CN107286905B - A method of it is prepared using lignin without aldehyde lignin-base based Wood Adhesives - Google Patents
A method of it is prepared using lignin without aldehyde lignin-base based Wood Adhesives Download PDFInfo
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- CN107286905B CN107286905B CN201710632040.1A CN201710632040A CN107286905B CN 107286905 B CN107286905 B CN 107286905B CN 201710632040 A CN201710632040 A CN 201710632040A CN 107286905 B CN107286905 B CN 107286905B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J197/00—Adhesives based on lignin-containing materials
- C09J197/005—Lignin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
Abstract
A method of it is prepared using lignin without aldehyde lignin-base based Wood Adhesives, is related to a kind of preparation method of based Wood Adhesives.The invention aims to solve the problems, such as in traditional timber adhesive that petroleum base component dosage is excessive and adhesive in there are toxic and volatile substances.Method: one, lignin-alkali-glyoxal mixed aqueous solution is configured；Two, the hydroxylating of lignin；Three, the preparation of adhesive to get to using lignin preparation without aldehyde lignin-base based Wood Adhesives.The present invention prepares the method without aldehyde lignin-base based Wood Adhesives using lignin for a kind of.
Description
Technical field
The present invention relates to a kind of preparation methods of based Wood Adhesives.
Background technique
China is timber consumption big country, but since nineteen nineties, the natural high-quality large diameter in China
Timber is fewer and fewer, in addition to this, due in international coverage the lumber market status that supply falls short of demand cause Russia, Southeast Asia with
And the imported log price of the country such as Africa increasingly goes up, China's woodwork relevant industries receive unprecedented pressure.For
Meet all trades and professions development and the needs of living standards of the people are improved to woodwork, many wood processing enterprises are early both at home and abroad
Sight is transferred on small dimension wood, brush wood and artificial fast growing wood.With brush wood, small dimension wood, low-grade wood and felling
Residue etc. is used as raw material, is fruitfully delayed using the method that wood adhesion technology prepares wood-based plate and other timber-works
The pressure of timber resources scarcity is solved.Synthesis tree of the adhesive still to be derived from petroleum resources used in current wood industry
Based on rouge adhesive, such as phenolic resin and Lauxite, such adhesive is not only had excellent performance, but also cheap, using skill
Art is mature.But there is also many deficiencies for existing based Wood Adhesives simultaneously: (1) petroleum base component dosage mistake in traditional timber adhesive
Height, such as 45% or more raw material of Lauxite is from petroleum, and phenolic resin is then up to 95%, petroleum resources are increasingly depleted to lead
Synthetic resin type adhesive production cost is caused to sharply increase；(2) formaldehyde (toxicity: LD in adhesive50Mouse > 42mg/kg), benzene
Phenol (toxicity: LD50Mouse > 270mg/kg) etc. toxic volatiles small molecule can cause damages to people's health, it is current big
Most wood-based plates all there are problems that the volatilization of different degrees of formaldehyde (E2 grades≤5.0mg/L, E1 grades≤1.5mg/L, E0 grades≤
0.5mg/L)；(3) traditional timber adhesive biological degradability is poor, can cause environmental pollution.Therefore, people urgently seek benefit
With the method for renewable resource preparation aldehyde-free wood adhesive.Currently, soybean protein base based Wood Adhesives and starch-base timber glue
Industrial applications are all successfully realized in glutinous agent etc., however the example of lignin-base based Wood Adhesives successful commercialization application but rarely has
Report.
Lignin is a kind of cheap, huge renewable biomass resources of yield, and structure contains various active official
It can roll into a ball, such as phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl, aldehyde radical, conjugated double bond, this prepares the base of different kind organism material also with it
Plinth.Lignin-base based Wood Adhesives refer to based on lignin or modified lignin resin, add a certain amount of curing agent and other are helped
A kind of based Wood Adhesives that agent is prepared.The most commonly used lignin is derived from pulping and paper-making industry in adhesive industry
By-product and by-product from biorefinery industry, the latter do not pass through the boiling processing of alkali or salt, palliating degradation degree is low,
The structure of script lignin is preferably remained, purity and activity are higher.Before preparing adhesive, it usually needs to lignin into
Row is modified, and to improve the content of particular functional group in lignin molecule, intensified response activity promotes the glue of lignin-base adhesive
Connect performance.The greenization of lignin is modified and prepares the technologies such as aldehyde-free wood adhesive using it and is for wood processing industry
Significance is suffered to entire lignin-base biological material processing industry.
Summary of the invention
The invention aims to solve that petroleum base component dosage in traditional timber adhesive is excessive and adhesive in deposit
The toxic and volatile substances the problem of, and provides and a kind of utilize method of the lignin preparation without aldehyde lignin-base based Wood Adhesives.
It is a kind of to prepare what the method without aldehyde lignin-base based Wood Adhesives was specifically realized by the following steps using lignin:
One, lignin-alkali-glyoxal mixed aqueous solution is configured:
Under conditions of low whipping speed is 400r/min~600r/min, lignin is added in the water solution A of alkali, is obtained
To mixture, glyoxal water solution is added into mixture, obtains homogeneous material, the water-soluble of alkali is finally added into homogeneous material
Liquid B to pH is 10~13, obtains lignin-alkali-glyoxal mixed aqueous solution；
The mass ratio of the water solution A of the lignin and alkali is 1:(0.75~1.5)；The lignin and glyoxal
The mass ratio of aqueous solution is 1:(0.75~4)；
The mass percent of alkali is 20%~40% in the water solution A of the alkali；Alkali in the water solution A of the alkali
For the mixture of one or both of sodium hydroxide and potassium hydroxide；The aqueous solution B of the alkali and the water solution A of alkali are same
Kind substance；
The mass percent of glyoxal is 30%~50% in the glyoxal water solution；
The lignin is that cornstalk biological refines lignin；
Two, the hydroxylating of lignin:
Lignin-alkali-glyoxal mixed aqueous solution is placed in three mouthfuls of glass reaction kettles with agitating paddle and condenser pipe
In, under conditions of low whipping speed is 200r/min~400r/min and reaction temperature is 40 DEG C~90 DEG C, 2h~10h is reacted,
It is cooled to room temperature after reaction, obtains modified lignin liquor；
Three, the preparation of adhesive:
Under agitation, epoxychloropropane and water-based emulsion are added into modified lignin liquor, is uniformly mixed,
Be utilized lignin preparation without aldehyde lignin-base based Wood Adhesives；
The mass ratio of the modified lignin liquor and epoxychloropropane is 1:(0.15~0.4)；Described changes
Property after lignin liquor and water-based emulsion mass ratio be 1:(0.1~0.3).
Water in the water solution A of the alkali, the aqueous solution B of alkali and glyoxal water solution is tap water or distilled water, excellent
It is selected as distilled water.
Water-based emulsion described in step 3 is acrylic emulsion or aqueous polyurethane emulsion.
Advantages of the present invention:
Utilize nontoxic, nonvolatile glyoxal (toxicity: LD50Mouse > 1280mg/kg) substitution formaldehyde (LD50Mouse >
42mg/kg), phenol (LD50Mouse > 270mg/kg) etc. toxic volatiles small molecule lignin is modified, in lignin
Certain hydroxyl and aldehyde radical isoreactivity functional group are introduced in molecule, improve the active purpose of lignin reaction to reach.Meanwhile
When preparing adhesive using modified lignin, the curing agent and auxiliary agent of any high toxicity (formaldehyde, phenol) are not added, thus
Reach the problem of there is no noxious material volatilizations during the entire process of preparing and applying from lignin modification to adhesive, especially
There is no the release of free formaldehyde.Petroleum base component only accounts for 25%~30% in the adhesive that this method obtains, and compares traditional timber
Adhesive (Lauxite 45%, phenolic resin 95%) has apparent reduction.
Functional group content in rear lignin molecule before modified and reactivity are analyzed, modified corn stover is wooden
Total hydroxy radical content of element is 23.86%, improves 13.41% compared to unmodified lignin, it is known that utilizes glyoxal modified corn
Straw lignin can reach desired effect, with the reactivity of isocyanates or epoxychloropropane better than unmodified wooden
Element.Aldehyde-free wood adhesive is prepared using modified lignin resin and prepares three layers of glued board under hot pressing condition using it, is obtained
Glued board good mechanical properties, dry glue intensity can reach 2.73MPa.
The present invention prepares the method without aldehyde lignin-base based Wood Adhesives using lignin for a kind of.
Detailed description of the invention
Fig. 1 is Fourier transform infrared spectroscopy figure, and a is unmodified Spruce lignin, and b is modified corn stover
Lignin solid powder；
Fig. 2 is DSC spectrogram, and 1 mixes for unmodified Spruce lignin with poly methylene poly phenyl poly isocyanate,
2 mix for modified Spruce lignin solid powder with poly methylene poly phenyl poly isocyanate；
Fig. 3 is DSC spectrogram, and 1 mixes for unmodified Spruce lignin with epoxychloropropane, and 2 be modified corn
Straw lignin solid powder is mixed with epoxychloropropane.
Specific embodiment
Specific embodiment 1: present embodiment be it is a kind of using lignin prepare without aldehyde lignin-base based Wood Adhesives
What method was specifically realized by the following steps:
One, lignin-alkali-glyoxal mixed aqueous solution is configured:
Under conditions of low whipping speed is 400r/min~600r/min, lignin is added in the water solution A of alkali, is obtained
To mixture, glyoxal water solution is added into mixture, obtains homogeneous material, the water-soluble of alkali is finally added into homogeneous material
Liquid B to pH is 10~13, obtains lignin-alkali-glyoxal mixed aqueous solution；
The mass ratio of the water solution A of the lignin and alkali is 1:(0.75~1.5)；The lignin and glyoxal
The mass ratio of aqueous solution is 1:(0.75~4)；
The mass percent of alkali is 20%~40% in the water solution A of the alkali；Alkali in the water solution A of the alkali
For the mixture of one or both of sodium hydroxide and potassium hydroxide；The aqueous solution B of the alkali and the water solution A of alkali are same
Kind substance；
The mass percent of glyoxal is 30%~50% in the glyoxal water solution；
The lignin is that cornstalk biological refines lignin；
Two, the hydroxylating of lignin:
Lignin-alkali-glyoxal mixed aqueous solution is placed in three mouthfuls of glass reaction kettles with agitating paddle and condenser pipe
In, under conditions of low whipping speed is 200r/min~400r/min and reaction temperature is 40 DEG C~90 DEG C, 2h~10h is reacted,
It is cooled to room temperature after reaction, obtains modified lignin liquor；
Three, the preparation of adhesive:
Under agitation, epoxychloropropane and water-based emulsion are added into modified lignin liquor, is uniformly mixed,
Be utilized lignin preparation without aldehyde lignin-base based Wood Adhesives；
The mass ratio of the modified lignin liquor and epoxychloropropane is 1:(0.15~0.4)；Described changes
Property after lignin liquor and water-based emulsion mass ratio be 1:(0.1~0.3).
The advantages of present embodiment:
Utilize nontoxic, nonvolatile glyoxal (toxicity: LD50Mouse > 1280mg/kg) substitution formaldehyde (LD50Mouse >
42mg/kg), phenol (LD50Mouse > 270mg/kg) etc. toxic volatiles small molecule lignin is modified, in lignin
Certain hydroxyl and aldehyde radical isoreactivity functional group are introduced in molecule, improve the active purpose of lignin reaction to reach.Meanwhile
When preparing adhesive using modified lignin, the curing agent and auxiliary agent of any high toxicity (formaldehyde, phenol) are not added, thus
Reach the problem of there is no noxious material volatilizations during the entire process of preparing and applying from lignin modification to adhesive, especially
There is no the release of free formaldehyde.Petroleum base component only accounts for 25%~30% in the adhesive that this method obtains, and compares traditional timber
Adhesive (Lauxite 45%, phenolic resin 95%) has apparent reduction.
Functional group content in rear lignin molecule before modified and reactivity are analyzed, modified corn stover is wooden
Total hydroxy radical content of element is 23.86%, improves 13.41% compared to unmodified lignin, it is known that utilizes glyoxal modified corn
Straw lignin can reach desired effect, with the reactivity of isocyanates or epoxychloropropane better than unmodified wooden
Element.Aldehyde-free wood adhesive is prepared using modified lignin resin and prepares three layers of glued board under hot pressing condition using it, is obtained
Glued board good mechanical properties, dry glue intensity can reach 2.73MPa.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: it is described in step 1 wooden
Element and the mass ratio of the water solution A of alkali are 1:1.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 1
The mass percent of alkali is 30% in the water solution A for the alkali stated.Other steps are the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: institute in step 1
The mass percent of glyoxal is 40% in the glyoxal water solution stated.Other steps are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: institute in step 1
The mass ratio of the lignin and glyoxal water solution stated is 1:3.Other steps are identical as specific embodiment one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: institute in step 1
The mass ratio of the lignin and glyoxal water solution stated is 1:(0.75~3).Other steps and one to five phase of specific embodiment
Together.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: in step 1 most
The aqueous solution B to pH that alkali is added in backward homogeneous material is 12.Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: in step 2
Under conditions of mixing speed is 300r/min and reaction temperature is 60 DEG C~90 DEG C, 4h~10h is reacted.Other steps and specific reality
It is identical to apply mode one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: in step 2
Under conditions of mixing speed is 300r/min and reaction temperature is 60 DEG C, 4h is reacted.Other steps and specific embodiment one to
Eight is identical.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: institute in step 3
The water-based emulsion stated is acrylic emulsion or aqueous polyurethane emulsion.Other steps and one to nine phase of specific embodiment
Together.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one:
It is a kind of to prepare what the method without aldehyde lignin-base based Wood Adhesives was specifically realized by the following steps using lignin:
One, lignin-alkali-glyoxal mixed aqueous solution is configured:
Under conditions of low whipping speed is 500r/min, lignin is added in the water solution A of alkali, mixture is obtained,
Glyoxal water solution is added into mixture, obtains homogeneous material, the aqueous solution B to pH that alkali is finally added into homogeneous material is
12, obtain lignin-alkali-glyoxal mixed aqueous solution；
The mass ratio of the water solution A of the lignin and alkali is 1:1；The matter of the lignin and glyoxal water solution
Amount is than being 1:3；
The water solution A of the alkali is the sodium hydrate aqueous solution that mass percent is 30%；The aqueous solution B of the alkali
The sodium hydrate aqueous solution for being 30% for mass percent；
The mass percent of glyoxal is 40% in the glyoxal water solution；
The lignin is that cornstalk biological refines lignin, i.e. Spruce lignin；
Two, the hydroxylating of lignin:
Lignin-alkali-glyoxal mixed aqueous solution is placed in three mouthfuls of glass reaction kettles with agitating paddle and condenser pipe
In, under conditions of low whipping speed is 300r/min and reaction temperature is 60 DEG C, 4h is reacted, is cooled to room temperature, obtains after reaction
Modified lignin liquor；
Three, the preparation of adhesive:
Under agitation, epoxychloropropane and water-based emulsion are added into modified lignin liquor, is uniformly mixed,
Be utilized lignin preparation without aldehyde lignin-base based Wood Adhesives；
The mass ratio of the modified lignin liquor and epoxychloropropane is 100:15；The modified wood
The mass ratio of quality solution and water-based emulsion is 100:15；The water-based emulsion is acrylic emulsion.
Embodiment two: the present embodiment is with one difference of embodiment: water-based emulsion described in step 3 is aqueous poly- ammonia
Ester lotion.Other steps are the same as example 1.
Embodiment three: the present embodiment is with one difference of embodiment: modified lignin liquor described in step 3
Mass ratio with epoxychloropropane is 100:20.Other steps are the same as example 1.
Example IV: the present embodiment is with one difference of embodiment: modified lignin liquor described in step 3
Mass ratio with epoxychloropropane is 100:20；Water-based emulsion described in step 3 is aqueous polyurethane emulsion.Other steps
It is the same as example 1.
Comparative experiments one:
One, lignin-alkali mixed liquor preparation:
Under conditions of low whipping speed is 500r/min, lignin is added in the water solution A of alkali, uniform object is obtained
Material, the aqueous solution B to pH that alkali is then added into homogeneous material is 12, obtains lignin-alkali mixed aqueous solution；
The mass ratio of the water solution A of the lignin and alkali is 1:0.8；
The water solution A of the alkali is the sodium hydrate aqueous solution that mass percent is 30%；The aqueous solution B of the alkali
The sodium hydrate aqueous solution for being 30% for mass percent；
Two, the preparation of adhesive:
Under agitation, epoxychloropropane is added into lignin-alkali mixed liquor, is uniformly mixed, is utilized wooden
Element preparation without aldehyde lignin-base based Wood Adhesives；The mass ratio of the lignin-alkali mixed liquor and epoxychloropropane is
100:30。
Comparative experiments two: this comparative experiments is with one difference of embodiment: under agitation, to modified lignin
Epoxychloropropane is added in solution, be uniformly mixed, be utilized lignin preparation without aldehyde lignin-base based Wood Adhesives；It is described
Modified lignin liquor and epoxychloropropane mass ratio be 100:30.Other steps are the same as example 1.
Under agitation, to pour into 500mL dense for the modified lignin liquor prepared by one step 2 of 100mL embodiment
It spends in the diluted hydrochloric acid aqueous solution for 1mol/L, lignin precipitation, modification is arrived into the lignin suction filtration of precipitation, washing, drying
Spruce lignin solid powder.By unmodified Spruce lignin and modified Spruce lignin solid powder
End carries out acetylation titration test, Fourier transform infrared spectroscopy test and DSC test simultaneously.
Unmodified Spruce lignin and modified Spruce lignin solid powder are subjected to acetylation simultaneously
Titration test, the variation of total hydroxy radical content in lignin molecule in modifying process can be obtained by this method.Unmodified jade
Total hydroxy radical content is 10.45% in rice straw lignin, and total hydroxy radical content is in modified Spruce lignin solid powder
23.86%, total hydroxy radical content is obviously improved in modified lignin, one times has been increased about, so that the reaction of lignin
Increased activity.
Fig. 1 is Fourier transform infrared spectroscopy figure, and a is unmodified Spruce lignin, and b is modified corn stover
Lignin solid powder.Choose 1510cm-1The phenyl ring absorption peak at place calculates separately 3430cm as internal standard peak-1Place and 1212cm-1Locate alcoholic extract hydroxyl group characteristic absorption peak and 1364cm-1And 1328cm-1Locate the peak area ratio of phenolic hydroxyl group characteristic absorption peak and internal standard peak
Value is counted in table 1.
1 different characteristic absorption peak of table and phenyl ring characteristic absorption peak area ratio
By ftir analysis it is found that compared with unmodified Spruce lignin, modified corn
Straw lignin solid powder does not form new functional group, but apparent change but has occurred in the content of certain functional groups
Change.3430cm-1Place is the characteristic absorption peak of hydroxyl；2935cm-1And 2848cm-1Place is the feature of methyl, methylene and methoxyl group
Absorption peak；1717cm-1Place is the characteristic absorption peak of carbonyl, aldehyde radical；1510cm-1Place is the characteristic absorption peak of phenyl ring；1364cm-1
And 1328cm-1Place is the characteristic absorption peak of phenolic hydroxyl group；1212cm-1Place is alcoholic extract hydroxyl group second feature absorption peak.Modified corn stalk
Stalk lignin solid powder hydroxyl characteristic absorption peak and alcoholic extract hydroxyl group second feature absorption peak have apparent enhancing, show through second two
The hydroxylating of aldehyde and lignin successfully introduces alcoholic extract hydroxyl group in lignin molecule, but is modified to phenolic hydroxyl group not
It is apparent to influence.Hydroxy radical content corresponds to peak area hydroxy radical content (3430cm in lignin-1、1212cm-1And 1328cm-1、
1364cm-1Locate summation) increase to modified 7.78 by 5.78 before modified, activation effect is obvious.Its result and acetyl
It is consistent to change total hydroxy radical content variation tendency that titration obtains.
Isocyanate group is a kind of active group, and energy and the substance containing active hydroxyl groups react.1g is unmodified
Spruce lignin and 0.3g poly methylene poly phenyl poly isocyanate (PAPI) mixing, sample carries out DSC as a comparative reference
1g modified Spruce lignin solid powder and 0.3g PAPI are mixed and carry out DSC test by test, two kinds of sample DSC spectrums
Figure is as shown in Figure 2.
Fig. 2 is DSC spectrogram, and 1 mixes for unmodified Spruce lignin with poly methylene poly phenyl poly isocyanate,
2 mix for modified Spruce lignin solid powder with poly methylene poly phenyl poly isocyanate；By DSC spectrogram it is found that
There is not particularly apparent reaction in unmodified Spruce lignin and poly methylene poly phenyl poly isocyanate (PAPI)
Peak, only at 90 DEG C there are a lesser peak, and wider distribution.And modified Spruce lignin solid powder and PAPI exists
75 DEG C or so there is an apparent reaction peak.On the one hand a certain amount of due to being introduced on lignin molecule during the reaction
Hydroxyl causes total hydroxy radical content in molecule to increase, reactivity enhancing.On the other hand, the lignin itself under the conditions of alkaline modification
Macromolecular effect is destroyed, and internal activity hydroxy is exposed, so that hydroxyl and isocyanate group are more easier to contact, therefore
The enhancing at reaction peak is caused, and mobile gently towards low temperature direction.DSC test shows that modification can significantly improve corn stover
The reactivity of lignin.
Contain active ring oxygroup in epoxychloropropane, can react under alkaline condition with lignin.1g is unmodified
Spruce lignin and 0.3g epoxychloropropane (ECH) mixing, sample carries out DSC test as a comparative reference, and 1g is modified
Spruce lignin solid powder and 0.3g ECH mixing carry out DSC test, two kinds of sample DSC spectrograms are as shown in Figure 3.
Fig. 3 is DSC spectrogram, and 1 mixes for unmodified Spruce lignin with epoxychloropropane, and 2 be modified corn
Straw lignin solid powder is mixed with epoxychloropropane.By DSC spectrogram it is found that unmodified lignin and epoxychloropropane
(ECH) occur multiple lesser reaction peaks between 65~95 DEG C, and there are one in this temperature range by modified lignin resin and ECH
A apparent response feature peak, and it is stronger, show that modified lignin and ECH reactivity enhance.In unmodified lignin and ECH
There are an endothermic peaks at 114 DEG C in spectrogram, probably due in system caused by the unreacted ECH of residual fraction.And innovation wood
Quality and ECH no apparent thermal change after 100 DEG C, show that most ECH are reacted with lignin completion.
By embodiment one, two, three, four, comparative experiments one and two using lignin preparation without aldehyde lignin-base timber
Adhesive is used to prepare three layers of glued board: choosing birch veneer is that dash board single side is applied core plate double spread by core plate and dash board
Glue, then overlapping forms three ply board base, by three ply board base hot pressing, heat pressing process are as follows: hot pressing temperature is 120 DEG C, and hot pressing pressure is
5.0MPa, hot pressing time 8min, resin added 0.04g/cm2~0.05g/cm2；The birch veneer having a size of 400mm ×
400mm × 1.5mm, moisture content 8%~12%.And name embodiment one using lignin preparation without aldehyde lignin-base timber
It is three layers of glued board a that adhesive, which prepares three layers of glued board, embodiment two using lignin preparation without aldehyde lignin-base timber
It is three layers of glued board b that adhesive, which prepares three layers of glued board, embodiment three using lignin preparation without aldehyde lignin-base timber
It is three layers of glued board c that adhesive, which prepares three layers of glued board, example IV using lignin preparation without aldehyde lignin-base timber
It is three layers of glued board d that adhesive, which prepares three layers of glued board, comparative experiments one using lignin preparation without aldehyde lignin sill
It is three layers of glued board e that material adhesive, which prepares three layers of glued board, comparative experiments two using lignin preparation without aldehyde lignin-base
It is three layers of glued board f that based Wood Adhesives, which prepare three layers of glued board,.
Three layers of glued board a, three layers of glued board b, three layers of glued board c, three layers of glued board d, three layers of glued board e and three layers of gluing
The mechanical experimental results of plate f are as shown in table 2.
2 mechanical experimental results of table
Note: wet strength 1 be test specimen temperature be 20 DEG C of ± 3 DEG C of cold water soaks for 24 hours after, the bonding strength that is measured under hygrometric state
(evaluation criterion of national Group III glued board)；Wet strength 2 is test specimen after temperature is 63 DEG C of ± 3 DEG C of Hot water immersion 3h, cooling,
The bonding strength (evaluation criterion of national II class glued board) measured under hygrometric state.
As known from Table 2, the test result of three layers of glued board e and three layers of glued board f can be seen that in Spruce lignin
Epoxychloropropane is only added on the basis of mixed liquor as curing agent can successfully realize the crosslinking curing of lignin to reach
The purpose of based Wood Adhesives is prepared, but the dry glue-joint strength of prepared glued board is slightly lower, it is to be improved.Meanwhile by the two
Test result comparison is the dry strength of prepared glued board, wet strong it is found that modified Spruce lignin activity is remarkably reinforced
Degree is obviously improved.By three layers of glued board a, three layers of glued board b, three layers of glued board c, three layers of glued board d and three layers of gluing
Plate f is compared it is found that adding a certain amount of acrylic emulsion and aqueous polyurethane emulsion on the basis of lignin adhesive
Equal water-based emulsions can be obviously improved the mechanical property of glued board, while reduce the curing agent such as epoxychloropropane to a certain extent
Dosage.Water-based emulsion can inherently play the role of splicing timber as a kind of adhesive, increase intensity, secondly, in hot pressing
Complicated physical-chemical reaction has occurred in system between various ingredients in the process, such as the active function groups in lotion can be with
Active group in lignin and curing agent reacts to each other to form cross-linked structure, to reach the work for promoting glue-joint strength
With.Prepared three layers of glued board f, three layers of glued board c and three layers of glued board d can reach II class in National Standards for Plywood requirement
The performance requirement (2 >=1.0MPa of wet strength) of plate.
Claims (8)
1. a kind of prepare the method without aldehyde lignin-base based Wood Adhesives using lignin, it is characterised in that a kind of to utilize lignin
Method of the preparation without aldehyde lignin-base based Wood Adhesives is specifically realized by the following steps:
One, lignin-alkali-glyoxal mixed aqueous solution is configured:
Under conditions of low whipping speed is 400r/min~600r/min, lignin is added in the water solution A of alkali, is mixed
Object is closed, glyoxal water solution is added into mixture, obtains homogeneous material, the aqueous solution B of alkali is finally added into homogeneous material
It is 10~13 to pH, obtains lignin-alkali-glyoxal mixed aqueous solution；
The mass ratio of the water solution A of the lignin and alkali is 1:(0.75~1.5)；The lignin and glyoxal are water-soluble
The mass ratio of liquid is 1:(3~4)；
The mass percent of alkali is 20%~40% in the water solution A of the alkali；Alkali in the water solution A of the alkali is hydrogen
The mixture of one or both of sodium oxide molybdena and potassium hydroxide；The aqueous solution B of the alkali and the water solution A of alkali are isoplassont
Matter；
The mass percent of glyoxal is 40%~50% in the glyoxal water solution；
The lignin is that cornstalk biological refines lignin；
Two, the hydroxylating of lignin:
Lignin-alkali-glyoxal mixed aqueous solution is placed in three mouthfuls of glass reaction kettles with agitating paddle and condenser pipe,
Under conditions of mixing speed is 200r/min~400r/min and reaction temperature is 40 DEG C~60 DEG C, 2h~10h is reacted, after reaction
It is cooled to room temperature, obtains modified lignin liquor；
Three, the preparation of adhesive:
Under agitation, epoxychloropropane and water-based emulsion are added into modified lignin liquor, is uniformly mixed, obtains
Using lignin preparation without aldehyde lignin-base based Wood Adhesives；
The mass ratio of the modified lignin liquor and epoxychloropropane is 1:(0.15~0.4)；Described is modified
Lignin liquor and water-based emulsion mass ratio be 1:(0.1~0.3).
2. it is according to claim 1 a kind of using method of the lignin preparation without aldehyde lignin-base based Wood Adhesives, it is special
Sign is that the mass ratio of the water solution A of lignin and alkali described in step 1 is 1:1.
3. it is according to claim 1 a kind of using method of the lignin preparation without aldehyde lignin-base based Wood Adhesives, it is special
Sign is that the mass percent of alkali in the water solution A of alkali described in step 1 is 30%.
4. it is according to claim 1 a kind of using method of the lignin preparation without aldehyde lignin-base based Wood Adhesives, it is special
Sign is that the mass percent of glyoxal in glyoxal water solution described in step 1 is 40%.
5. it is according to claim 1 a kind of using method of the lignin preparation without aldehyde lignin-base based Wood Adhesives, it is special
Sign is that the mass ratio of lignin and glyoxal water solution described in step 1 is 1:3.
6. it is according to claim 1 a kind of using method of the lignin preparation without aldehyde lignin-base based Wood Adhesives, it is special
The aqueous solution B to pH that sign is that alkali is finally added in step 1 into homogeneous material is 12.
7. it is according to claim 1 a kind of using method of the lignin preparation without aldehyde lignin-base based Wood Adhesives, it is special
Under conditions of sign is in step 2 that low whipping speed is 300r/min and reaction temperature is 60 DEG C, 4h is reacted.
8. it is according to claim 1 a kind of using method of the lignin preparation without aldehyde lignin-base based Wood Adhesives, it is special
Sign is that water-based emulsion described in step 3 is acrylic emulsion or aqueous polyurethane emulsion.
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| EP4093832A4 (en) * | 2020-01-23 | 2024-01-24 | Univ Michigan State | Lignin-based phenolic adhesives, related compositions, and related methods |
| CN111635732A (en) * | 2020-06-20 | 2020-09-08 | 师宗腾信木业有限责任公司 | Glue for high-weather-resistance plywood and processing technology thereof |
| CN113444479B (en) * | 2021-05-13 | 2023-03-21 | 广西大学 | Preparation method of lignin-based formaldehyde-free adhesive |
| CN115466585B (en) * | 2021-12-25 | 2023-11-10 | 闽南师范大学 | Lignin-based waterborne polyurethane-acrylate wood adhesive and preparation method thereof |
| CN114536487B (en) * | 2022-02-22 | 2022-10-21 | 陕西科技大学 | Method for glueless gluing of plates |
| CN115449329A (en) * | 2022-09-22 | 2022-12-09 | 广西科学院 | Method for modifying adhesive by lignin |
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| CN102061141A (en) * | 2009-11-11 | 2011-05-18 | 青岛生物能源与过程研究所 | Method for preparing environmentally-friendly adhesive for lignin-based timber |
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| CN103031108A (en) * | 2011-10-08 | 2013-04-10 | 中国科学院青岛生物能源与过程研究所 | Method for preparing lignin-based adhesive |
| US8674019B2 (en) * | 2012-04-27 | 2014-03-18 | Georgia-Pacific Chemicals Llc | Composite products made with lewis acid catalyzed binder compositions that include tannins and multifunctional aldehydes |
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| CN102061141A (en) * | 2009-11-11 | 2011-05-18 | 青岛生物能源与过程研究所 | Method for preparing environmentally-friendly adhesive for lignin-based timber |
| CN102199268A (en) * | 2011-04-08 | 2011-09-28 | 华南理工大学 | Laccase activated and modified sulfonated soda lignin amphiphilic polymer and preparation method and application thereof |
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