
| CN102617819A (en) * | 2012-04-23 | 2012-08-01 | 浙江农林大学 | Production method for dialdehyde starch adhesive |
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