CN114456754A - Biomass-based phenolic resin adhesive and preparation method thereof - Google Patents
Biomass-based phenolic resin adhesive and preparation method thereof Download PDFInfo
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- CN114456754A CN114456754A CN202210315469.9A CN202210315469A CN114456754A CN 114456754 A CN114456754 A CN 114456754A CN 202210315469 A CN202210315469 A CN 202210315469A CN 114456754 A CN114456754 A CN 114456754A
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- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention relates to a biomass-based phenolic resin adhesive and a preparation method thereof, wherein the product is prepared from biomass hydrolysate or nano-cellulose, formaldehyde, phenol, an alkaline catalyst and a formaldehyde catcher, firstly, biomass material is hydrolyzed or nano-cellulose is prepared, and then the biomass hydrolysate or nano-cellulose is used for replacing formaldehyde to synthesize a biomass-based phenolic resin adhesive, the plywood obtained by pressing the biomass-based phenolic resin adhesive and a wood board has excellent bonding performance, the bonding strength of the plywood obtained by pressing the biomass-based phenolic resin adhesive is 0.88-1.45MPa, and the bonding strength of the plywood reaches 1.2-2.0 times of that of common phenolic resin and is higher than the national class I board requirement.
Description
Technical Field
The invention relates to the technical field of phenolic resin, in particular to a biomass-based phenolic resin adhesive and a preparation method thereof.
Background
Phenol formaldehyde resin (PF) is the earliest resin to be industrialized in the world, and is widely used as a wood adhesive for manufacturing particle boards, plywood, Oriented Strand Boards (OSB), and the like, due to its advantages of excellent mechanical properties, water resistance, low price, and the like. The main synthetic raw materials of the traditional phenolic resin adhesive are phenol and formaldehyde based on fossil, which are not only non-renewable, but also harmful to human bodies and the environment. Therefore, the synthesis of phenolic resin adhesives by using renewable biomass-based products instead of fossil-based products has become a research hotspot in recent years.
Lignocellulosic biomass contains significant amounts of lignin, cellulose, and hemicellulose. The lignin contains groups such as phenolic hydroxyl, alcoholic hydroxyl and the like; both cellulose and hemicellulose structures contain (hemi) acetal groups. At present, the production of biomass-based phenolic resin by using different lignin raw materials instead of phenol at home and abroad has made considerable progress, but the research on the preparation of phenolic resin instead of formaldehyde is less. In the existing research, researchers use glyoxal, furfural, glucose and the like to replace formaldehyde to prepare phenolic resin, for example, Ramires and the like synthesize a novel resin by using glyoxal and phenol as raw materials and resorcinol as a curing agent, and the impact strength of the resin can reach 12 J.m.-1(ii) a Liuhuan and the like utilize furfural to replace formaldehyde to react with phenol to prepare phenol furfural resin, and the results show that various performances of the phenol furfural resin all accord with the national standard; wang et al prepared a novel phenolic resin with glucose instead of formaldehyde, and the results show that the prepared resin has good thermal stability. Although the above materials can replace formaldehyde to react with phenol to form a novel phenolic resin, the cost is increased significantly. For example, formaldehyde is 1600 yuan/ton, while glyoxal, furfural and glucose used to replace formaldehyde are 8500 yuan/ton, 10000 yuan/ton and 3500 yuan/ton, respectively. The invention uses green renewable waste biomass materials as raw materials, can be directly used for replacing formaldehyde after being simply hydrolyzed and neutralized by alkali, and has simple operation and obviously reduced production cost.
CN110156945A discloses a preparation method of a formaldehyde-free biomass-based adhesive, which belongs to the field of biomass energy chemical industry and mainly comprises the following steps: (1) producing a furfural solution by using biomass hemicellulose; (2) producing an alkali lignin solution by using biomass lignin; (3) preparing biomass phenol by biomass pyrolysis; (4) and then biomass phenol, alkali lignin and furfural are used as raw materials to prepare the formaldehyde-free biomass-based adhesive with excellent performance. The invention provides an effective way for producing the environment-friendly adhesive by taking biomass as a raw material. However, the patent technology has the following problems: (1) the bonding strength is slightly weak; (2) the production process is complex and the reaction conditions are harsh. For example, the production process of the furfural solution in step (1) is as follows: adding biomass and 2 wt% sulfuric acid solution into a reaction kettle, heating and refluxing for 2h, filtering hydrolysis residues, repeating the steps for a plurality of times until the concentration of xylose in the hydrolysis solution is 15 wt% -17 wt%, then spraying the xylose solution into a catalyst prepared from the sulfuric acid solution and sodium chloride solution, and condensing and refluxing to obtain the furfural aqueous solution. Wherein, the preparation of the xylose solution is a discontinuous reaction process, and hydrolysis residues need to be filtered out after the reaction is stopped. Secondly, the preparation of the phenol-containing boiling water by biomass heat-clearing needs to be carried out at 500-700 ℃, and the reaction conditions are harsh.
CN110903446A discloses a method for preparing a lignin-based phenolic resin adhesive by using lignin to replace formaldehyde, and the patent technology is also developed by the invention group and comprises the following steps: step a: weighing phenol, lignin or nano lignin, formaldehyde and alkaline substances; step b: b, adding two thirds of other raw materials in the step a into a container containing phenol, heating to 60-65 ℃, preserving heat and stirring for 10-30 min; step c: adding the rest raw materials in the step a again, slowly heating to 70-95 ℃ and keeping constant for 1-5 h; step d: cooling to room temperature to obtain lignin-based phenolic resin, and storing the prepared resin at the temperature below 25 ℃. The method has the beneficial effects that the method for preparing the lignin phenolic resin by directly replacing part of formaldehyde with lignin or nano lignin reduces the requirement on formaldehyde in the production process, reduces the formaldehyde release amount of wooden furniture in daily life, and is green and safe in the production process and more beneficial to large-scale industrial production. The production efficiency of the patent in the process of preparing the nano lignin is low; the method comprises the following steps of adding a large amount of water into lignin, carrying out ultrasonic treatment to obtain a nano lignin dispersion with low content, and repeatedly preparing for many times to obtain a sufficient amount of nano lignin raw material for replacing formaldehyde; and the filtration means such as centrifugation is required to remove the excess water, which increases the production cost. The method can directly replace formaldehyde by using the hydrolysate only by performing acid hydrolysis on the biomass material and neutralizing the biomass material by using alkali, and has mild reaction conditions and simple process flow.
Cellulose is a biomass resource with the most abundant reserves in the nature, has the advantages of wide source, good biocompatibility, biodegradability, natural reproducibility and the like, and is widely concerned. The cellulose structure contains (hemi) acetal group, and can be converted into aldehyde substances through acid hydrolysis and dehydration, thereby being very suitable for replacing formaldehyde to synthesize phenolic resin. The biomass resources in China are quite rich, cellulose is extracted from biomass and is used for producing wood adhesives, a new way is provided for chemical deep processing and high-value utilization of waste agriculture and forestry biomass such as cotton straws, corn straws and corncobs, and harm to human health caused by the utilization of fossil-based raw materials for producing phenolic resin can be reduced.
Disclosure of Invention
The invention aims to provide a biomass-based phenolic resin adhesive.
The invention also aims to provide a preparation method of the biomass-based phenolic resin adhesive.
The biomass-based phenolic resin adhesive is prepared from the following components: biomass hydrolysate or nano-cellulose, formaldehyde, phenol, an alkaline catalyst and a formaldehyde catching agent;
the phenol: the total molar ratio of formaldehyde to biomass hydrolysate is 1:1.2-2.7 or phenol: the total molar ratio of the formaldehyde to the nano-cellulose is 1: 1.2-2.7;
the substitution rate of the biomass hydrolysate or the nano-cellulose for formaldehyde is 5-30 wt%;
the adding amount of the alkaline catalyst is 2-15 wt% of the total mass of the phenol, the formaldehyde and the biomass hydrolysate or 2-15 wt% of the total mass of the phenol, the formaldehyde and the nano cellulose;
the addition amount of the formaldehyde catching agent is 2-6 wt% of the total mass of phenol, formaldehyde and biomass hydrolysate or the addition amount of the formaldehyde catching agent is 2-6 wt% of the total mass of phenol, formaldehyde and nano cellulose.
The preparation method of the invention is to prepare the biomass-based phenolic resin adhesive by using the biomass hydrolysate or the nano-cellulose to replace formaldehyde, and comprises the following steps:
1) hydrolysis of biomass material or preparation of nanocellulose
Hydrolyzing a biomass material rich in cellulose in an acid catalyst to obtain a biomass hydrolysate; reacting the biomass material rich in cellulose with the mixed solution of alkali/urea at low temperature, and adding water for dialysis to obtain the nano-cellulose.
2) Biomass hydrolysate or nano-cellulose replacing formaldehyde to synthesize biomass-based phenolic resin adhesive
Stirring the biomass hydrolysate or the nano-cellulose and a formaldehyde solution at room temperature for 5-20min to prepare a mixed solution; adding two-thirds of the mixed solution, phenol and an alkaline catalyst into a reactor, and reacting for 10-30min at 50-70 ℃; continuously adding the residual mixed solution and the alkaline catalyst into the reactor, and reacting for 1-5h at the temperature of 70-95 ℃; adding a formaldehyde catching agent into the reactor, reacting for 10-40min at 70-95 ℃, and cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
The preparation method of the biomass hydrolysate comprises the following steps: adding 10-80g of biomass material rich in cellulose into 100-800g of 0.1-5mol/L acid catalyst to react for 2-5h under the conditions of stirring speed of 500-600rpm at 150 ℃ and 130 ℃ to obtain a biomass hydrolysate;
the preparation method of the nano-cellulose comprises the following steps: 25g of cellulose-rich biomass material was taken and 500g of sodium hydroxide in a ratio of 7:12: 81: urea: and (3) mixing the water with the solution, stirring for 3h at the temperature of minus 10 ℃, centrifuging the obtained product to obtain a supernatant, dropwise adding 50mL of distilled water into the supernatant, dialyzing to be neutral, and drying the obtained product to obtain the nano-cellulose.
Preferably, the method for synthesizing the biomass-based phenolic resin adhesive by using the biomass hydrolysate to replace formaldehyde comprises the following steps: stirring 3-50g of biomass hydrolysate or nano-cellulose and 100-180g of 37% formaldehyde at room temperature for 5-20min to prepare a mixed solution; adding two thirds of the mixed solution, 50-100g of phenol and 20-60g of 8mol/L alkaline catalyst into a reactor, and reacting for 10-30min at 50-70 ℃; continuously adding the rest mixed solution and 15-25g of 8mol/L alkaline catalyst into the reactor, and reacting for 1-5h at the temperature of 70-95 ℃; adding 8-15g of formaldehyde catching agent into the reactor, reacting for 10-40min at 70-95 ℃, and cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
The mass ratio of the biomass hydrolysate or the nano-cellulose to the formaldehyde is 1:19-3: 7.
The biomass material rich in cellulose is waste agriculture and forestry biomass, and can be corn stalks, corn cobs, cotton stalks, cotton or commercially available microcrystalline cellulose.
The acid used for hydrolyzing the biomass material is one of sulfuric acid, hydrochloric acid and oxalic acid.
The alkali used for preparing the nano-cellulose is one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
The alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide; the formaldehyde scavenger is one or more of urea, ammonia water and melamine.
Has the advantages that:
1. the invention uses green renewable waste biomass materials as raw materials, and the waste biomass materials are simply hydrolyzed and neutralized by alkali to directly replace formaldehyde, thereby not only having simple operation, but also obviously reducing the production cost. Solves the technical problem that the cost is obviously increased because the raw materials of glyoxal and phenol are adopted by Ramires and the like in the prior art.
2. The invention has simple process and high bonding strength, and solves the following problems of CN110156945A in the prior art: weak bonding strength, complex production process and harsh reaction conditions.
3. The method can directly replace formaldehyde with the hydrolysate only after the biomass material is subjected to acid hydrolysis, and has mild reaction conditions and simple process flow. The following problems of CN110903446A in the prior art are solved: the production efficiency is low in the process of preparing the nano lignin; the nano lignin dispersoid with very low content can be obtained only by adding a large amount of water into lignin and carrying out ultrasonic treatment, so that the nano lignin raw material with enough amount can be obtained to replace formaldehyde by repeated preparation for many times; filtration means such as centrifugation is required to remove excess water, which inevitably increases the production cost.
4. According to the invention, a biomass raw material rich in cellulose is hydrolyzed to obtain an aldehyde-group-containing hydrolysate or prepared into nano-cellulose, and the biomass hydrolysate or the nano-cellulose is used for directly replacing formaldehyde to prepare the biomass-based phenolic resin adhesive. Compared with the traditional preparation method of the phenolic resin adhesive, the biomass-based product is used for replacing formaldehyde, so that a new way is provided for chemical deep processing and high-value utilization of biomass resources, and the harm to human health caused by the production of the phenolic resin adhesive by using fossil-based raw materials is reduced.
5. The method for preparing the biomass-based phenolic resin by directly replacing formaldehyde with the biomass hydrolysate or the nano-cellulose has the advantages of stable reaction, easy operation and easy industrial production, and can ensure that the physical properties of the prepared phenolic resin adhesive such as viscosity, pH, solid content and the like meet the requirements of GB/T14074-; the plywood obtained by pressing the adhesive and the wood board has excellent bonding performance, the bonding strength of the plywood obtained by pressing the biomass-based phenolic resin adhesive is 0.88-1.45MPa, and the bonding strength of the plywood reaches 1.2-2.0 times of that of common phenolic resin and is higher than the national class I board requirement.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Step 1: adding 10g of corn straw into 100g of 0.7mol/L sulfuric acid solution, reacting for 3h at the temperature of 130 ℃ and the stirring speed of 500rpm to obtain a corn straw hydrolysate, and adding alkali to adjust the corn straw hydrolysate to be neutral for later use;
step 2: taking 3.4g of the corn straw hydrolysate obtained in the step 1 and 175.7g of 37% formaldehyde (the mass ratio of the corn straw hydrolysate to the formaldehyde is 1:19), and stirring for 10min at room temperature to prepare a mixed solution; adding two thirds of the mixed solution, 94g of phenol and 56g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 10min at 65 ℃; continuously adding the rest mixed solution and 24g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 3.5h at the temperature of 85 ℃; adding 13.5g of urea into the reactor, reacting for 30min at 85 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Example 2
Step 1: adding 20g of corncob into 200g of 1mol/L sulfuric acid solution, reacting for 2h at the stirring speed of 600rpm at 150 ℃ to obtain a corncob hydrolysate, and adding alkali to adjust the corncob hydrolysate to be neutral for later use;
step 2: stirring 5.8g of the corncob hydrolysate obtained in the step 1 and 140g of 37% formaldehyde (the mass ratio of the corncob hydrolysate to the formaldehyde is 1:9) at room temperature for 15min to prepare a mixed solution; adding two thirds of the mixed solution, 54g of phenol and 30g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 15min at 70 ℃; continuously adding the rest mixed solution and 15g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 4 hours at the temperature of 80 ℃; and adding 8g of ammonia water into the reactor, reacting for 30min at 85 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Example 3
Step 1: adding 25g of corncob into 500g of sodium hydroxide/urea mixed solution (sodium hydroxide, urea and water are 7:12:81) and stirring for 3h at the temperature of minus 10 ℃, centrifuging the obtained product to obtain supernatant, dropwise adding 50mL of distilled water into the supernatant, dialyzing to be neutral, and drying the obtained product to obtain the nano-cellulose.
Step 2: taking 11g of the nano-cellulose obtained in the step 1 and 118.8g of 37% formaldehyde (the mass ratio of the nano-cellulose to the formaldehyde is 1:4), and stirring for 20min at room temperature to prepare a mixed solution; adding two thirds of the mixed solution, 94g of phenol and 44.8g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 10min at 70 ℃; continuously adding the rest mixed solution and 22.4g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 3 hours at the temperature of 85 ℃; adding 13.5g of urea into the reactor, reacting for 35min at 90 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Example 4
Step 1: adding 25g of corncob into 250g of 0.7mol/L sulfuric acid solution, reacting for 3h at the temperature of 130 ℃ and the stirring speed of 600rpm to obtain a corncob hydrolysate, and adding alkali to adjust the corncob hydrolysate to be neutral for later use;
step 2: stirring 11g of the corncob hydrolysate obtained in the step 1 and 118.8g of 37% formaldehyde (the mass ratio of the corncob hydrolysate to the formaldehyde is 1:4) at room temperature for 20min to prepare a mixed solution; adding two thirds of the mixed solution, 94g of phenol and 44.8g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 10min at 70 ℃; continuously adding the rest mixed solution and 22.4g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 3 hours at the temperature of 85 ℃; adding 13.5g of urea into the reactor, reacting for 35min at 90 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Example 5
Step 1: adding 25g of cotton into 250g of 0.5mol/L sulfuric acid solution, reacting for 4 hours at 140 ℃ and at a stirring speed of 800rpm to obtain a cotton hydrolysate, and adding alkali to adjust the mixture to be neutral for later use;
step 2: stirring 12.7g of the cotton hydrolysate obtained in the step 1 and 102.8g of 37% formaldehyde (the mass ratio of the cotton hydrolysate to the formaldehyde is 3:7) at room temperature for 10min to prepare a mixed solution; adding two thirds of the mixed solution, 94g of phenol and 56g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 20min at the temperature of 60 ℃; continuously adding the rest mixed solution and 24g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 3 hours at the temperature of 90 ℃; adding 13.5g of melamine into the reactor, reacting for 40min at 90 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Example 6
Step 1: adding 80g of microcrystalline cellulose into 800g of 1mol/L sulfuric acid solution, reacting for 2h at the stirring speed of 600rpm at 150 ℃ to obtain a microcrystalline cellulose hydrolysate, and adding alkali to adjust the microcrystalline cellulose hydrolysate to be neutral for later use;
step 2: adding 46g of the microcrystalline cellulose hydrolysate obtained in the step 1, 94g of phenol and 52g of 8mol/L sodium hydroxide solution into a reactor, and reacting at 70 ℃ for 15 min; continuing to add 23g of the microcrystalline cellulose hydrolysate obtained in the step 1 and 26g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 4 hours at 80 ℃; and adding 12g of urea into the reactor, reacting for 30min at 85 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Experimental example: in order to verify the scientificity and the rationality of the invention, the following experimental research of methodology was carried out:
i, equipment and materials.
Second, Experimental methods
The method sets 13 groups in total, and the method is used in the embodiments 1 to 6; comparative example set 9, the feasibility of the process was verified.
(II) the procedure of comparative example 9 group was:
comparative example 1
Adding 94g of phenol, 207g of formaldehyde solution and 56g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 10min at the temperature of 65 ℃; continuously adding 54g of formaldehyde solution and 24g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 3.5 hours at the temperature of 85 ℃; adding 13.5g of urea into the reactor, reacting for 30min at 85 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Comparative example 2
Stirring 5.8g of corncob and 140g of 37% formaldehyde (the mass ratio of the corncob to the formaldehyde is 1:9) at room temperature for 15min to prepare a mixed solution; adding two thirds of the mixed solution, 54g of phenol and 30g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 15min at 70 ℃; continuously adding the rest mixed solution and 15g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 4 hours at the temperature of 80 ℃; and adding 8g of ammonia water into the reactor, reacting for 30min at 85 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Comparative example 3
Stirring 11g of microcrystalline cellulose and 118.8g of 37% formaldehyde (the mass ratio of the cellulose to the formaldehyde is 1:4) at room temperature for 20min to prepare a mixed solution; adding two thirds of the mixed solution, 94g of phenol and 44.8g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 10min at 70 ℃; continuously adding the rest mixed solution and 22.4g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 3 hours at the temperature of 85 ℃; adding 13.5g of urea into the reactor, reacting for 35min at 90 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Comparative example 4
Step 1: adding 25g of corncob into 250g of 0.7mol/L sulfuric acid solution, reacting for 3h at the stirring speed of 600rpm at room temperature to obtain a corncob hydrolysate, and adding alkali to adjust the corncob hydrolysate to be neutral for later use;
step 2: stirring 11g of the corncob hydrolysate obtained in the step 1 and 118.8g of 37% formaldehyde (the mass ratio of the corncob hydrolysate to the formaldehyde is 1:4) at room temperature for 20min to prepare a mixed solution; adding two thirds of the mixed solution, 94g of phenol and 44.8g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 10min at 70 ℃; continuously adding the rest mixed solution and 22.4g of 8mol/L sodium hydroxide solution into the reactor, and reacting for 3 hours at the temperature of 85 ℃; adding 13.5g of urea into the reactor, reacting for 35min at 90 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Comparative example 5
Step 1: adding 25g of cotton into 250g of 0.5mol/L sulfuric acid solution, reacting for 4 hours at 140 ℃ and at a stirring speed of 800rpm to obtain a cotton hydrolysate, and adding alkali to adjust the mixture to be neutral for later use;
step 2: stirring 12.7g of the cotton hydrolysate obtained in the step 1 and 102.8g of 37% formaldehyde (the mass ratio of the cotton hydrolysate to the formaldehyde is 3:7) at room temperature for 10min to prepare a mixed solution; adding two thirds of the mixed solution, 94g of phenol and 56g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 20min at the temperature of 60 ℃; and continuously adding the residual mixed solution and 24g of 8mol/L sodium hydroxide solution into the reactor, reacting for 3 hours at the temperature of 90 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Comparative example 6
Step 1: adding 80g of microcrystalline cellulose into 800g of 1mol/L sulfuric acid solution, reacting for 2h at the stirring speed of 600rpm at 150 ℃ to obtain a microcrystalline cellulose hydrolysate, and adding alkali to adjust the microcrystalline cellulose hydrolysate to be neutral for later use;
and 2, step: adding 46g of the microcrystalline cellulose hydrolysate obtained in the step 1 and 94g of phenol into a reactor, and reacting for 15min at 70 ℃; continuing to add 23g of the microcrystalline cellulose hydrolysate obtained in the step 1 into the reactor, and reacting for 4 hours at 80 ℃; and adding 12g of urea into the reactor, reacting for 30min at 85 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two ply veneers were pressed and tested for their properties and the results are given in table 1.
Comparative example 7
Step 1: adding 100g of microcrystalline cellulose into 1000g of 1mol/L sulfuric acid solution, reacting for 2h at the stirring speed of 600rpm at 150 ℃ to obtain a microcrystalline cellulose hydrolysate, and adding alkali to adjust the microcrystalline cellulose hydrolysate to be neutral for later use;
step 2: adding 67g of the microcrystalline cellulose hydrolysate obtained in the step 1, 94g of phenol and 75g of 8mol/L sodium hydroxide solution into a reactor, and reacting for 4 hours at 80 ℃; and adding 12g of urea into the reactor, reacting for 30min at 85 ℃, and rapidly cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
Poplar two-ply plywood was pressed and tested for properties, and the results are shown in table 1.
Comparative example 8 (patent publication No. CN110156945A technical solution of example 1)
The plywood test results are listed in table 1.
Comparative example 9 (patent publication No. CN110903446A technical solution of example 1)
The plywood test results are listed in table 1.
Thirdly, obtaining a result: see Table 1
TABLE 1 physical Properties of Biomass-based phenolic resin adhesives with different substitution rates
As can be seen from Table 1, the biomass-based phenolic resin adhesive which is easy to glue, excellent in bonding performance and low in formaldehyde or free of formaldehyde is prepared by using biomass materials, acidic solution, phenol and formaldehyde as basic raw materials and adding a basic catalyst and a formaldehyde catching agent, and test results show that plywood prepared by pressing the biomass-based phenolic resin adhesive and a wood board has excellent gluing performance. The bonding strength of the plywood obtained by pressing the biomass-based phenolic resin adhesive is 0.88-1.45MPa and is superior to that of a comparative example.
Compared with example 3, in example 4, the biomass-based phenolic resin adhesive prepared by hydrolyzing the corncobs with the acid solution to obtain the corncob hydrolysate and the biomass-based phenolic resin adhesive prepared by hydrolyzing the corncobs with the alkali/urea solution to obtain the nanocellulose in example 3 have the advantages that the bonding strength of the plywood is obviously improved. It can be seen that the biomass-based phenolic resin adhesive prepared by using the biomass hydrolysate can obtain better adhesive performance than the biomass-based phenolic resin adhesive prepared by using the nano-cellulose. Compared with the comparative example 1, in the examples 3 and 4, the bonding performance of the biomass-based phenolic resin adhesive prepared by using the corncob hydrolysate or the nano-cellulose is obviously improved compared with that of the pure phenolic resin adhesive, the biomass hydrolysate or the nano-cellulose can replace formaldehyde in a phenolic resin formula to prepare the adhesive, and the plywood pressed by using the biomass-based phenolic resin adhesive has excellent bonding strength.
Compared with the example 4, the cellulose hydrolysate in the example 6 completely replaces formaldehyde in the phenolic resin adhesive formula, although the bonding strength of the plywood in the example 6 is reduced compared with that of the plywood in the example 4, the bonding strength of the plywood pressed by the traditional phenolic resin adhesive in the comparative example 1 is obviously improved, and the plywood in the example 6 can achieve no formaldehyde release, because the biomass hydrolysate can not only replace formaldehyde and phenol to react in a reaction system with phenol, but also can serve as a filler to enhance the mechanical property of the adhesive, so that the bonding strength of the plywood is improved.
Compared with the embodiment 2, the corncob in the comparative example 2 is not hydrolyzed by acid, the qualification rate is 0, the plywood bonding strength is greatly reduced, and the free phenol content is increased, because the corncob is directly added, the corncob is difficult to react with phenol or formaldehyde, the adhesive is obviously layered after the reaction is finished, and meanwhile, the phenol in the adhesive is remained, so that the free phenol content is increased, and the plywood bonding strength is reduced.
Compared with the embodiment 3, the raw materials for replacing formaldehyde are respectively cellulose and nano-cellulose, the cellulose is used for replacing the formaldehyde in the comparative example 3, the reaction activity of the cellulose and phenol is low, the bonding strength of the plywood is reduced and is lower than 0.7MPa of the national standard, residual cellulose appears in a reaction system, and the qualified rate of the adhesive is reduced. It can be seen that the adhesive prepared by using the nanocellulose has more excellent gluing performance.
Comparative example 4 compared with example 4, the hydrolysis temperatures of the corncobs were 130 ℃ and 130 ℃, respectively, and the other conditions were the same, resulting in that the bonding strength of the plywood in comparative example 4 was doubled from that of example 4, and the yield of the plywood was also reduced, because the corncobs were difficult to be effectively hydrolyzed at room temperature, resulting in insufficient aldehydes in the preparation of phenolic resin, resulting in the performance of the plywood being reduced.
Compared with the embodiment 5, the embodiment 5 has the advantages that the urea is not used in the formula of the adhesive in the embodiment 5, so that the performance of the plywood is reduced, because the urea can absorb unreacted formaldehyde in the preparation of the adhesive, and can accelerate the curing of the biomass-based phenolic resin adhesive, and the curing rate is reduced in the pressing process of the plywood, so that the performance of the plywood is finally reduced.
Compared with example 6, in comparative example 6, the alkali catalyst is not used, so that the plywood bonding strength is obviously reduced, and the plywood yield is also reduced, because the alkali catalyst firstly reacts with phenol in a reaction system to form phenol anions, and then reacts with formaldehyde. It can be seen that the adhesive prepared by using the alkali catalyst has high qualification rate and excellent gluing performance.
Comparative example 7 has a higher free phenol content and a significantly lower bond strength than example 6. This is because the cellulose hydrolysate and the alkaline catalyst in comparative example 7 were added at one time, resulting in phenol not reacting sufficiently with the cellulose hydrolysate, and finally the amount of phenol reacted in the reaction system increased, the free phenol content of the adhesive increased, and the plywood performance decreased.
Therefore, the biomass-based phenolic resin adhesive is prepared by using biomass materials, an acidic solution, phenol and formaldehyde as basic raw materials and adding a basic catalyst and a formaldehyde catcher, so that a plywood with high qualification rate and excellent bonding strength can be obtained, the use amount of the formaldehyde in the adhesive formula can be obviously reduced, the plywood is more green and environment-friendly, and when the formaldehyde substitution rate of a biomass hydrolysate is 100%, the bonding strength of the plywood is also higher than the national standard, so that the adhesive has a good application prospect.
While the invention has been described in detail in the foregoing by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that certain changes and modifications may be made therein based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The biomass-based phenolic resin adhesive is characterized by being prepared from the following components: biomass hydrolysate or nano-cellulose, formaldehyde, phenol, an alkaline catalyst and a formaldehyde catching agent;
the phenol: the total molar ratio of formaldehyde to biomass hydrolysate is 1:1.2-2.7 or phenol: the total molar ratio of the formaldehyde to the nano-cellulose is 1: 1.2-2.7;
the substitution rate of the biomass hydrolysate or the nano-cellulose for formaldehyde is 5-30 wt%;
the adding amount of the alkaline catalyst is 2-15 wt% of the total mass of the phenol, the formaldehyde and the biomass hydrolysate or 2-15 wt% of the total mass of the phenol, the formaldehyde and the nano cellulose;
the addition amount of the formaldehyde scavenger is 2-6 wt% of the total mass of phenol, formaldehyde and a biomass hydrolysate, or the addition amount of the formaldehyde scavenger is 2-6 wt% of the total mass of phenol, formaldehyde and nanocellulose.
2. The method for preparing the biomass-based phenolic resin adhesive according to claim 1, wherein the preparation method is to use biomass hydrolysate or nano-cellulose to replace formaldehyde to prepare the biomass-based phenolic resin adhesive, and comprises the following steps:
1) hydrolysis of biomass material or preparation of nanocellulose
Hydrolyzing a biomass material rich in cellulose in an acid catalyst to obtain a biomass hydrolysate; reacting the biomass material rich in cellulose with the mixed solution of alkali/urea at low temperature, and adding water for dialysis to obtain the nano-cellulose.
2) Biomass hydrolysate or nano-cellulose replacing formaldehyde to synthesize biomass-based phenolic resin adhesive
Stirring the biomass hydrolysate or the nano-cellulose and a formaldehyde solution at room temperature for 5-20min to prepare a mixed solution; adding two-thirds of the mixed solution, phenol and an alkaline catalyst into a reactor, and reacting for 10-30min at 50-70 ℃; continuously adding the rest mixed solution and the alkaline catalyst into the reactor, and reacting for 1-5h at the temperature of 70-95 ℃; adding a formaldehyde catching agent into the reactor, reacting for 10-40min at 70-95 ℃, and cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
3. The method for preparing the biomass hydrolysate according to claim 2, wherein the method for preparing the biomass hydrolysate comprises the following steps: 10-80g of biomass material rich in cellulose is added into 100-800g of 0.1-5mol/L acid catalyst to react for 2-5h under the conditions of stirring speed of 500-600rpm at 150 ℃ and 130 ℃ to obtain a biomass hydrolysate.
4. The method according to claim 2, wherein the nanocellulose is prepared by: 25g of cellulose-rich biomass material was taken and 500g of sodium hydroxide in a ratio of 7:12: 81: urea: and (3) mixing the water with the solution, stirring for 3h at the temperature of minus 10 ℃, centrifuging the obtained product to obtain a supernatant, dropwise adding 50mL of distilled water into the supernatant, dialyzing to be neutral, and drying the obtained product to obtain the nano cellulose.
5. The preparation method of claim 2, wherein the biomass hydrolysate is used for replacing formaldehyde to synthesize the biomass-based phenolic resin adhesive by the following steps: stirring 3-50g of biomass hydrolysate or nano-cellulose and 100-180g of 37% formaldehyde at room temperature for 5-20min to prepare a mixed solution; adding two thirds of the mixed solution, 50-100g of phenol and 20-60g of 8mol/L alkaline catalyst into a reactor, and reacting for 10-30min at 50-70 ℃; continuously adding the rest mixed solution and 15-25g of 8mol/L alkaline catalyst into the reactor, and reacting for 1-5h at the temperature of 70-95 ℃; adding 8-15g of formaldehyde scavenger into the reactor, reacting for 10-40min at 70-95 ℃, and cooling to room temperature to obtain the biomass-based phenolic resin adhesive.
6. The method of claim 2, wherein the mass ratio of biomass hydrolysate or nanocellulose to formaldehyde is from 1:19 to 3: 7.
7. The method of claim 2, wherein the cellulose-rich biomass material is waste agriculture and forestry biomass, such as corn stover, corn cobs, cotton stover, cotton, or commercially available microcrystalline cellulose.
8. The method according to claim 2, wherein the acid used for hydrolyzing the biomass material is one of sulfuric acid, hydrochloric acid, and oxalic acid.
9. The biomass-based phenolic resin adhesive according to claim 1, wherein the alkali used for preparing the nano-cellulose is one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
10. The biomass-based phenolic resin adhesive according to claim 1, wherein the alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide; the formaldehyde scavenger is one or more of urea, ammonia water and melamine.
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