CN107841270A - The preparation method of lignin phenol formaldehyde resin adhesive - Google Patents
The preparation method of lignin phenol formaldehyde resin adhesive Download PDFInfo
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- CN107841270A CN107841270A CN201711212549.7A CN201711212549A CN107841270A CN 107841270 A CN107841270 A CN 107841270A CN 201711212549 A CN201711212549 A CN 201711212549A CN 107841270 A CN107841270 A CN 107841270A
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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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
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
Abstract
The present invention provides a kind of preparation method of lignin phenol formaldehyde resin adhesive, by preparing activation lignin and phenol reactant part fortified phenol with microbial fermentation, using hyper-branched polyester as medium, load negative ion powder using porous material silica flour and be prepared with lignin fortified phenol and formaldehyde reaction；Phenolic resin adhesive abrasion resistance prepared by the present invention is high, and curing rate is fast, and bonding strength is high, the burst size of harmful substance formaldehyde is few simultaneously, with air contact energy releasing negative oxygen ion, has good air-filtering ability, belong to environment-friendly type macromolecule material, possess outstanding development potentiality.
Description
Technical field
The invention belongs to chemical field of polymer material preparing technology, more particularly to a kind of lignin phenol formaldehyde resin adhesive
Preparation method.
Background technology
In modern industrial production, phenol is the larger stone of the non-renewable toxicity largely used in phenolic resin building-up process
Change raw material.Therefore, the industrial chemicals for seeking a kind of alternative phenol of environment-friendly type is the focus that scholars study.Lignin is nature
The second largest renewable resource of cellulose is only second in boundary, while is also the maximum aromatic compound of natural yield.Lignin
It is using phenyl-propane as construction unit, passes through the highly cross-linked tridimensional network natural aromatic chemical combination of carbon-carbon bond and ehter bond
Thing.Due to having alcoholic extract hydroxyl group and phenolic hydroxyl group isoreactivity functional group on molecule, similar to phenolic resin structure, lignin can be replaced partly
Substituting phenol prepares modified phenol formaldehyde resin adhesive with pulping waste liquor and sticks agent, can both reduce cost, reach the purpose that biomass resource efficiently utilizes,
And the poisonous remnants such as the glutinous agent free phenol of modified phenol formaldehyde resin adhesive with pulping waste liquor prepared are relatively low, have environment protection significance.
Patent of invention CN201310246863.2, organic method lignin prepare the side of synvaren instead of phenol
Method, mainly solve in existing synvaren preparation process largely using the larger petrochemical material of non-renewable toxicity
Technical problem, preparation of the phenol for synvaren is substituted using organic method lignin, greatly reduces phenolic resin
The usage amount of the larger petrochemical material-phenol of non-renewable toxicity, not only makes production phenolic resin cost significantly in building-up process
Reduce, the performance of phenolic resin can also be improved by the use of organic method lignin, acquisition bonding strength is higher, formaldehyde is released
Put synvaren lower, that performance is more stable.
Patent of invention CN201410018573.7, a kind of preparation method of lignin-base Environmental protection phenol formaldehyde resin adhesive, bag
Include：Step 1, compose nuclear magnetic resonance technique using quantitative phosphorus and quantitative analysis carried out to the hydroxyl of lignin raw material, by phenolic hydroxyl group and
The active sites points when being reacted with formaldehyde in unit mass lignin raw material are calculated in alcoholic extract hydroxyl group number；Step 2, mixing wood
Quality raw material and phenol, form raw mixture, make the amount of substance of lignin raw material and phenol ratio 1 during mixing:9~8:2；Step
Rapid 3, calculate formaldehyde total amount；Step 4, the raw mixture obtained in step 2 and formaldehyde, aqueous slkali hybrid reaction, are prepared wooden
Plain basic ring protects phenolic resin adhesive.The present invention is solving conventional wooden element base phenolic resin adhesive product costliness and formaldehyde dirt
Biomass refining accessory substance lignin has been obtained higher value application on the basis of dye problem, there is greatly economic and society's meaning
Justice.
Patent of invention CN201510352326.5, one kind prepare lignin phenolic resin using microwave-CuO processing papermaking wastewaters
The method of adhesive, with being filtered after microwave and CuO processing papermaking wastewaters, with salt acid for adjusting pH=2 ~ 3 or so, baking oven is placed in setting
Determine to stand a period of time at temperature, filter, washed to neutrality while hot, it is dry that lignin by acid separation is standby；Take dried wood
Quality part substitutes phenol, and by phenolate, methylolation and phenol aldehyde reaction prepare lignin-phenolic resin adhesive；The hair
The bright substitution rate for improving lignin Pyrogentisinic Acid, reduces cost, reduces the pollution to environment, and the bonding strength of adhesive
Greatly, free formaldehyde content is low, and properties meet national standard.
The shortcomings of wear-resisting low, cost is high, solidification temperature is high and hot pressing time is long, the opposing party be present in phenolic resin adhesive
Face, preparing raw material is non-renewable fossil energy product, and without the feature of environmental protection, the presence of formaldehyde is even more to cause the peace of phenolic resin
Full property is low.
The content of the invention
The deficiency existing for the phenolic resin adhesive for preparing in the prior art, the present invention provide a kind of Lignin phenolic
The preparation method of Resin adhesive.
The present invention is achieved by the following technical solutions：
A kind of preparation method of lignin phenol formaldehyde resin adhesive, is prepared by following steps：
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 60 ~ 70%, add reed slag
The Tween-80 of amount 0.05 ~ 0.15%, packed after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 2 ~ 3 days,
Cultivation matrix is obtained, then in being inoculated with phoenix tail mushroom on cultivation matrix, is persistently cultivated 12 ~ 16 days, cultivation temperature is maintained at 37 ~ 45
℃；
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3 ~ 3.5, under normal temperature
45 ~ 60min is reacted, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）40 ~ 50 parts of water, 0.5 ~ 0.7 part of dispersant, 5040,0.2 ~ 0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, first
It is scattered to stir and evenly mix, add powder quartz ore and ball milling is carried out into porcelain mill, control the solid-to-liquid ratio to be（2~5）:1, choose ball
Expect that ratio is（3~5）:1 Ceramic Balls, sequentially add 0.3% dispersant and 0.1% defoamer, and rotating speed is 70 revs/min, ball milling
Time is 3.0 ~ 4.0h, prepares konilite slurry, then adds hydroxyethyl cellulose, prevents the sedimentation of konilite slurry, obtains
The konilite slurry arrived；
（2）40 ~ 50 parts of water, 5 ~ 10 parts of hydroxy ethyl fiber solution mixing are taken by ratio of weight and the number of copies, by negative ion powder according to solid-to-liquid ratio
For 1:1 ratio adds, and is then transferred to vertical mixing mill, ratio of grinding media to material is（3~5）:1 Ceramic Balls, sequentially add 0.3% it is scattered
The defoamer A10 of agent 5040 and 0.1%, 1 ~ 2h of ball milling, obtain anion agent slurry；
（3）It is according to mass ratio by konilite slurry and anion slurry（12~25）:1 mixing, is added to sand mill, ratio of grinding media to material
For（3~5）：1 zirconium ball 30 ~ 60min of wet grinding, is fitted into centrifuge tube, is washed with deionized 3 ~ 4 times, is air-dried under normal temperature,
Obtain quartz-anion composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 20 ~ 30 parts of propane, constant temperature melts in 210 DEG C of oil baths
Melt, trimesic acid is added, with 0.1 ~ 0.5 part of stannous octoate；After 3.0 ~ 5.0h of heating stirring, vacuumize and keep strong stirring
1.0 ~ 2.0h is reacted, reaction is poured into methanol and precipitated, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol while hot after terminating,
40 ~ 60h is dried at 100 DEG C, obtains hyper-branched polyester solid；
4th, lignin phenol formaldehyde resin adhesive is prepared
By ratio of weight and the number of copies, 20 ~ 30 parts of lignin of activation is taken, quartz -24 ~ 40 parts of anion composite granule, hyper-branched polyester is solid
1 ~ 5 part of body, 15 ~ 20 parts of phenol, 1 ~ 5 part of sodium hydroxide, 20 ~ 25 parts of formaldehyde, 20 ~ 50 parts of water, it is well mixed and adds in reactor,
80 ~ 100 DEG C are warming up to, 1 ~ 2h of isothermal reaction can obtain lignin phenol formaldehyde resin adhesive.
Pseudomonas aeruginosa and phoenix-tail mushroom solid state fermentation reed slag, it can effectively decompose cellulose in reed slag and wooden
Element；Rhamnolipid caused by pseudomonas aeruginosa fermentation can promote decomposition of the phoenix-tail mushroom secretion laccase to reed slag lignin, living
Change and improve methylol, phenolic hydroxyl group, alcoholic extract hydroxyl group content on lignin molecule, so as to improve lignin and the phenolic resin degree of polymerization.
Quartzy main component is silica, has porous performance, can load more negative oxygen ions, adsorbs free formaldehyde
And phenol, while negative ion powder contacts with moisture in air or oxygen, releasing negative oxygen ion after ionizing, and improves air matter
Amount；The many combination hyper-branched polyesters of quartzy loose structure energy, further improve the degree of polymerization of phenolic resin adhesive.Bear from
Sub- addition be 4 ~ 8% between when, purifying formaldehyde rate changes small, but anion between 91 ~ 94%, more than 8% after-purification rate
The Percentage bound of powder and silica flour reduces with the increase of negative ion powder addition, therefore is best with 4 ~ 8%.
Hyper-branched polyester has highly branched molecular structure, and radical species are more, and solubility high viscosity is low, can effectively carry
The polymerization speed of high phenolic resin, improve the intensity of resin glue；The characteristics of its radical species is more simultaneously, can more it combine free
Phenol and formaldehyde, reduce the release of phenol and formaldehyde so as to improve Environmental security；On the other hand, phenolic resin is due to lignin
With the addition of silica flour complex, gel-forming property is influenceed, this influence can be eliminated using hyper-branched polyester.
As a further improvement on the present invention, step 1（1）Described pseudomonas aeruginosa fills liquid prior to activation medium
Measure in the conical flask for 20%, inoculum concentration 5%, 37 DEG C, 12 ~ 16h of activation culture under 200rpm.
As a further improvement on the present invention, the activation medium is prepared by following density component material：Vegetable seed
Oily 30g/L, Dried Corn Steep Liquor Powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L,
CaCl20.05g/L, NaCl 1.5g/L, adjust pH to 6.5 ~ 7.0.
In best medium, the rhamnolipid average product that pseudomonas aeruginosa ferments to obtain is 30.41 ~ 34.52g/L.
As a further improvement on the present invention, step 2（1）Described powder quartz ore fineness is 200 ~ 300 mesh.
The granule size of konilite determines its dispersive property and absorption property, and granularity is smaller to disperse better but adsorption capacity
It is low, therefore in order to preferably disperse to adsorb negative ion powder simultaneously, the silica flour using 200 ~ 300 mesh is best.
As a further improvement on the present invention, the double [4- of 2,2- described in step 3（2- hydroxy ethoxies）Phenyl] propane with
The mol ratio of benzenetricarboxylic acid is（2~4）:1.
The mol ratio of two kinds of monomers influences hyper-branched polyester molecular weight and the dissaving polymer of terminal groups, and 2,2- is double
[4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:Terminal groups dispersiveness big poly- can be obtained when 1
Ester, there are more binding sites（Group）, so as to promote the intensity of resin reaction polymerization speed and resin, anti-wear performance.
As a further improvement on the present invention, the quartz described in step 4-anion composite granule is consolidated with hyper-branched polyester
Body amount ratio is（8~15）：1.
The content of hyper-branched polyester influences resin integrally curing conversion ratio, and content high resin solidification conversion ratio is low, and content is low
Resin bonding strength and anti-wear performance are low, when hyperbranched poly ester content is 5 ~ 15%, the solidification conversion ratio of phenolic resin for 95 ~
98%, anti-wear performance and bond strength rate of change are small, overall resin property are influenceed little.
Beneficial effects of the present invention：
1st, preparation technology of the present invention requires low, it is not necessary to high capital equipment and raw material, has good economic benefit；
2nd, the phenolic resin adhesive that the present invention is prepared into is safe and reliable, and burst size of methanal is low, while can also discharge beneficial bear
Oxonium ion, environmental pollution is low, meets demand of the people to environment-friendly materials；
3rd, phenolic resin adhesive abrasion resistance prepared by the present invention is high, and curing rate is fast, and required hot pressing temperature is low, glued strong
Degree is high, has excellent water-fast weather-resistant property.
Embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 60%, add reed slag quality
0.05% Tween-80, pack after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 2 days, cultivated
Matrix, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 12 days, cultivation temperature is maintained at 37 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 12h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 6.5；
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, it is 3 to add acetic acid to pH, is reacted under normal temperature
45min, solid residue is then filtered to remove, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）40 parts of water, 0.5 part of dispersant, 5040,0.2 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 200 mesh and ball milling is carried out into porcelain mill, it is 2 to control solid-to-liquid ratio:1, choose ball material
Than for 3:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
3.0h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）40 parts of water, the mixing of 5 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio adds, and is then transferred to vertical mixing mill, ratio of grinding media to material 3:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 1h, obtain anion agent slurry；
（3）According to mass ratio it is 12 by konilite slurry and anion slurry：1 mixing, is added to sand mill, ratio of grinding media to material 3：1
Zirconium ball wet grinding 30min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 20 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.1
Part stannous octoate；After heating stirring 3.0h, vacuumize and keep strong stirring to react 1.0h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 40h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin adhesive is prepared
By ratio of weight and the number of copies, take and activate 20 parts of lignin, quartz -24 parts of anion composite granule, 3 parts of hyper-branched polyester solid,
15 parts of phenol, 1 part of sodium hydroxide, 20 parts of formaldehyde, 20 parts of water, it is well mixed and adds in reactor, be warming up to 80 DEG C, isothermal reaction
1h can obtain lignin phenol formaldehyde resin adhesive；
Embodiment 2
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 70%, add reed slag quality
0.15% Tween-80, pack after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 3 days, cultivated
Matrix, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 16 days, cultivation temperature is maintained at 45 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 16h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 7.0
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3.5, anti-under normal temperature
60min is answered, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）50 parts of water, 0.7 part of dispersant, 5040,0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 300 mesh and ball milling is carried out into porcelain mill, it is 5 to control solid-to-liquid ratio:1, choose ball material
Than for 5:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
4.0h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）50 parts of water, the mixing of 10 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio add, be then transferred to vertical mixing mill, ratio of grinding media to material 5:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 2h, obtain anion agent slurry；
（3）According to mass ratio it is 25 by konilite slurry and anion slurry:1 mixing, is added to sand mill, ratio of grinding media to material 5：1
Zirconium ball wet grinding 60min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 30 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.5
Part stannous octoate；After heating stirring 5.0h, vacuumize and keep strong stirring to react 2.0h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 60h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin adhesive is prepared
By ratio of weight and the number of copies, take and activate 30 parts of lignin, quartz -30 parts of anion composite granule, 2 parts of hyper-branched polyester solid,
20 parts of phenol, 5 parts of sodium hydroxide, 25 parts of formaldehyde, 50 parts of water, it is well mixed and adds in reactor, be warming up to 100 DEG C, constant temperature is anti-
2h is answered to can obtain lignin phenol formaldehyde resin adhesive.
Embodiment 3
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 65%, add reed slag quality
0.1% Tween-80, packed after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 3 days, obtain cultivation base
Matter, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 14 days, cultivation temperature is maintained at 40 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 14h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 6.5 ~ 7.0
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3.3, anti-under normal temperature
50min is answered, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）45 parts of water, 0.6 part of dispersant, 5040,0.25 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 220 mesh and ball milling is carried out into porcelain mill, it is 3 to control solid-to-liquid ratio:1, choose ball material
Than for 4:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
3.5h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）45 parts of water, the mixing of 8 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio adds, and is then transferred to vertical mixing mill, ratio of grinding media to material 4:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 1.5h, obtain anion agent slurry；
（3）According to mass ratio it is 20 by konilite slurry and anion slurry:1 mixing, is added to sand mill, ratio of grinding media to material 4：1
Zirconium ball wet grinding 50min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 25 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.4
Part stannous octoate；After heating stirring 4.0h, vacuumize and keep strong stirring to react 1.5h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 50h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin adhesive is prepared
By ratio of weight and the number of copies, take and activate 25 parts of lignin, quartz -40 parts of anion composite granule, 5 parts of hyper-branched polyester solid,
17 parts of phenol, 5 parts of sodium hydroxide, 23 parts of formaldehyde, 45 parts of water, it is well mixed and adds in reactor, be warming up to 90 DEG C, isothermal reaction
1.5h can obtain lignin phenol formaldehyde resin adhesive.
Embodiment 4
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 62%, add reed slag quality
0.15% Tween-80, pack after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 2 days, cultivated
Matrix, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 16 days, cultivation temperature is maintained at 40 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 12h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 6.5 ~ 7.0
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3.3, anti-under normal temperature
50min is answered, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）42 parts of water, 0.5 part of dispersant, 5040,0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 220 mesh and ball milling is carried out into porcelain mill, it is 2 to control solid-to-liquid ratio:1, choose ball material
Than for 5:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
3.0h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）40 parts of water, the mixing of 10 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio add, be then transferred to vertical mixing mill, ratio of grinding media to material 5:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 2.0h, obtain anion agent slurry；
（3）According to mass ratio it is 15 by konilite slurry and anion slurry:1 mixing, is added to sand mill, ratio of grinding media to material 5：1
Zirconium ball wet grinding 60min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 25 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.4
Part stannous octoate；After heating stirring 5.0h, vacuumize and keep strong stirring to react 1.0h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 40h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin adhesive is prepared
By ratio of weight and the number of copies, take and activate 30 parts of lignin, quartz -40 parts of anion composite granule, 4 parts of hyper-branched polyester solid,
20 parts of phenol, 6 parts of sodium hydroxide, 25 parts of formaldehyde, 30 parts of water, it is well mixed and adds in reactor, be warming up to 90 DEG C, isothermal reaction
1.5h can obtain lignin phenol formaldehyde resin adhesive.
Embodiment 5
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 65%, add reed slag quality
0.15% Tween-80, pack after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 3 days, cultivated
Matrix, then in being inoculated with phoenix tail mushroom on cultivation matrix, persistently cultivate 16 days, cultivation temperature is maintained at 40 DEG C；
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C,
Activation culture 12h under 200rpm；The activation medium is prepared by following density component material：Rapeseed oil 30g/L, corn
Paste dry powder 6g/L, NaNO36g/L, K2HPO40.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L,
NaCl 1.5g/L, adjust pH to 6.5；
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3.5, anti-under normal temperature
60min is answered, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）45 parts of water, 0.7 part of dispersant, 5040,0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, it is mixed first to disperse stirring
It is even, add the powder quartz ore that fineness is 300 mesh and ball milling is carried out into porcelain mill, it is 4 to control solid-to-liquid ratio:1, choose ball material
Than for 4:1 Ceramic Balls, 0.3% dispersant and 0.1% defoamer are sequentially added, rotating speed is 70 revs/min, Ball-milling Time is
4.0h, konilite slurry is prepared, then adds hydroxyethyl cellulose, prevent the sedimentation of konilite slurry, obtained konilite
Slurry；
（2）45 parts of water, the mixing of 10 parts of hydroxy ethyl fiber solution are taken by ratio of weight and the number of copies, according to solid-to-liquid ratio are 1 by negative ion powder:1
Ratio add, be then transferred to vertical mixing mill, ratio of grinding media to material 5:1 Ceramic Balls, sequentially add 0.3% He of dispersant 5040
0.1% defoamer A10, ball milling 2h, obtain anion agent slurry；
（3）According to mass ratio it is 15 by konilite slurry and anion slurry：1 mixing, is added to sand mill, ratio of grinding media to material 3：1
Zirconium ball wet grinding 50min, be fitted into centrifuge tube, be washed with deionized 3 ~ 4 times, under normal temperature air-dry, obtain quartz-bear from
Sub- composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 30 parts of propane, constant temperature melts in 210 DEG C of oil baths,
Add trimesic acid（2,2- double [4-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is 2:1）, with 0.5
Part stannous octoate；After heating stirring 4.0h, vacuumize and keep strong stirring to react 2.0h, reaction pours into methanol while hot after terminating
Middle precipitation, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol, 48h is dried at 100 DEG C, hyper-branched polyester is obtained and consolidates
Body；
4th, lignin phenol formaldehyde resin adhesive is prepared
By ratio of weight and the number of copies, take and activate 30 parts of lignin, quartz -30 parts of anion composite granule, 3 parts of hyper-branched polyester solid,
20 parts of phenol, 5 parts of sodium hydroxide, 25 parts of formaldehyde, 40 parts of water, it is well mixed and adds in reactor, be warming up to 80 DEG C, isothermal reaction
1h can obtain lignin phenol formaldehyde resin adhesive；
The lignin phenol formaldehyde resin adhesive performance such as table 1 being prepared by embodiment 1 ~ 5.
The embodiment phenolic resin adhesive performance of table 1
From the data in table 1, it can be seen that lignin phenol formaldehyde resin adhesive burst size of methanal produced by the present invention and free-phenol meet state
Family's standard, bonding strength meet national I class and the requirement of II class plate, there is excellent anti-wear performance, waterproof and weather-resistant property.
Above example is only the exemplary embodiment of the present invention, is not used in the limitation present invention, protection scope of the present invention
It is defined by the claims.Those skilled in the art can make various repair to the present invention in the essence and protection domain of the present invention
Change or equivalent substitution, this modification or equivalent substitution also should be regarded as being within the scope of the present invention.
Claims (6)
1. a kind of preparation method of lignin phenol formaldehyde resin adhesive, it is characterised in that be prepared by following steps：
First, activation lignin is prepared
（1）Take reed stems and leaves, be ground into reed slag, sprinkle water it is moistened to water content be 60 ~ 70%, add reed slag
The Tween-80 of amount 0.05 ~ 0.15%, packed after well mixed, after inoculation pseudomonas aeruginosa carries out sterile solid culture 2 ~ 3 days,
Cultivation matrix is obtained, then in being inoculated with phoenix tail mushroom on cultivation matrix, is persistently cultivated 12 ~ 16 days, cultivation temperature is maintained at 37 ~ 45
℃；
（2）Take culture ripe and extract the cultivation matrix after phoenix-tail mushroom, be milled to powder, addition acetic acid to pH is 3 ~ 3.5, under normal temperature
45 ~ 60min is reacted, is then filtered to remove solid residue, obtains activating lignin；
2nd, quartz-anion composite granule is prepared
（1）40 ~ 50 parts of water, 0.5 ~ 0.7 part of dispersant, 5040,0.2 ~ 0.3 parts of defoamer A10 are mixed by ratio of weight and the number of copies, first
It is scattered to stir and evenly mix, add powder quartz ore and ball milling is carried out into porcelain mill, control the solid-to-liquid ratio to be（2~5）:1, choose ball
Expect that ratio is（3~5）:1 Ceramic Balls, sequentially add 0.3% dispersant and 0.1% defoamer, and rotating speed is 70 revs/min, ball milling
Time is 3.0 ~ 4.0h, prepares konilite slurry, then adds hydroxyethyl cellulose, prevents the sedimentation of konilite slurry, obtains
The konilite slurry arrived；
（2）40 ~ 50 parts of water, 5 ~ 10 parts of hydroxy ethyl fiber solution mixing are taken by ratio of weight and the number of copies, by negative ion powder according to solid-to-liquid ratio
For 1:1 ratio adds, and is then transferred to vertical mixing mill, ratio of grinding media to material is（3~5）:1 Ceramic Balls, sequentially add 0.3% it is scattered
The defoamer A10 of agent 5040 and 0.1%, 1 ~ 2h of ball milling, obtain anion agent slurry；
（3）It is according to mass ratio by konilite slurry and anion slurry（12~25）:1 mixing, is added to sand mill, ratio of grinding media to material
For（3~5）：1 zirconium ball 30 ~ 60min of wet grinding, is fitted into centrifuge tube, is washed with deionized 3 ~ 4 times, is air-dried under normal temperature,
Obtain quartz-anion composite granule；
3rd, hyper-branched polyester is prepared
By quality parts ratio, the double [4- of 2,2- are taken（2- hydroxy ethoxies）Phenyl] 20 ~ 30 parts of propane, constant temperature melts in 210 DEG C of oil baths
Melt, trimesic acid is added, with 0.1 ~ 0.5 part of stannous octoate；After 3.0 ~ 5.0h of heating stirring, vacuumize and keep strong stirring
1.0 ~ 2.0h is reacted, reaction is poured into methanol and precipitated, tetrahydrofuran is dissolved in after filtering and is precipitated again in methanol while hot after terminating,
40 ~ 60h is dried at 100 DEG C, obtains hyper-branched polyester solid；
4th, lignin phenol formaldehyde resin adhesive is prepared
By ratio of weight and the number of copies, 20 ~ 30 parts of lignin of activation is taken, quartz -24 ~ 40 parts of anion composite granule, hyper-branched polyester is solid
1 ~ 5 part of body, 15 ~ 20 parts of phenol, 1 ~ 5 part of sodium hydroxide, 20 ~ 25 parts of formaldehyde, 20 ~ 50 parts of water, it is well mixed and adds in reactor,
80 ~ 100 DEG C are warming up to, 1 ~ 2h of isothermal reaction can obtain lignin phenol formaldehyde resin adhesive.
2. the preparation method of lignin phenol formaldehyde resin adhesive according to claim 1, it is characterised in that：Step 1（1）
In the conical flask that described pseudomonas aeruginosa is 20% prior to activation medium liquid amount, inoculum concentration 5%, 37 DEG C, 200rpm
12 ~ 16h of lower activation culture.
3. the preparation method of lignin phenol formaldehyde resin adhesive according to claim 1, it is characterised in that：Step 2（1）
Described powder quartz ore fineness is 200 ~ 300 mesh.
4. the preparation method of lignin phenol formaldehyde resin adhesive according to claim 1, it is characterised in that：Described in step 3
Double [the 4- of 2,2-（2- hydroxy ethoxies）Phenyl] mol ratio of propane and trimesic acid is（2~4）:1.
5. the preparation method of lignin phenol formaldehyde resin adhesive according to claim 1, it is characterised in that：Described in step 4
Quartz-anion composite granule be with hyper-branched polyester solid amount ratio（8~15）：1.
6. the preparation method of lignin phenol formaldehyde resin adhesive according to claim 2, it is characterised in that：The activation training
Base is supported to be prepared by following density component material：Rapeseed oil 30g/L, Dried Corn Steep Liquor Powder 6g/L, NaNO36g/L, K2HPO4
0.9g/L, NaH2PO40.6g/L, MgSO40.3g/L, CaCl20.05g/L, NaCl 1.5g/L, regulation pH to 6.5 ~ 7.0 are
Can.
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| CN201711212549.7A CN107841270B (en) | 2017-11-28 | 2017-11-28 | Preparation method of lignin phenolic resin adhesive |
| PCT/CN2018/000045 WO2019104815A1 (en) | 2017-11-28 | 2018-01-25 | Method for preparing lignin-phenol-formaldehyde resin adhesive |
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Cited By (3)
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| CN109181612A (en) * | 2018-09-14 | 2019-01-11 | 齐鲁工业大学 | A kind of water resistance biology base adhesive and preparation method thereof |
| CN111909646A (en) * | 2020-08-07 | 2020-11-10 | 湖南福湘木业有限责任公司 | Mould-proof modification method for soybean-based adhesive |
| CN114919032A (en) * | 2022-04-07 | 2022-08-19 | 江苏苏林木业有限公司 | Method for producing density board by using lignin adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112521910B (en) * | 2020-12-10 | 2022-07-12 | 合肥学院 | Preparation method of high-strength bio-based adhesive for sponge |
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