CN110003493A - In-situ modified dregs of beans, adhesive and the preparation method and application thereof - Google Patents
In-situ modified dregs of beans, adhesive and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110003493A CN110003493A CN201910298546.2A CN201910298546A CN110003493A CN 110003493 A CN110003493 A CN 110003493A CN 201910298546 A CN201910298546 A CN 201910298546A CN 110003493 A CN110003493 A CN 110003493A
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- Prior art keywords
- beans
- dregs
- adhesive
- preparation
- situ modified
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
Abstract
The present invention provides a kind of in-situ modified dregs of beans, adhesive and the preparation method and application thereof.In-situ modified dregs of beans is made in dregs of beans and modifying agent after mixing, after crushing.The research of the invention finds that can be realized modifying agent using the heat generated in crushing process and sufficiently reacted with dregs of beans, reach dregs of beans crushing and is completed at the same time purpose with modification, it is high that reactivity is made, in-situ modified bean cake powder easy to use, particularly useful for making adhesive.The present invention also provides using the in-situ modified dregs of beans as adhesive made of raw material and its application.Under the in-situ modified bean cake powder drying regime can long term storage, convenient transportation, when use directly adds water and common urea and alkali, is uniformly mixed, enormously simplifies actual production technique, reduce raw material transportation cost.The formaldehydeless release of adhesive thoroughly solves the problems, such as artificial board formaldehyde release；Its glue-joint strength is high, has excellent water-resistance, can satisfy the requirement of II class glued board.
Description
Technical field
The invention belongs to adhesive technology fields, and in particular to a kind of in-situ modified dregs of beans, the gluing being processed into using it
Agent and its application.
Background technique
Timber industry is with the adhesive overwhelming majority based on " three aldehyde ", and the wood-based plate and its product of preparation are in use
The problems such as there are Form aldehyde releases.In order to solve the problems, such as that existing timber industry adhesive exists and harm, exploitation are environmentally protective
No aldehyde adhesive is of great significance.
Soybean is the most abundant vegetable protein sources in the world, and protein content is very high in soybean, soybean protein molecule
On have a large amount of amino, carboxyl, hydroxyl, phenolic hydroxyl group isopolarity group, very strong hydrogen bond, Van der Waals can be formed with timber component
Power, hydrophobicity effect and a small amount of covalent bond, therefore be the no aldehyde adhesive raw material of extraordinary wood-based plate.But it is glued strong
Spending low and water resistance difference is always to limit the bottleneck problem of soybean protein base adhesive development, and people take different sides thus
Method is modified it.Research confirms that the crosslinking agents such as polyamine epichlorohydrin resin (PAE), polyisocyanates can be with
The reaction of soybean protein residue, to increase the cohesive strength of adhesive itself, effectively improves the water-fast splicing of Soy-based Protein adhesive
Performance.
However, in actual production, adhesive needs extemporaneous preparation when in use, crosslinking agent etc. is with Soy-based Protein raw material
It is added in batches, causes production process cumbersome, process operability is poor；The cross linker active phase is short, and solid content is low, cannot store up for a long time
It deposits, liquid cross-linker transportation cost is higher, and limitation significantly is promoted the use of without aldehyde adhesive.
Summary of the invention
In view of the above deficiencies, the present invention provides a kind of wood-based plate Soy-based Protein adhesives and preparation method thereof.
A purpose of the invention is to be to provide a kind of in-situ modified dregs of beans.In-situ modified dregs of beans prepared by the present invention is used for
Adhesive is prepared, reactivity is high, and easy to use, production cost is low.
Another object of the present invention is that providing more than one states the Soy-based Protein glue that in-situ modified dregs of beans is raw material preparation
Glutinous agent, the adhesive have the advantages that glue-joint strength is high, water-tolerant, formaldehydeless release, are suitble to industrialized production.
The present invention in experimental study it was unexpectedly observed that after mixing by dregs of beans and modifying agent, dregs of beans pulverizer is added,
It using the heat generated in crushing process, realizes modifying agent and is sufficiently reacted with dregs of beans, reach dregs of beans crushing and modification is complete simultaneously
At purpose.Reactivity height, in-situ modified bean cake powder easy to use, particularly useful for making adhesive are obtained.Further
In depth the study found that realizing that the in-situ modified key factor of dregs of beans includes: 1) in crushing process to the extruding force of dregs of beans；2) powder
The heat generated during broken；Its direct performance is the temperature change of dregs of beans in crushing process.The study found that when in crushing process
When the temperature of dregs of beans is increased to 50-90 DEG C preferably 65-75 DEG C or so, modified effect is best.Based on the studies above, spy proposes this hair
It is bright.
Specifically, the present invention provides a kind of preparation method of in-situ modified dregs of beans, including dregs of beans is mixed with modifying agent
After uniformly, crush.
Further, the temperature that dregs of beans is controlled in crushing process is increased to 50-90 DEG C preferably 65-75 DEG C or so.
Further, in crushing process, control control is 10 ± 2 minutes or so to the extrusion process residence time of dregs of beans.
Further, the present invention is crushed using super fine flour mill, carries out sub-sieve using bull cage type powder.
The present invention has also advanced optimized the weight ratio of dregs of beans and modifying agent, wherein when the weight ratio of dregs of beans and modifying agent
For 1-25:100, preferably 3-17:100, when more preferable 5-10:100, modified effect is best, is more advantageous to and prepares adhesive.
The modifying agent is to enable to the modified satisfaction of dregs of beans to prepare the purpose of adhesive, such as epoxy chlorine can be selected
Propane, glycidol ether, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane (KH560), N hydroxymethyl acrylamide, horse
Come one of acid anhydrides, triglycidyl isocyanurate or any several mixture.
The dregs of beans is defatted soybean dregs of beans；Preferably, the protein content of the dregs of beans is 43-65%, fat content
≤ 1.2%.
The invention also includes the in-situ modified dregs of beans of above method preparation.
The invention also includes the in-situ modified dregs of beans of above method preparation to prepare the application on adhesive.
Specifically, the present invention also provides a kind of adhesives, are raw material by above-mentioned in-situ modified bean cake powder, alkali, urea, water etc.
It is made.Common preparation method is to take each raw material according to the ratio, is stirred evenly.
For the correlated performance for preferably improving adhesive, such as solidification temperature, bonding strength etc., the present invention is also into one
Step optimizes the consumption proportion of each raw material.
Specifically, the present invention provides a kind of adhesive, the raw material including following parts by weight:
It is further preferred that the adhesive includes the raw material of following parts by weight:
Wherein, one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide etc. can be selected in the alkali
Mixed base.
Further, the solid content of the adhesive is 25-45%wt and/or viscosity is 200-2000mPas,
And/or the active phase is 5-15 days.
The invention also includes above-mentioned adhesive answering in fields such as timber, bamboo wood, furniture, printed matter, fitting-up, buildings
With.
Particularly, the invention also includes contain above-mentioned adhesive timber processed goods, bamboo processing product, such as glued board,
Wood-based plates such as particieboard, medium density fibre board (MDF) and core-board etc..
It is as follows that adhesive of the present invention carries out cost analysis: currently, the price of low content of free formaldehyde content urea-formaldehyde glue and sticks agent exists
2500 yuan/ton or so；For the price of adhesive of the present invention at 2000-3500 yuan/ton or so, use cost is lower, especially reduces
Transportation cost simplifies production technology, has good promotion prospect.
Beneficial effects of the present invention are as follows:
Adhesive is made using in-situ modified bean cake powder as raw material in the present invention, can under the in-situ modified bean cake powder drying regime
Long term storage, convenient transportation, when use, directly add water and common urea and alkali, are uniformly mixed, enormously simplify practical life
Production. art reduces raw material transportation cost.
Form aldehyde release is not present in the wood-based plate of the formaldehydeless release of adhesive of the present invention, manufacture, thoroughly solves artificial
Plate Form aldehyde release problem；Its glue-joint strength is high, has excellent water-resistance, can satisfy the requirement of II class glued board, and through 100 DEG C of water
It boils and does not come unglued, can be used for producing the wood-based plates such as glued board, particieboard, medium density fibre board (MDF) and core-board.
Primary raw material dregs of beans of the present invention is cereal crops industrial wood waste, is a kind of reproducible resource, can solve simultaneously
The certainly higher cost problem of the recycling problem of cereal crops waste material and biomass adhesive solves synthetic adhesive and provides to fossil
Problem is depended in source unduly, meets environmental protection and sustainable development requirement, has important economic and social profit.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
Pulverizer used below is super fine flour mill, carries out sub-sieve using bull cage type powder.
The dregs of beans is defatted soybean dregs of beans；Protein content is 43-65%, fat content≤1.2%.
Embodiment 1
5kg γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH560) and 100kg dregs of beans are uniformly mixed, are added
Pulverizer makes in crushing process dregs of beans temperature be increased to 90 DEG C, and the extrusion process residence time is 10 minutes, and original position is made in sub-sieve
Modified bean pulp powder.
Embodiment 2
A kind of adhesive is formulated as follows:
Urea and sodium hydroxide: being distributed in water by preparation method by formula, stir evenly (speed of agitator is 1200 turns/
Minute), obtain the mixed solution containing alkali and urea；In-situ modified bean cake powder prepared by embodiment 1 is added under stirring conditions
It stirs evenly.
Experimental example 1
The performance indicator of adhesive prepared by embodiment 2 is as shown in table 1.
The performance indicator of 1 adhesive of table
Embodiment 3
The epoxychloropropane of 10kg and 100kg dregs of beans are uniformly mixed, pulverizer is added, makes dregs of beans temperature in crushing process
88 DEG C or so are increased to, the extrusion process residence time is 10 minutes, and in-situ modified bean cake powder is made in sub-sieve.
Embodiment 4
A kind of adhesive is formulated as follows:
Urea and sodium hydroxide: being distributed in water by preparation method by formula, stir evenly (speed of agitator is 1200 turns/
Minute), obtain the mixed solution containing alkali and urea；In-situ modified bean cake powder prepared by embodiment 3 is added under stirring conditions
It stirs evenly.
Experimental example 2
The performance indicator of adhesive prepared by embodiment 4 is as shown in table 2.
The performance indicator of 2 adhesive of table
Experimental example 3
Comparative example 1: using conventional use of urea-formaldehyde resin adhesive in wood-based plate manufacture.
Comparative example 2: agent is sticked using conventional use of melamine resin adehsive in wood-based plate manufacture.
The adhesive of adhesive and comparative example 1-2 prepared by the embodiment of the present invention 2,4 is utilized respectively to manufacture three layers of gluing
Plate, using following preparation technology parameter:
Veneer: poplar, moisture content 8-12%, thickness 1.6mm；
Sizing: core plate gluing, glue-spread 270-325g/m2(two-sided)；
Digestion time: 30-90min；
Hot pressing: hot pressing temperature is 120 DEG C；Hot pressing pressure is 1.0-1.3Mpa；Hot pressing time is 10min (100s/min)
Three layers of glued board of above-mentioned technique manufacture are according to GB/T17657-1999 " wood-based plate and face artificial board physicochemical property
Experimental method " its burst size of methanal and bonding strength (II class) are detected, the results are shown in Table 3.
The burst size of methanal and bonding strength of 3 glued board of table
| Test specimen | Burst size of methanal (mg/L) | Bonding strength (MPa) |
| Embodiment 2 | 0.02 | 1.24±0.05 |
| Embodiment 4 | 0.03 | 1.01±0.02 |
| Comparative example 1 | 1.46 | 0.56 |
| Comparative example 2 | 0.38 | 0 (coming unglued) |
1: II class glued board standard of note: E0 standard is≤0.5mg/L；E1 standard is 0.5-1.5mg/L；E2 standard is 1.5-
5.0mg/L。
Note 2: the Form aldehyde release from timber itself, similarly hereinafter.
Testing result shows that burst size of methanal is respectively less than in the glued board prepared using Soy-based Protein adhesive of the present invention
The water-fast intensity of 0.1mg/L, the glued board of manufacture are high, are all satisfied the requirement of II class glued board.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of preparation method of in-situ modified dregs of beans, which is characterized in that including by dregs of beans and modifying agent after mixing, powder
It is broken；The temperature that dregs of beans is controlled in crushing process is increased to 50-90 DEG C.
2. preparation method according to claim 1, which is characterized in that the temperature for controlling dregs of beans in crushing process is increased to
65-75℃。
3. preparation method according to claim 1 or 2, which is characterized in that in crushing process, control the extruding to dregs of beans
The journey residence time is 10 ± 2 minutes, and/or；It is separated using bull cage type powder.
4. preparation method according to claim 1-3, which is characterized in that the weight ratio of dregs of beans and modifying agent is 1-
25:100, preferably 3-17:100, more preferably 5-10:100.
5. preparation method according to claim 1-4, which is characterized in that the modifying agent selects epoxy chloropropionate
Alkane, glycidol ether, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane (KH560), N hydroxymethyl acrylamide, Malaysia
One of acid anhydrides, triglycidyl isocyanurate or any several mixture；And/or
The dregs of beans is defatted soybean dregs of beans；Preferably, the protein content of the dregs of beans be 43-65%, fat content≤
1.2%.
6. the in-situ modified dregs of beans of any one of claim 1-5 the method preparation.
7. in-situ modified dregs of beans described in claim 6 is preparing the application on adhesive.
8. a kind of adhesive, raw material includes in-situ modified bean cake powder, alkali, urea and water described in claim 6；
Preferably, the adhesive, the raw material including following parts by weight:
It is further preferred that the adhesive includes the raw material of following parts by weight:
Preferably, the alkali selects the mixed of one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide etc.
Close alkali；
Preferably, the solid content of the adhesive is 25-45%wt and/or viscosity is 200-2000mPas, and/or living
Property the phase be 5-15 days.
9. the preparation method of adhesive described in claim 8, including each raw material is taken according to the ratio, it stirs evenly.
10. adhesive described in claim 8 or the adhesive of claim 9 the method preparation are in timber, bamboo wood, furniture, print
Brush product, fitting-up or the application of building field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910298546.2A CN110003493A (en) | 2019-04-15 | 2019-04-15 | In-situ modified dregs of beans, adhesive and the preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910298546.2A CN110003493A (en) | 2019-04-15 | 2019-04-15 | In-situ modified dregs of beans, adhesive and the preparation method and application thereof |
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| CN110003493A true CN110003493A (en) | 2019-07-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171314A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Modified PAE resin crosslinking agent, modified adhesive and application |
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Application publication date: 20190712 |