CN115781858B - E (E) NF Preparation method of graded lignan-based particle board - Google Patents
E (E) NF Preparation method of graded lignan-based particle board Download PDFInfo
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Abstract
The invention discloses E NF A preparation method of a graded lignan-based shaving board belongs to the technical field of artificial board production. The method comprises the following steps: mixing lignin, polyphenol, aldehyde and a catalyst, and performing polymerization reaction to obtain a first-stage reaction product; then continuing to add aldehyde and catalyst to perform polymerization reaction to reach target viscosity, adding aldehyde trapping agent, and cooling to 40-45 ℃ to obtain lignin-based adhesive; fully mixing and sizing the lignin-based adhesive with the surface layer and the core layer shavings, adding an oxidation-reduction catalyst, and paving the surface layer and the core layer by adopting a sandwich structure; hot pressing to obtain E by adopting program controlled pressure process NF And (3) grading the lignin-based particle board. The invention takes polyphenol as active auxiliary agent, which not only can improve the pre-pressing formability of wood shavings, but also can promote the quick solidification of lignin-based adhesives, so that the mechanical properties of the flakeboard such as internal bonding strength, surface bonding strength, elastic modulus, static bending strength and the like meet the use requirement in a wet state, and the environmental protection grade reaches E NF The requirements of the grade artificial board.
Description
Technical Field
The invention relates to the technical field of particle board preparation, in particular to an E NF A preparation method of a graded lignan-based particle board.
Background
The agriculture and forestry residues have the advantages of wide sources, reproducibility, degradability and the like, and are important strategic resources for national economy and social development. Most of agriculture and forestry residues such as branch materials, urban landscape trees and the like are used as low-value fuel, so that the problems of resource waste and environmental pollution are caused. The shaving board is prepared from wood shavings through the procedures of sizing, hot pressing and the like, has good physical and mechanical properties and workability, and is widely applied to the fields of building decoration, furniture, floors, doors and windows, packaging materials and the like. Annual output of the chipboard in China is 4000 ten thousand cubic meters, and the consumption of the adhesive is 400 ten thousand tonsWherein more than 80% of the adhesive is melamine modified urea resin adhesive. The potential formaldehyde release hazard of the aldehyde adhesive and the wooden products thereof is an important technical bottleneck for restricting the green transformation and upgrading of the wood adhesive and developing novel high-quality artificial boards in China. Along with the improvement of the living standard of people in China, people are more and more concerned about the influence of living environment on health, E NF The grade chipboard has the characteristics of green and environment protection, and the market demand increases year by year. In recent years, polyisocyanate (pMDI) adhesives have been used for the production of E due to their advantages of no formaldehyde addition, high mechanical strength and low dosage NF The pMDI adhesive has poor initial adhesion and poor plate blank molding before curing, and needs to be in line with expensive tackifying resin, so that the gluing and conveying processes are easy to react with water vapor to be cured to block pipelines and bond steel belts, and a large amount of release agent is needed to be used, thereby increasing the price; the molecular structure of the pMDI adhesive lacks flexibility, so that the surface layer of the fiberboard is too hard, and the outstanding problems of easy edge breakage and the like in routing are caused, so that the pMDI adhesive cannot be used for the production of the particle board for a long time. The biomass adhesive has the advantages of wide raw material source, low price, reproducibility, simple production process, safety, environmental protection and the like, and is used for developing a novel green wood adhesive with high performance and high environmental protection to prepare high-quality E NF The grade artificial board is an important development direction of the current wood adhesive industry.
Lignin as a residue in the biorefinery industry has the advantages of wide sources, renewable, degradable and the like. It is counted that only the pulp and paper industry produces about 5000 ten thousand tons of industrial lignin annually worldwide, most of which are not fully utilized as low-value fuels or abandoned in natural environments.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an E NF The preparation method of the graded lignin-based chipboard has the advantages that the prepared lignin-based chipboard has short curing time, high mechanical property and environmental protection grade meeting E through a simple and green preparation process NF The national standard requirement of the grade artificial board.
In order to solve the technical problems, the invention adopts the following technical scheme:
e (E) NF The preparation method of the graded lignan-based particle board comprises the following steps:
1) Mixing lignin, polyphenol, aldehyde and a catalyst, and carrying out polymerization reaction at 85-95 ℃ to obtain a first-stage reaction product; wherein, the weight fractions of lignin, polyphenol, aldehyde and catalyst are respectively 100-120 parts, 80-100 parts, 80-90 parts and 60-80 parts;
2) Adding aldehyde and catalyst into the first stage reaction product, continuing polymerization reaction to target viscosity, adding aldehyde trapping agent, cooling to 40-45deg.C to obtain E NF Lignin-based adhesive for the grade chipboard; wherein, the weight fractions of aldehyde and catalyst are 150-200 parts, 100-150 parts respectively;
3) Fully mixing the lignin-based adhesive with the surface layer and the core layer shavings respectively, adding an oxidation-reduction catalyst, and paving the surface layer and the core layer by adopting a sandwich structure;
4) Adopting program to control hot-pressing pressure, time and temperature to obtain E NF And (3) grading the lignin-based particle board.
The polyphenol is at least one of phenol, resorcinol, catechol and tannin.
The aldehyde is at least one of formaldehyde, glyoxal and 2, 5-furandicarboxaldehyde, and the aldehyde in step 1) is the same as or different from the aldehyde in step 2).
The lignin is at least one of biorefinery alkali lignin and pulping industry alkali lignin.
The catalyst is at least one of sodium hydroxide solution, potassium hydroxide solution and polyether amine, and the catalyst in the step 1) is the same as or different from the catalyst in the step 2).
The aldehyde trapping agent is at least one of urea, dicyandiamide and melamine.
The target viscosity is 60-1000 mPa.s.
The redox catalyst is at least FeSO 4 -H 2 O 2 、FeCl 3 -(NH 4 )SO 3 、(NH 4 ) 2 S 2 O 8 One of them.
The sizing amount of the lignin-based adhesive is 30-120 kg/m 3 。
The hot pressing time is 30-60 s/mm, and the hot pressing temperature is 180-220 ℃.
The beneficial effects are that: compared with the prior art, the invention has the following technical advantages:
1) E of the invention NF The preparation process of graded lignan-based shaving board includes the reaction of lignin, polyphenol and dialdehyde to prepare E NF A graded lignin-based adhesive; then take E as NF The graded lignan-based adhesive is fully mixed with the surface/core layer shavings and the oxidation-reduction catalyst respectively, and the E is prepared by hot press curing NF And (3) grading the lignin-based particle board. The preparation process is simple and green, and the prepared lignin-based shaving board has the characteristics of short curing time, high mechanical property and the like;
2) The invention takes polyphenol as active auxiliary agent, which not only can improve the pre-pressing formability of wood shavings, but also can promote the quick solidification of lignin-based adhesives, so that the mechanical properties of the shaving board such as internal bonding strength, surface bonding strength, elastic modulus, static bending strength and the like meet the furniture use requirement in a wet state, and the environmental protection grade reaches E NF The requirements of the grade artificial board.
Drawings
FIG. 1 is a FT-IR spectrum of LPRs5 resin before and after curing;
FIG. 2 is a DSC chart of the curing process of LPRs5 resin and lignin phenolic resin.
Detailed Description
The invention will be further illustrated with reference to specific examples. The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are intended to limit the scope of the invention, any and all products that come within the meaning of the invention or that combine the features of the invention with other prior art are within the scope of the invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Comparative example 1
The lignin phenolic resin is prepared by stepwise polycondensation of lignin, phenol and formaldehyde under the action of alkaline solution, and has the advantages of high bonding strength, weather resistance, good water resistance, ageing resistance and the like. Here, lignin phenolic resin with a lignin to phenol mass ratio of 1:1 was selected as a comparative example.
The lignin phenolic resin preparation process is carried out by adopting the prior art (the preparation method is referred to as Zhao Hui, xu Yanru and Ren Hao. The application performance of the high-substitution lignin phenolic resin in plywood is compared with that of [ J ]. Forest chemical and industry, 2022,42 (04): 75-80; yang S, wen JL, yuan TQ, sun RC. Characterization and phenolation of biorefinery technical lignins for lignin-Phenol-formaldehyde resin adhesive systems, RSC Advances.2014; 4 (101): 57996-8004; younesi-Kordkheii H. Maleated lignin coreaction with Phenol-formaldehyde resins for improved wood adhesives performance, international Journal of Adhesion and Adhesives, 2022 Mar 1;113:103080;Younesi-Kordkheii H, pizzi A, A Comparison among Lignin Modification Methods on the Properties of Lignin-Phe-Formaldehyde Resin as Wood Adhesives, polymers 2021 Oct 12;13 (20): 3502.) and the main preparation process is as follows:
adding phenol, water, a first batch of sodium hydroxide solution and lignin powder into a reaction kettle, starting stirring to carry out lignin phenolization, adding a first batch of formaldehyde (40% of the total dosage), and controlling the polymerization temperature to be 80-89 ℃ to react for 60min to carry out methylolation reaction; adding a second batch of formaldehyde (40% of the total dosage) and a second batch of sodium hydroxide solution (30% of the total dosage), controlling the polymerization temperature to be 80-89 ℃ and reacting for 60min, and carrying out polycondensation reaction; adding a third batch of formaldehyde solution (20% of the total dosage) and a third batch of sodium hydroxide solution (40% of the total dosage) into urea (the dosage of the urea is 15% of the mass fraction of phenol), cooling to below 40 ℃, and discharging to obtain the lignin phenolic resin.
Example 1
E (E) NF The preparation method of the graded lignan-based particle board comprises the following specific steps:
1) Mixing 100g lignin, 80 g phenol, 80 g formaldehyde and 60 g sodium hydroxide solution, and carrying out polymerization reaction at 85-95 ℃ for 45 min to obtain a first-stage reaction product;
2) Adding 150 g formaldehyde and 100g sodium hydroxide solution into the first stage reaction product, polymerizing to 150 mPa.s, adding 15 g urea, cooling to 40-45deg.C to obtain E NF Lignin-based adhesives LPRs1 for the grade chipboard;
3) Fully mixing the lignin-based adhesive LPRs1 with the surface layer wood shavings and the core layer wood shavings respectively, wherein the sizing amount is 30 kg/m 3 Adding FeSO 4 -H 2 O 2 The catalyst, the surface layer and the core layer are paved by adopting a sandwich structure;
4) Adopting program to control hot-pressing pressure, hot-pressing at 180 deg.C for 60 s/mm to obtain E NF Graded lignin-based particle board PBs1.
The obtained LPRs1 resin has pH value of 11.4 and solid content of 46.0%, which are similar to the lignin phenolic resin of comparative example (pH value of 11.6 and solid content of 45.3%). 100. When the temperature is lower than the temperature, the gel time of the LPRs1 resin is 20 min plus or minus 1 min, which is obviously lower than that of lignin phenolic resin (gel time is 28 min plus or minus 2 min), thus showing that the lignin reactivity is obviously improved.
The obtained PBs1 particle board has the bonding strength of 0.41 MPa, static bending strength of 16.43 MPa and elastic modulus of 3347.02 MPa, and the test result of the perforation method formaldehyde release amount of 0.51 mg/100g, meets E NF Furniture type shaving boards used in a stage wet state are required.
Example 2
E (E) NF The preparation method of the graded lignan-based particle board comprises the following specific steps:
1) Mixing 100g lignin, 90 g resorcinol, 90 g2, 5-furan dicarboxaldehyde and 80 g sodium hydroxide solution, and polymerizing at 85-95 ℃ for 60min to obtain a first-stage reaction product;
2) Adding 150 g formaldehyde and 150 g sodium hydroxide solution to the first stage reaction product, and polymerizing to 200 mPa.s, adding 15 g dicyandiamide, cooling to 40-45 ℃ to obtain E NF Lignin-based adhesives LPRs2 for the grade chipboard;
3) Fully mixing the lignin-based adhesive LPRs2 with the surface layer wood shavings and the core layer wood shavings respectively, wherein the sizing amount is 50 kg/m 3 Adding FeSO 4 -H 2 O 2 The catalyst, the surface layer and the core layer are paved by adopting a sandwich structure;
4) Adopting program to control hot-pressing pressure, hot-pressing at 200 ℃ to 45 s/mm to prepare E NF Graded lignin-based particle board PBs2.
The resulting LPRs2 resins had pH and solids levels of 11.8 and 51.4, respectively, similar to the comparative lignin phenolic resin and the example LPRs1 resins. 100. When the temperature is lower than the temperature, the gel time of the LPRs2 resin is 19 min plus or minus 1 min, which is similar to that of the LPRs1 resin of the embodiment and is obviously lower than that of the lignin phenolic resin (gel time is 28 min plus or minus 2 min), which indicates that the lignin reactivity is obviously improved.
The obtained PBs2 particle board has the bonding strength of 0.44 MPa, static bending strength of 14.41 MPa and elastic modulus of 2695.77 MPa, and the formaldehyde release amount test result by the perforation method is 0.33 mg/100g, which accords with E NF Furniture type shaving boards used in a stage wet state are required.
Example 3
E (E) NF The preparation method of the graded lignan-based particle board comprises the following specific steps:
1) Mixing 120 g lignin, 100g tannin, 80 g of 2, 5-furan dicarboxaldehyde and 80 g sodium hydroxide solution, and carrying out polymerization reaction at 85-95 ℃ for 75 min to obtain a first-stage reaction product;
2) Adding 150 g of 2, 5-furan dicarboxaldehyde and 130 g sodium hydroxide solution into the reaction product of the first stage, performing polymerization reaction until reaching 500 mPa.s, adding 5 g dicyandiamide, and cooling to 40-45 ℃ to obtain E NF Lignin-based adhesives LPRs3 for the grade chipboard;
3) Fully mixing the lignin-based adhesive LPRs3 with the surface layer wood shavings and the core layer wood shavings respectively, wherein the sizing amount is 100 kg/m 3 Adding FeSO 4 -H 2 O 2 The catalyst, the surface layer and the core layer are paved by adopting a sandwich structure;
4) Adopting program to control hot-pressing pressure, hot-pressing at 210 ℃ for 30 s/mm to prepare E NF Graded lignin-based particle board PBs3.
The resulting LPRs3 resins had pH and solids levels of 10.9 and 52.4%, respectively. 100. When the temperature is lower than the temperature, the gel time of the LPRs3 resin is 22 min plus or minus 1 min, which is obviously lower than that of lignin phenolic resin (gel time is 28 min plus or minus 2 min), thus showing that the lignin reactivity is obviously improved.
The obtained PBs3 particle board has the bonding strength of 0.55 MPa, static bending strength of 16.07 MPa and elastic modulus of 2720.08 MPa, and the formaldehyde release amount by the perforation method is not detected and accords with E NF Furniture type shaving boards used in a stage wet state are required.
Example 4
E (E) NF The preparation method of the graded lignan-based particle board comprises the following specific steps:
1) Mixing 120 g lignin, 100g tannin and resorcinol in a weight ratio of 1:1 mixture, 80 g formaldehyde and 2, 5-furan dicarboxaldehyde in a weight ratio of 1:2 mixture and 90 g sodium hydroxide solution, and carrying out polymerization reaction at 85-95 ℃ for 65 min to obtain a first-stage reaction product;
2) Adding 150 g formaldehyde and 2, 5-furan dicarboxaldehyde mixture with a weight ratio of 1:2 and 150 g sodium hydroxide solution into the reaction product of the first stage, carrying out polymerization reaction until 400 mPa.s, adding 10 g urea and dicyandiamide mixture with a weight ratio of 1:1, and cooling to 40-45 ℃ to obtain E NF Lignin-based adhesives LPRs4 for the particle board;
3) Fully mixing the lignin-based adhesive LPRs4 with the surface layer wood shavings and the core layer wood shavings respectively, wherein the sizing amount is 120 kg/m 3 Adding FeSO 4 -H 2 O 2 The catalyst, the surface layer and the core layer are paved by adopting a sandwich structure;
4) Adopting program to control hot-pressing pressure, hot-pressing at 200 ℃ to 60 s/mm to prepare E NF Graded lignin-based particle board PBs4.
The resulting LPRs4 resin had pH and solids content of 12.0 and 50.4%, respectively. 100. When the temperature is lower than the temperature, the gel time of the LPRs4 resin is 17 min plus or minus 1 min, which is obviously lower than that of lignin phenolic resin (gel time is 28 min plus or minus 2 min), thus showing that the lignin reactivity is obviously improved.
The obtained PBs4 particle board has the bonding strength of 0.79 MPa, static bending strength of 17.47 MPa and elastic modulus of 2755.08 MPa, and the formaldehyde release amount by the perforation method is not detected and accords with E NF Furniture type shaving boards used in a stage wet state are required.
Example 5
E (E) NF The preparation method of the graded lignan-based particle board comprises the following specific steps:
1) Mixing 120 g lignin, 100g tannin and phenol in a weight ratio of 1:2, 90 g glyoxal and 2, 5-furan dicarboxaldehyde in a weight ratio of 1:2 and 70 g sodium hydroxide solution, and carrying out polymerization reaction at 85-95 ℃ for 75 min to obtain a first-stage reaction product;
2) Adding 150 g formaldehyde, glyoxal and 2, 5-furan dicarboxaldehyde mixture with the weight ratio of 1:1:2 and 150 g sodium hydroxide solution into the reaction product of the first stage, carrying out polymerization reaction until 300 mPa.s, adding 20 g urea and dicyandiamide mixture with the weight ratio of 1:1, and cooling to 40-45 ℃ to obtain E NF Lignin-based adhesives LPRs5 for the particle board;
3) Fully mixing the LPRs5 adhesive with the surface layer wood shavings and the core layer wood shavings respectively, wherein the sizing amount is 80 kg/m 3 Adding FeSO 4 -H 2 O 2 The catalyst, the surface layer and the core layer are paved by adopting a sandwich structure;
4) Adopting program to control hot-pressing pressure, hot-pressing at 200 ℃ to 45 s/mm to prepare E NF And (5) grading woody base particle board PBs5.
The resulting LPRs4 resin had pH and solids content of 11.0 and 48.4%, respectively. 100. When the temperature is lower than the temperature, the gel time of the LPRs5 resin is 18 min plus or minus 1 min, which is obviously lower than that of lignin phenolic resin (gel time is 28 min plus or minus 2 min), thus showing that the lignin reactivity is obviously improved.
The obtained PBs5 particle board has an internal bonding strength of 0.67 MPa, static bending strength of 15.27 MPa, elastic modulus of 2560.56 MPa, and 1 m 3 The formaldehyde release amount by the climate box method is 0.011 mg/m 3 Is in accordance with E NF Furniture type shaving boards used in a stage wet state are required.
Example 6 product Performance test
Resin viscosity test: the rotational viscosity of the resin is measured by adopting a rotational viscometer at the temperature of 25+/-2 ℃, namely the viscosity of the resin is the viscosity of the resin.
Gel time: taking 5 g resin into a test tube, immersing the test tube into boiling water at 100 ℃, and recording the time for the resin to coagulate into clusters, namely the gel time.
The internal bond strength, static bending strength and elastic modulus of the shaving board were tested according to the furniture shaving board standard used in the P6 grade wet state in GB/T4897-2015 shaving board.
The formaldehyde emission is controlled according to the perforation method of GB/18580-2017 artificial board for interior decoration material and the formaldehyde emission limit in the product thereof and the classification of GB/T39600-2021 artificial board and the formaldehyde emission of the product thereof 1 m 3 And (5) determining by a climatic box method.
FIG. 1 is a FT-IR spectrum of the LPRs5 resin before and after curing, and it was found that the FT-IR spectrum of the LPRs5 resin before and after curing showed a significant C=O peak in the resin after curing, which is an explanation of FeSO 4 -H 2 O 2 The catalyst promotes the oxidation of a portion of the hydroxyl groups in the resin to carbonyl groups.
FIG. 2 is a DSC curve of the curing process of LPRs5 resin and lignin phenolic resin, comparing the curing exotherm peaks of LPRs5 resin and lignin phenolic resin to demonstrate that the curing reactivity of LPRs5 resin is higher than lignin phenolic resin.
TABLE 1 results of product Performance test
From the results in table 1, it can be seen that:
1) Preparation of E from glyoxal and 2, 5-furandicarboxaldehyde partially or fully substituted for formaldehyde NF Compared with the lignin phenolic resin adhesive of the comparative example, the lignin-based adhesive has the advantages that the free formaldehyde content is reduced by more than 70%, which shows that the lignin-based adhesive prepared by the invention is environment-friendly and remarkably improved;
2) Compared with the performance of the particle board, the particle board prepared from the common lignin phenolic resin has poorer mechanical property, the internal bonding strength is only 0.22MPa, and the formaldehyde release amount is realizedAs high as 8.462mg/100g, E cannot be reached NF The requirement of the particle board is that lignin phenolic resin is solidified at a low speed, and cannot be matched with the particle board production process.
Thus, the invention breaks through FeSO 4 -H 2 O 2 The oxidation-reduction catalytic lignin-based adhesive rapid curing technology is adopted, and the prepared shaving board meets the standard requirements of furniture type shaving boards used in a P6 level wet state in GB/T4897-2015 shaving board. The formaldehyde emission is controlled according to the perforation method of GB/18580-2017 artificial board for interior decoration material and the formaldehyde emission limit in the product thereof and the classification of GB/T39600-2021 artificial board and the formaldehyde emission of the product thereof 1 m 3 Climate box method measurement, meets E NF The requirements of the grade chipboard.
Claims (7)
1. E (E) NF The preparation method of the graded lignan-based particle board is characterized by comprising the following steps:
1) Mixing lignin, polyphenol, aldehyde and a catalyst, and carrying out polymerization reaction at 85-95 ℃ to obtain a first-stage reaction product; wherein, the weight fractions of lignin, polyphenol, aldehyde and catalyst are respectively 100-120 parts, 80-100 parts, 80-90 parts and 60-80 parts;
2) Adding aldehyde and catalyst into the first stage reaction product, continuing polymerization reaction to target viscosity, adding aldehyde trapping agent, cooling to 40-45deg.C to obtain E NF Lignin-based adhesive for the grade chipboard; wherein, the weight fractions of aldehyde and catalyst are 150-200 parts, 100-150 parts respectively;
3) Fully mixing the lignin-based adhesive with the surface layer and the core layer shavings respectively, adding an oxidation-reduction catalyst, and paving the surface layer and the core layer by adopting a sandwich structure;
4) Adopting program to control hot-pressing pressure, time and temperature to obtain E NF A graded lignin-based particle board;
the polyphenol is tannin; the aldehyde is at least one of glyoxal and 2, 5-furan dicarboxaldehyde, and formaldehyde is added or not added; the aldehyde in step 1) is the same or different from the aldehyde in step 2);
the redox reactionThe catalyst being at least FeSO 4 -H 2 O 2 、FeCl 3 -(NH 4 )SO 3 、(NH 4 ) 2 S 2 O 8 One of them.
2. E according to claim 1 NF The preparation method of the graded lignin-based particle board is characterized in that the lignin is at least one of biorefinery alkali lignin and pulping industry alkali lignin.
3. E according to claim 1 NF A process for the preparation of a graded wood based particle board, characterized in that the catalyst is at least one of sodium hydroxide solution, potassium hydroxide solution and polyetheramine, the catalyst in step 1) being the same or different from the catalyst in step 2).
4. E according to claim 1 NF The preparation method of the graded wood element-based particle board is characterized in that the aldehyde trapping agent is at least one of urea, dicyandiamide and melamine.
5. E according to claim 1 NF The preparation method of the graded wood element-based shaving board is characterized in that the target viscosity is 60-1000 mPa.s.
6. E according to claim 1 NF The preparation method of the graded lignin-based chipboard is characterized in that the sizing amount of the lignin-based adhesive is 30-120 kg/m 3 。
7. E according to claim 1 NF The preparation process of the graded wood base shaving board is characterized in that the hot pressing time is 30-60 s/mm, and the hot pressing temperature is 180-220 ℃.
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| DE4030718A1 (en) * | 1990-09-28 | 1992-04-02 | Univ Dresden Tech | Lignin based binder prodn. from black liquor or thick liquor - by concn. of liquor, addn. of alkali, addn. of phenol and formaldehyde or para:formaldehyde and condensn. |
| CN103358385B (en) * | 2012-04-01 | 2015-07-01 | 中国科学院过程工程研究所 | Method for producing non-formaldehyde environment-friendly particle boards by utilizing alkali lignin as binder |
| CN108587538B (en) * | 2018-05-15 | 2021-01-22 | 北京林业大学 | Preparation method of green phenolic resin adhesive with high lignin substitution ratio |
| CN108822779A (en) * | 2018-06-26 | 2018-11-16 | 北京林业大学 | A kind of low-temperature setting lignin-base condensation copolymerization resin adhesive and preparation method |
| CN113801616B (en) * | 2020-10-22 | 2023-05-12 | 广州源海新材料科技有限公司 | Modified lignin weather-resistant adhesive |
| CN113478605B (en) * | 2021-07-27 | 2022-11-04 | 北京林业大学 | Super-strong reed straw particle board and preparation method thereof |
| CN115449329A (en) * | 2022-09-22 | 2022-12-09 | 广西科学院 | Method for modifying adhesive by lignin |
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