CN107502250B - Preparation method of biomass oil/glucose resin adhesive - Google Patents
Preparation method of biomass oil/glucose resin adhesive Download PDFInfo
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- CN107502250B CN107502250B CN201710908183.0A CN201710908183A CN107502250B CN 107502250 B CN107502250 B CN 107502250B CN 201710908183 A CN201710908183 A CN 201710908183A CN 107502250 B CN107502250 B CN 107502250B
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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
- C08G8/34—Chemically modified polycondensates by natural resins or resin acids, e.g. rosin
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Abstract
The invention relates to a preparation method of a biomass oil/glucose resin adhesive, belonging to the technical field of biomass oil application and adhesive preparation, and comprising the following specific steps: adding biomass oil, phenol, an alkali catalyst and water into a reaction kettle in proportion, firstly carrying out phenolization reaction, then adding formaldehyde and a cross-linking agent for hydroxymethylation reaction, and finally adding glucose for multicomponent copolymerization reaction. The invention has the advantages that the reactivity of the biomass oil is improved by the phenolization modification and the hydroxymethylation modification, so that the multicomponent copolymerization condensation reaction is realized, and the polymerization degree of the polymer is improved by adding the cross-linking agent, so that the gluing performance is improved.
Description
Technical Field
The invention belongs to the technical field of biomass oil application and adhesive preparation, and particularly relates to a preparation method of a biomass oil/glucose resin adhesive.
Background
The biomass resource is used for replacing fossil resources, and the reduction of the use amount of phenol is a development trend of the adhesive industry. The biomass oil/phenol/formaldehyde resin adhesive prepared by partially substituting phenol with the biomass oil is proved to be an excellent wood adhesive and can be widely applied to the production of plywood, laminated wood, shaving board, oriented shaving board, medium-density fiberboard and the like.
CN101974301A discloses a preparation method of a biomass oil-phenol-formaldehyde copolycondensation resin wood adhesive. The invention firstly refines and purifies the bio-oil, and then adds the sulfur, the alkali catalyst and the urea to prepare the adhesive with the substitution rate of 60-75 percent, and the bonding strength is 0.93-1.41 MPa. CN101602838A discloses a preparation method of wood pyrolysis oil modified phenolic resin for artificial boards. The method mixes, copolymerizes and condenses the biomass oil, phenol, formaldehyde, glutaraldehyde or glyoxal and compound alkali catalyst to produce adhesive with substitution rate of 40-60% and bonding strength of 0.78-1.04 MPa. CN101328396A discloses a method for preparing an adhesive with a substitution rate of 40% by adding pyrolysis oil in the middle stage and adding formaldehyde and a catalyst in batches, wherein the bonding strength of the adhesive is 0.95 MPa. CN101519572 discloses a method for preparing a phenolic resin adhesive by using biomass oil, wherein the substitution rate of the prepared biomass oil phenolic resin adhesive is 50%, and the bonding strength is 1.40 MPa.
At present, most of the published patents relate to a preparation method of a biomass oil-phenol-formaldehyde resin adhesive, and prove that copolymerization and condensation are effective methods for preparing the biomass oil adhesive, but the problems of reduced bonding strength and high formaldehyde consumption of products with high substitution rate exist.
Therefore, there is a need in the art for a new solution to solve this problem.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the biomass oil/glucose resin adhesive is provided for solving the technical problems of high biomass oil substitution rate, low adhesive bonding strength, high formaldehyde consumption and the like of the existing biomass oil adhesive.
A preparation method of biomass oil/glucose resin adhesive comprises the following steps which are carried out in sequence,
step one, phenolization modification
Respectively measuring biomass oil and phenol, wherein the mass of the biomass oil accounts for 25-75% of the total mass of the biomass oil and the phenol,
measuring an alkali catalyst which is 10-20% of the total mass of the biomass oil and the phenol, obtaining the addition amount of the alkali catalyst and water mixed by a mass concentration formula under the condition that the mass concentration of the alkali catalyst is 8-15%, and measuring,
adding the measured biomass oil, phenol, an alkali catalyst and water into a reaction kettle, heating to 60 ℃, and stirring for reaction for 1h to obtain a phenolated modified liquid;
step two: modification of hydroxymethylation
Mixing a formaldehyde solution and a cross-linking agent, dropwise adding the mixture into the phenolic modified liquid obtained in the step one, keeping the temperature of the reaction kettle at 60 ℃, and continuously stirring for 0.5-2 h to obtain hydroxymethylation modified liquid;
step three: crosslinking condensation copolymerization
And D, adding glucose into the hydroxymethylation modified liquid obtained in the step two, stirring, heating the reaction kettle to 80 ℃, continuously stirring for 3 hours, discharging the product when the viscosity of the reactant reaches 300-700 mPa.s, and obtaining the biomass oil/glucose resin adhesive.
The biomass oil is obtained by biomass pyrolysis, and the biomass is one or a mixture of more than two of rice hulls, plant straws, lignin, wood processing waste and bamboo processing waste.
The alkali catalyst in the first step is one or a mixture of more than two of sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide.
The mass concentration of the formaldehyde solution in the second step is 37 percent, and the adding amount W of the formaldehyde solutionFComprises the following steps: wF＝[WP+WBIO-OIL]/MP×1.3×MF÷37％×(1-Y)，
In the formula, WPThe charging amount of phenol in the step one, WBIO-OILThe feeding amount of the biomass oil in the step one, MPIs the molar mass of phenol, MFIs the molar mass of formaldehyde, and Y is the substitution rate of glucose for formaldehyde.
And the cross-linking agent in the second step is furfural or glyoxal.
The addition amount of the cross-linking agent is 5-30% of the total mass of the biomass oil and the phenol.
The adding amount of the glucose in the third step is 25 to 85 percent of the total mass of the glucose and the formaldehyde solution.
Through the design scheme, the invention can bring the following beneficial effects:
1. the invention prepares a novel adhesive, namely a bio-oil/glucose resin adhesive.
2. Compared with the traditional condensation reaction, the phenolization modification increases the reactive active sites of the biomass oil, and the hydroxymethylation modification improves the polycondensation reaction activity of the biomass oil, so that the multicomponent copolymerization condensation reaction is realized.
3. The addition of the cross-linking agent in the preparation process improves the polymerization degree of the polymer, thereby improving the bonding performance of the polymer.
4. The biomass oil adhesive with high bonding performance and high substitution rate can be prepared by adopting a multi-component copolymerization condensation method.
Detailed Description
A preparation method of a biomass oil/glucose resin adhesive comprises the following specific steps:
the method comprises the following steps: phenolization modification
Adding biomass oil, phenol, an alkali catalyst and water into a reaction kettle according to the mass ratio, heating to 60 ℃, stirring and reacting for 1h to prepare a phenolated modified liquid;
the feeding amount of the biomass oil is 25-75% of the total mass of the biomass oil and the phenol, the feeding amount of the alkali catalyst is 10-20% of the total mass of the biomass oil and the phenol, and the adding amount of the water is calculated according to the final mass concentration of the alkali catalyst reaching 8-15%.
Step two: modification of hydroxymethylation
Uniformly mixing a formaldehyde solution and a cross-linking agent, slowly dripping the mixture into the phenolic modified liquid prepared in the step one, and continuously stirring and reacting for 0.5-2 h at the temperature of 60 ℃ to prepare a hydroxymethylation modified liquid;
the mass concentration of the formaldehyde solution is 37 percent, and the addition amount W of the formaldehyde solutionFAccording to the formula:
WF＝[WP+WBIO-OIL]/MP×1.3×MFcalculation of 37% × (1-Y),
in the formula, WP、WBIO-OILRespectively the feeding amount of the phenol and the biomass oil in the step one, MPIs the molar mass of phenol, MFThe molar mass of the formaldehyde, and the replacement rate of the glucose for replacing the formaldehyde;
the addition amount of the cross-linking agent is 5-30% of the total mass of the biomass oil and the phenol;
step three: crosslinking copolymerization
And (3) heating the hydroxymethylation modified solution prepared in the second step to 80 ℃, adding glucose in the heating process, continuously stirring and reacting for 3 hours, finishing the copolymerization and condensation reaction when the viscosity of the reactant reaches 300-700 mPa.s, and discharging to prepare the biomass oil/glucose resin adhesive.
The adding amount of the glucose is 25-85% of the total mass of the glucose and the formaldehyde solution.
The biomass oil/glucose resin adhesive is prepared by phenolization modification, hydroxymethylation modification and crosslinking condensation copolymerization.
The alkali catalyst in phenolization modification is one or a mixture of sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide.
The cross-linking agent is furfural or glyoxal.
The biomass oil is obtained by biomass pyrolysis, and the biomass is one or more of rice hulls, plant straws, lignin, wood processing waste and bamboo processing waste.
The invention is further illustrated by the following specific examples.
Example 1: 30g of biomass oil, 10g of phenol, 8g of an alkali catalyst and 46g of water are added into a reaction kettle, a stirrer is started, the temperature is set to be 60 ℃, and phenolization reaction is carried out for 1 hour. After the reaction is finished, 22.37g of mixed solution of 37% of formaldehyde solution and 6g of furfural is added dropwise, and stirring is continued for 0.5 h. After the hydroxymethylation reaction is finished, the temperature of the reaction kettle is raised to 80 ℃, 22.38g of glucose is added in the process of raising the temperature, and the stirring reaction is continued for 3 hours. When the viscosity of the reaction product reaches 492 mPas, the copolymerization and condensation reaction is finished, and the product is discharged.
Example 2: 24g of biomass oil, 16g of phenol, 6g of an alkali catalyst and 46g of water are added into a reaction kettle, a stirrer is started, the temperature is set to be 60 ℃, and phenolization reaction is carried out for 1 hour. After the reaction is finished, 11.19g of 37% formaldehyde solution and 2g of furfural mixed solution are added dropwise, and stirring is continued for 0.5 h. After the hydroxymethylation reaction is finished, the temperature of the reaction kettle is raised to 80 ℃, 33.56g of glucose is added in the process of raising the temperature, and the stirring reaction is continued for 3 hours. When the viscosity of the reaction product reaches 445 mPas, the copolymerization and condensation reaction is finished, and the product is discharged.
Example 3: 30g of biomass oil, 10g of phenol, 8g of an alkali catalyst and 46g of water are added into a reaction kettle, a stirrer is started, the temperature is set to be 60 ℃, and phenolization reaction is carried out for 1 hour. After the reaction, 11.19g of 37% formaldehyde solution and 6g of furfural mixed solution were added dropwise, and stirring was continued for 1 hour. After the hydroxymethylation reaction is finished, the temperature of the reaction kettle is raised to 80 ℃, 33.56g of glucose is added in the process of raising the temperature, and the stirring reaction is continued for 3 hours. And finishing the copolymerization condensation reaction when the viscosity of the reactant reaches 480 mPas, and discharging.
Example 4: 20g of biomass oil, 20g of phenol, 8g of an alkali catalyst and 46g of water are added into a reaction kettle, a stirrer is started, the temperature is set to be 60 ℃, and phenolization reaction is carried out for 1 hour. After the reaction is finished, 6.71g of 37% formaldehyde solution and 4g of furfural mixed solution are added dropwise, and stirring is continued for 1 h. After the hydroxymethylation reaction is finished, the temperature of the reaction kettle is raised to 80 ℃, 38.04g of glucose is added in the process of raising the temperature, and the reaction is continued to be stirred for 3 hours. And finishing the copolymerization condensation reaction when the viscosity of the reactant reaches 474mPa & s, and discharging.
Example 5: 24g of biomass oil, 16g of phenol, 8g of an alkali catalyst and 46g of water are added into a reaction kettle, a stirrer is started, the temperature is set to be 60 ℃, and phenolization reaction is carried out for 1 hour. After the reaction is finished, 22.37g of mixed solution of 37% of formaldehyde solution and 2g of furfural is added dropwise, and stirring is continued for 0.5 h. After the hydroxymethylation reaction is finished, the temperature of the reaction kettle is raised to 80 ℃, 22.38g of glucose is added in the process of raising the temperature, and the stirring reaction is continued for 3 hours. When the viscosity of the reactant reaches 453 mPas, the copolymerization and condensation reaction is finished, and the product is discharged.
The prepared adhesive indexes under different experimental conditions are shown in table 1:
TABLE 1 indexes of biomass oil/glucose resin adhesives prepared with different formaldehyde substitution rates
According to the invention, phenol and formaldehyde are used as modifiers, firstly, biomass oil and phenol are subjected to phenolization modification to prepare phenolized modified liquid, then, the phenolized modified liquid and formaldehyde are subjected to hydroxymethylation modification to prepare hydroxymethylated modified liquid, then, glucose is used for partially replacing formaldehyde, meanwhile, a cross-linking agent is added, and then, the biomass oil/glucose resin adhesive taking the biomass oil and the glucose as main reaction raw materials is prepared through multi-element synergistic cross-linking copolymerization. When the substitution rate of the phenol is more than 75%, the use amount of the formaldehyde can be reduced by more than 60%, and the bonding strength of the product is improved.
The invention has the advantages that the reactivity of the biomass oil is improved by the phenolization modification and the hydroxymethylation modification, so that the multicomponent copolymerization condensation reaction is realized, and the polymerization degree of the polymer is improved by adding the cross-linking agent, so that the gluing performance is improved.
Claims (7)
1. A preparation method of a biomass oil/glucose resin adhesive is characterized by comprising the following steps: comprises the following steps which are sequentially carried out,
step one, phenolization modification
Respectively measuring biomass oil and phenol, wherein the mass of the biomass oil accounts for 25-75% of the total mass of the biomass oil and the phenol,
measuring an alkali catalyst which is 10-20% of the total mass of the biomass oil and the phenol, obtaining the addition amount of the alkali catalyst and water mixed by a mass concentration formula under the condition that the mass concentration of the alkali catalyst is 8-15%, and measuring,
adding the measured biomass oil, phenol, an alkali catalyst and water into a reaction kettle, heating to 60 ℃, and stirring for reaction for 1h to obtain a phenolated modified liquid;
step two: modification of hydroxymethylation
Mixing a formaldehyde solution and a cross-linking agent, dropwise adding the mixture into the phenolic modified liquid obtained in the step one, keeping the temperature of the reaction kettle at 60 ℃, and continuously stirring for 0.5-2 h to obtain hydroxymethylation modified liquid;
step three: crosslinking condensation copolymerization
And D, adding glucose into the hydroxymethylation modified liquid obtained in the step two, stirring, heating the reaction kettle to 80 ℃, continuously stirring for 3 hours, discharging the product when the viscosity of the reactant reaches 300-700 mPa.s, and obtaining the biomass oil/glucose resin adhesive.
2. The method for preparing the biomass oil/glucose resin adhesive according to claim 1, which is characterized by comprising the following steps: the biomass oil is obtained by biomass pyrolysis, and the biomass is one or a mixture of more than two of rice hulls, plant straws, lignin, wood processing waste and bamboo processing waste.
3. The method for preparing the biomass oil/glucose resin adhesive according to claim 1, which is characterized by comprising the following steps: the alkali catalyst in the first step is one or a mixture of more than two of sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide.
4. The method for preparing the biomass oil/glucose resin adhesive according to claim 1, which is characterized by comprising the following steps: the mass concentration of the formaldehyde solution in the second step is 37 percent, and the adding amount W of the formaldehyde solutionFComprises the following steps: wF＝[WP+WBIO-OIL]/MP×1.3×MF÷37％×(1-Y)，
In the formula, WPThe charging amount of phenol in the step one, WBIO-OILThe feeding amount of the biomass oil in the step one, MPIs the molar mass of phenol, MFIs the molar mass of formaldehyde, and Y is the substitution rate of glucose for formaldehyde.
5. The method for preparing the biomass oil/glucose resin adhesive according to claim 1, which is characterized by comprising the following steps: and the cross-linking agent in the second step is furfural or glyoxal.
6. The method for preparing the biomass oil/glucose resin adhesive according to claim 1 or 5, which is characterized in that: the addition amount of the cross-linking agent is 5-30% of the total mass of the biomass oil and the phenol.
7. The method for preparing the biomass oil/glucose resin adhesive according to claim 1, which is characterized by comprising the following steps: the adding amount of the glucose in the third step is 25 to 85 percent of the total mass of the glucose and the formaldehyde solution.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519572A (en) * | 2009-04-13 | 2009-09-02 | 北京海润川投资咨询有限公司 | Method for preparing phenol formaldehyde adhesive by bio oil |
| CN102527923A (en) * | 2012-01-04 | 2012-07-04 | 福州大学 | Glucose-phenol resin adhesive for foundry and a preparation method of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519572A (en) * | 2009-04-13 | 2009-09-02 | 北京海润川投资咨询有限公司 | Method for preparing phenol formaldehyde adhesive by bio oil |
| CN102527923A (en) * | 2012-01-04 | 2012-07-04 | 福州大学 | Glucose-phenol resin adhesive for foundry and a preparation method of same |
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