CN113861364A - Method for preparing biomass polyurethane based on high-activity lignin polyphenol and product - Google Patents

Method for preparing biomass polyurethane based on high-activity lignin polyphenol and product Download PDF

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CN113861364A
CN113861364A CN202111187657.XA CN202111187657A CN113861364A CN 113861364 A CN113861364 A CN 113861364A CN 202111187657 A CN202111187657 A CN 202111187657A CN 113861364 A CN113861364 A CN 113861364A
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lignin
polyphenol
polyurethane
stirring
dissolving
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刘琳
王邓峰
姚菊明
陈阳柳
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Zhejiang Sci Tech University ZSTU
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials

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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a method for preparing biomass polyurethane based on high-activity lignin polyphenol and a product, wherein the preparation method comprises the following steps: 1) mixing a hydrogen bond donor reagent and choline chloride, adding a first catalyst, and stirring to prepare a eutectic solvent; placing plant raw materials in a eutectic solvent, stirring and dissolving, adding ethanol, fully shaking, and filtering to obtain a filtrate as a lignin dissolving solution; washing and filtering the lignin dissolving solution by using pure water, and drying to obtain powdery lignin polyphenol; 2) dissolving lignin polyphenol in an organic solvent, adding the organic solvent into a polyethylene glycol solution, fully stirring to prepare a white material, slowly dropwise adding isocyanate and a second catalyst, and stirring to obtain a polyurethane prepolymer; dripping a chain extender, violently stirring uniformly, and pouring into a grinding tool to prepare polyurethane; 3) and reacting and curing the polyurethane at high temperature to obtain the high-elasticity high-strength biomass polyurethane. The biomass polyurethane product is prepared by the method.

Description

Method for preparing biomass polyurethane based on high-activity lignin polyphenol and product
Technical Field
The invention relates to the field of biomass polyurethane preparation, in particular to a method for preparing biomass polyurethane based on high-activity lignin polyphenol and a product.
Background
Polyurethane is used as a block polymer with soft and hard chain segments, has the characteristic of controllable structural performance, and is widely applied to the light weight of structural parts of automobiles and buildings. However, the existing polyurethane performance regulation is mostly realized based on regulation of the types and the proportions of petrochemical polyol and isocyanate, and has the problem of difficult degradation. Meanwhile, the traditional polyurethane synthesis process is complex, and requires environments such as vacuum, dehydration and nitrogen protection, and has higher requirements on equipment and processes. Therefore, the design of the high-strength high-elasticity biomass polyurethane synthesis process with the recoverable performance has important significance for the development of the polyurethane industry.
At present, lignin polyphenol as a hydroxyl-rich substance can be applied to biomass polyurethane synthesis. However, most of lignin extraction in industry is based on acidolysis, high-temperature alkali dissolution, enzymolysis and other methods, and has the defects of large molecular weight, large steric hindrance, low reaction activity and the like of products, poor dispersion performance in liquid, and unsatisfactory use of the lignin as a raw material for polyurethane synthesis, which results in the harsh reaction environment required in the polyurethane polymerization process and poor mechanical properties of polyurethane synthesis.
Patent CN201811334960.6 discloses a lignin polyurethane preparation method, which utilizes acid catalysis, compound polyol as liquefier, extracts lignin under high pressure and high pressure, and purifies by dialysis, the prepared lignin can be applied to polyurethane preparation, and partial substitution of petrochemical polyol can be realized by liquefying lignin; patent CN200910193436.6 discloses a lignin polyurethane and a preparation method thereof, which mainly dissolves lignin extracted and separated from residues of fuel ethanol production from straws by using sodium hydroxide with an organic solvent, removes the residues, then uses water to precipitate, separates the lignin, modifies with epoxide, dissolves in polyol, and finally compounds with raw materials such as isocyanate to obtain the polyurethane material. Patent CN202010024715.6 discloses a hydroxyl-enriched acetic lignin polyurethane adhesive and a preparation method thereof, wherein an organic solvent is used to extract a biomass raw material to obtain refined acetic lignin, and the refined acetic lignin is aligned to perform demethylation modification.
The existing lignin has the problems of low reaction activity, few reaction sites, high cost of the polyurethane adhesive, difficult degradation and the like. It is worth pointing out that the lignin liquefaction extraction process has higher cost of lignin liquefaction due to higher energy consumption, the lower reaction activity of the raw materials has stricter requirements on the synthesis process, and the reaction process can be realized by nitrogen protection and a vacuum environment.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a method for preparing biomass polyurethane based on high-activity lignin polyphenol, which is used for extracting high-phenolic hydroxyl-content high-reactivity lignin based on a eutectic solvent system, so as to simplify the extraction process, reduce the polymerization conditions and improve the polyurethane reactivity, and a product.
The purpose of the invention can be realized by the following technical scheme: the method for preparing the biomass polyurethane based on the high-activity lignin polyphenol comprises the following steps:
1) mixing a hydrogen bond donor reagent and choline chloride, adding a first catalyst, and stirring at 80-140 ℃ for 0.5-1h to prepare a eutectic solvent; placing plant raw materials in a eutectic solvent, stirring and dissolving for 12 hours, then adding ethanol, enabling the volume ratio of the ethanol to the eutectic solvent to be 1-5:1, fully shaking, and filtering to obtain filtrate as a lignin dissolving solution; washing and filtering the lignin dissolving solution by using pure water, and drying at 60 ℃ to obtain powdery lignin polyphenol;
2) dissolving lignin polyphenol in an organic solvent, adding the organic solvent into a polyethylene glycol solution, fully stirring to prepare a white material, slowly dropwise adding isocyanate and a second catalyst, and stirring for 1h to obtain a polyurethane prepolymer; then dripping a chain extender under the condition of 40-70 ℃, violently and uniformly stirring, and pouring into a grinding tool to prepare polyurethane;
3) and reacting the polyurethane at high temperature for 5-10min, and curing for 1-10h to obtain the high-elasticity high-strength biomass polyurethane.
In the method for preparing the biomass polyurethane based on the high-activity lignin polyphenol, in the step 1), the hydrogen bond donor reagent and the choline chloride are mixed and configured according to a molar ratio of 1-10:1, wherein the hydrogen bond donor is at least one of oxalic acid, citric acid, malic acid, lactic acid and fructose. Preferred hydrogen bond donors are oxalic acid and lactic acid.
In the above method for preparing biomass polyurethane based on high-activity lignin polyphenol, in step 1), the first catalyst is a metal catalyst, specifically at least one of ferric chloride, ferric oxide, zinc chloride, zinc oxide, cupric chloride, cupric oxide, and cobalt oxide.
In the method for preparing the biomass polyurethane based on the high-activity lignin polyphenol, in the step 1), the plant raw material is at least one of softwood, hardwood and bamboo raw materials and grass raw materials, and the plant raw material has the size specification of 10-100 mesh particles, 2-4 cm long and 1-2 cm wide wood chips or bamboo chips and 2-4 cm long and grass raw materials; the dissolving temperature of the plant raw materials in the eutectic solvent is 60-140 ℃.
In the method for preparing the biomass polyurethane based on the high-activity lignin polyphenol, in the step 1), the eutectic solvent is at least one of a choline chloride/oxalic acid system, a choline chloride/glycerol system, a choline chloride/lactic acid system, a choline chloride/citric acid system, a choline chloride/malic acid system and a choline chloride/glycerol/potassium carbonate system, and the eutectic solvent is preferably a choline chloride/oxalic acid system and a choline chloride/lactic acid system. The size of the eutectic solvent is below 200 meshes.
In the method for preparing the biomass polyurethane based on the high-activity lignin polyphenol, in the step 2), the dissolving solution of the lignin polyphenol and the polyethylene glycol solution are mixed according to the molar ratio of 0.1-0.5: 1; the molar ratio of the sum of the molar numbers of the lignin polyphenol solution and the polyethylene glycol solution to the isocyanate is 0.3-0.6: 1; the molar ratio of the chain extender to the isocyanate is 0.4-0.7: 1; the temperature of dripping isocyanate is 60-85 ℃; the mass ratio of the second catalyst to the lignin dissolving solution is 0.001-0.005:1, w/w; the weight average molecular weight of the polyethylene glycol solution is 200-1000; the stirring speed is 100-500 r/min.
In the above method for preparing biomass polyurethane based on high-activity lignin polyphenol, in step 2), the organic solvent is at least one of 1, 4-dioxane, dimethyl sulfoxide, N-dimethylformamide, dichloromethane and acetone. Among them, 1, 4-dioxane, dimethyl sulfoxide and N, N-dimethylformamide are preferable.
In the above method for preparing biomass polyurethane based on high-activity lignin polyphenol, in step 2), the isocyanate includes at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI).
In the method for preparing the biomass polyurethane based on the high-activity lignin polyphenol, in the step 2), the second catalyst is at least one of dibutyltin dilaurate, triethylenediamine, triethanolamine, stannous octoate and organic lithium, organic bismuth and organic zinc catalysts; the chain extender is at least one of 1, 4-butanediol, ethylenediamine, 3' -dichloro-4, 4-diaminodiphenylmethane, 1, 4-cyclohexanediol, hydrogenated bisphenol A, dimethylene phenyl glycol, hydroquinone bis-beta-hydroxyethyl ether, resorcinol hydroxyl ether, -glycerol allyl ether, glycidyl allyl ether, dicumyl peroxide and sulfur.
A product for preparing biomass polyurethane based on high-activity lignin polyphenol is prepared by the method of any one of the above methods.
Compared with the prior art, the method for preparing the biomass polyurethane based on the high-activity lignin polyphenol and the product have the following beneficial effects:
1. the extraction process has the advantages of environment-friendly process raw materials, no waste discharge, low energy consumption and high reaction activity of the extract.
2. The green process designed based on the invention for extracting the lignin polyphenol effectively solves the problems of low activity and poor liquefaction capability of the product, can be used for preparing high-performance biomass polyurethane, does not need harsh reaction environment, greatly simplifies the synthesis conditions and shortens the synthesis time.
3. The polyurethane prepared by the method has high-strength and high-elasticity mechanical properties, can realize the functions of ultraviolet shielding and the like, and greatly expands the application field of the biomass polyurethane.
Drawings
FIG. 1 is a UV spectrum of a lignin solution of the present invention.
FIG. 2 is an infrared spectrum of lignin polyurethane in the present invention.
FIG. 3 stress-strain curves for lignin polyurethanes in accordance with the present invention.
FIG. 4 shows the phenolic hydroxyl content and the extraction rate of lignin extracted from different eutectic systems in the invention.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
As shown in fig. 1-4.
Example 1:
1) and preparing a eutectic solvent: mixing oxalic acid and choline chloride according to a certain molar ratio, and stirring for 1h at 100 ℃ to prepare a first solution;
2) and lignin dissolution: placing 60-mesh bamboo powder into the first solution according to a bath ratio of 10:1, stirring and dissolving at 100 ℃ for 12h, then adding ethanol (ethanol: eutectic solvent, v/v) according to a volume ratio of 1-5:1, fully shaking, and filtering through 200-mesh filter cloth to obtain a filtrate, namely a second solution;
3) and lignin purification: adding pure water (pure water: the second solution, v/v) into the second solution according to the volume ratio of 2-5:1, standing for 24h until lignin is completely separated out, performing vacuum filtration by using 0.2-0.45 mu m filter paper, fully drying and grinding filter residues at 60 ℃ to obtain lignin powder, and performing rotary evaporation on the filtered solution at 80 ℃ to recover the solvent;
4) dissolving 2.0g of lignin prepared in the step 3) in 20mL of 1, 4-dioxane, adding the dissolved lignin into 30mL of polyethylene glycol (Mn 1000) solution, and fully stirring to prepare a white material. Then slowly dripping 15mL of isocyanate and 0.2mL of stannous isooctanoate at the temperature of 85 ℃, and stirring for 1h at 300r/min to obtain the polyurethane prepolymer. Vacuum dehydrating and introducing nitrogen for protection, then dripping a chain extender at the temperature of 40-70 ℃, heating to 110 ℃, and violently stirring for 1-3 min;
5) reacting the polyurethane obtained in the step 4) at 110 ℃ for 2-4h, and curing at 80 ℃ for 24 h. The high-elasticity high-strength lignin polyurethane is prepared.
Examples 2 to 5: the oxalic acid in the example 1 is replaced by any one of citric acid, lactic acid, glycerol, malic acid and fructose, and the rest conditions are the same as the example 1.
Examples 6 to 10: the Hexamethylene Diisocyanate (HDI) in example 1 was changed to Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Lysine Diisocyanate (LDI), and the other conditions were the same as in example 1.
The results of mechanical property analysis of the lignin polyurethanes synthesized in examples 6 to 10 are shown in Table 1.
TABLE 1 Effect of different isocyanates on the mechanical Properties of Lignin polyurethanes
Figure BDA0003299928080000061
Figure BDA0003299928080000071
As can be seen from Table 1, the isocyanate species has an important influence on the mechanical properties of lignin polyurethane extracted from the eutectic solvent, and the isocyanate species containing benzene rings has better mechanical properties as a whole, which is shown in that the breaking strength is stronger, but the breaking elongation is reduced along with the increase of the molecular cohesion.
Examples 11 to 15: the ratio of lignin to PEG-1000 in example 1 was changed to 10%, 20%, 30%, 40%, 50%, 60% (lignin: PEG-1000, molar ratio), and the other conditions were the same as in example 1.
The results of mechanical property analysis of the lignin polyurethanes synthesized in examples 11 to 15 are shown in Table 2.
TABLE 2 influence of Lignin content on mechanical Properties of Lignin polyurethanes
Figure BDA0003299928080000072
As can be seen from Table 2, with the increase of the ratio of lignin, the content of hard chain segments in polyurethane molecules is increased, the mechanical properties of the product are increased continuously, when the ratio of lignin replacing PEG-1000 reaches 60%, the breaking strength of the polyurethane at the moment can reach 20.3MPa, but with the increase of the ratio, the breaking elongation is reduced to 30.5%, and the product is hardened as a whole.
Examples 16 to 19: the isocyanate to polyol molar ratios in the examples were changed to 1.4:1, 1.6:1, 1.8: 1 and 2.0:1, the other conditions being the same as in example 1.
The results of mechanical property analysis of the lignin polyurethanes synthesized in examples 16 to 19 are shown in Table 3.
TABLE 3 influence of isocyanate ratio on mechanical Properties of Lignin polyurethanes
Figure BDA0003299928080000081
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (10)

1. The method for preparing the biomass polyurethane based on the high-activity lignin polyphenol is characterized by comprising the following steps of:
1) mixing a hydrogen bond donor reagent and choline chloride, adding a first catalyst, and stirring at 80-140 ℃ for 0.5-1h to prepare a eutectic solvent; placing plant raw materials in a eutectic solvent, stirring and dissolving for 12 hours, then adding ethanol, enabling the volume ratio of the ethanol to the eutectic solvent to be 1-5:1, fully shaking, and filtering to obtain filtrate as a lignin dissolving solution; washing and filtering the lignin dissolving solution by using pure water, and drying at 60 ℃ to obtain powdery lignin polyphenol;
2) dissolving lignin polyphenol in an organic solvent, adding the organic solvent into a polyethylene glycol solution, fully stirring to prepare a white material, slowly dropwise adding isocyanate and a second catalyst, and stirring for 1h to obtain a polyurethane prepolymer; then dripping a chain extender under the condition of 40-70 ℃, violently and uniformly stirring, and pouring into a grinding tool to prepare polyurethane;
3) and reacting the polyurethane at high temperature for 5-10min, and curing for 1-10h to obtain the high-elasticity high-strength biomass polyurethane.
2. The method for preparing biomass polyurethane according to claim 1, wherein in the step 1), the hydrogen bond donor reagent and the choline chloride are mixed and configured in a molar ratio of 1-10:1, wherein the hydrogen bond donor is at least one of oxalic acid, citric acid, malic acid, lactic acid and fructose.
3. The method for preparing biomass polyurethane according to claim 1, wherein in step 1), the first catalyst is a metal catalyst, and specifically is at least one of ferric chloride, ferric oxide, zinc chloride, zinc oxide, cupric chloride, cupric oxide and cobalt oxide.
4. The method for preparing biomass polyurethane based on high-activity lignin polyphenol as claimed in claim 1, wherein in step 1), the plant raw material is at least one of softwood, hardwood, bamboo and grass raw materials, the plant raw material has the size specification of 10-100 mesh particles, 2-4 cm long and 1-2 cm wide wood chips or bamboo chips and 2-4 cm long and grass raw materials; the dissolving temperature of the plant raw materials in the eutectic solvent is 60-140 ℃.
5. The method for preparing biomass polyurethane according to claim 1, wherein in the step 1), the eutectic solvent is at least one of choline chloride/oxalic acid system, choline chloride/glycerol system, choline chloride/lactic acid system, choline chloride/citric acid system, choline chloride/malic acid system and choline chloride/glycerol/potassium carbonate system, and the size of the eutectic solvent is below 200 mesh.
6. The method for preparing biomass polyurethane based on high-activity lignin polyphenol as claimed in claim 1, wherein in step 2), the solution of lignin polyphenol is mixed with polyethylene glycol solution according to molar ratio of 0.1-0.5: 1; the molar ratio of the sum of the molar numbers of the lignin polyphenol solution and the polyethylene glycol solution to the isocyanate is 0.3-0.6: 1; the molar ratio of the chain extender to the isocyanate is 0.4-0.7: 1; the temperature of dripping isocyanate is 60-85 ℃; the mass ratio of the second catalyst to the lignin dissolving solution is 0.001-0.005:1, w/w; the weight average molecular weight of the polyethylene glycol solution is 200-1000; the stirring speed is 100-500 r/min.
7. The method for preparing biomass polyurethane according to claim 1, wherein in step 2), the organic solvent is at least one of 1, 4-dioxane, dimethyl sulfoxide, N, N-dimethylformamide, dichloromethane and acetone.
8. The method for preparing biomass polyurethane according to claim 1, wherein in the step 2), the isocyanate comprises at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), and Lysine Diisocyanate (LDI).
9. The method for preparing biomass polyurethane according to claim 1, wherein in step 2), the second catalyst is at least one of dibutyltin dilaurate, triethylenediamine, triethanolamine, stannous octoate, organic lithium, organic bismuth and organic zinc catalysts; the chain extender is at least one of 1, 4-butanediol, ethylenediamine, 3' -dichloro-4, 4-diaminodiphenylmethane, 1, 4-cyclohexanediol, hydrogenated bisphenol A, dimethylene phenyl glycol, hydroquinone bis-beta-hydroxyethyl ether, resorcinol hydroxyl ether, -glycerol allyl ether, glycidyl allyl ether, dicumyl peroxide and sulfur.
10. Product for the production of biomass polyurethanes based on highly active lignin polyphenols, characterized in that it is obtained by the process according to any one of claims 1 to 9.
CN202111187657.XA 2021-10-12 2021-10-12 Method for preparing biomass polyurethane based on high-activity lignin polyphenol and product Pending CN113861364A (en)

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CN115232176A (en) * 2022-07-14 2022-10-25 华南理工大学 Method for extracting lignin by using ternary eutectic solvent

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114032254A (en) * 2022-01-10 2022-02-11 中国农业科学院农业环境与可持续发展研究所 Method for promoting anaerobic methane production by treating straws with ultrasonic-assisted ternary DES (data encryption standard)
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CN115216027A (en) * 2022-08-15 2022-10-21 齐鲁工业大学 Preparation method of lignin with high phenolic hydroxyl content
CN115216027B (en) * 2022-08-15 2023-11-10 齐鲁工业大学 Preparation method of lignin with high phenolic hydroxyl content

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Application publication date: 20211231