CN111073325A - Lignin/fiber thermoplastic composite material and preparation method thereof - Google Patents
Lignin/fiber thermoplastic composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J2397/00—Characterised by the use of lignin-containing materials
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a lignin/fiber thermoplastic composite material and a preparation method thereof, belonging to the field of thermoplastic composite materials. Two types of modified lignin capable of being dynamically and chemically crosslinked are constructed based on Diels-Alder reaction; fully blending the two modified lignins, the flame retardant and the fiber; and crosslinking and curing the mixture at 60-90 ℃ by utilizing the temperature responsiveness of Diels-Alder reaction to form the composite material. The composite material can generate Diels-Alder reversible reaction at 110-130 ℃, and is recovered to a liquid/solid mixed state before solidification, and the composite material can be recycled, mechanically separated from impurities and remolded for reuse according to the characteristic. Compared with the existing material, the composite material of the invention is biodegradable, can resist ultraviolet aging, has simple and convenient preparation method, can be repeatedly utilized, and is more environment-friendly.
Description
Technical Field
The invention belongs to the field of thermoplastic composite materials, and particularly relates to a lignin/fiber thermoplastic composite material and a preparation method thereof.
Background
The thermoplastic material has the characteristics of convenient processing, wide application and excellent mechanical property, is widely applied to various industries, and is an indispensable important material in the social production and development process. However, today's thermoplastic materials are sourced from petroleum-based products, are difficult to degrade, and cause environmental pollution and additional carbon emissions during use. In recent years, the preparation of thermoplastic materials from biomass feedstocks has been sought to mitigate the negative effects of petroleum-based materials.
Lignin is the second largest biomass resource with yield second to cellulose in nature, and is known as one of the green resources with development prospect in the new century. The natural polymer of the lignin is rich in various functional groups such as benzene rings, phenolic hydroxyl groups and the like, and has good ultraviolet resistance and oxidation resistance. Lignin is also one of the few raw materials with thermoplastic and vitrification properties in natural macromolecular resources, and people research the preparation of lignin-based thermoplastic materials by virtue of the characteristics. But the melting temperature of the lignin is higher, so the lignin-based thermoplastic material has the defect of high energy consumption in the processing and recycling processes. In addition, the lignin thermoplastic materials of today have the disadvantages of low strength, high brittleness and poor toughness, which limits the expansion of their applications.
Disclosure of Invention
In order to overcome the defects and shortcomings, the invention aims to provide the lignin/fiber thermoplastic composite material and the preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a lignin/fiber thermoplastic composite material is characterized by comprising the following steps:
(1) under the protection of nitrogen, fully mixing lignin and isocyanate, dissolving the lignin and the isocyanate in dimethyl sulfoxide, adding a catalyst dibutyltin dilaurate, and finally adding furfuryl amine to react to obtain a system 1;
(2) under the protection of nitrogen, fully mixing lignin and isocyanate, dissolving the lignin and the isocyanate in dimethyl sulfoxide, adding a catalyst dibutyltin dilaurate, and finally adding N-carbamyl maleimide to react to obtain a system 2;
(3) under the protection of nitrogen, mixing the system 1 and the system 2, adding polyethylene glycol for full dissolution, adding isocyanate, and continuously stirring to obtain a system 3;
(4) and uniformly dispersing the fiber and the flame retardant in the system 3, transferring the mixture into a mold, and curing the mixture into the lignin/fiber thermoplastic composite material.
Preferably, in the step (1), the reaction temperature is 50-80 ℃, and the reaction time is 1-3 h; the molar ratio of the total hydroxyl groups of the lignin to isocyanate and furfuryl amine is 1 (1-1.5) to 0.8-2.5; the addition amount of the dibutyltin dilaurate is 0.02-0.08 percent of the total mass of the lignin; the sum of the mass fractions of the lignin, the isocyanate and the furfuryl amine in the dimethyl sulfoxide is 15-45%.
Preferably, in the step (2), the reaction temperature is 50-80 ℃, and the reaction time is 1-3 h; the molar ratio of the total hydroxyl groups of the lignin to isocyanate and N-carbamyl maleimide is 1 (1-1.5) to 0.8-2.5; the addition amount of the dibutyltin dilaurate is 0.02-0.08 percent of the total mass of the lignin; the sum of the mass fractions of the lignin, the isocyanate and the N-carbamyl maleimide in the dimethyl sulfoxide is 15-45%.
Preferably, in the step (3), when the system 1 and the system 2 are mixed, the mass ratio of the lignin in the system 1 and the lignin in the system 2 is 1 (0.8-1.2); the molar ratio of hydroxyl of the polyethylene glycol to the complementary isocyanate is 1 (0.8-1.5).
Preferably, in the step (4), the addition amount of the fiber is 0.1-1.5% of the mass of the system 3; the addition amount of the flame retardant is 5-10% of the mass of the system 3; the curing temperature is 60-90 ℃.
Preferably, the lignin/fiber thermoplastic composite material obtained in the step (4) is softened or liquefied at high temperature, and then impurity separation and remodeling are carried out for recycling; the softening or liquefying temperature of the lignin/fiber thermoplastic composite material is 110-130 ℃.
Preferably, in the step (1) and the step (2), the lignin is one or a combination of more of enzymatic hydrolysis lignin, papermaking lignin, alkali lignin, organic solvent lignin and lignosulfonate, and lignin modified by acylation, esterification, etherification, phenolization, alkylation or demethylation of the enzymatic hydrolysis lignin, the papermaking lignin, the alkali lignin, the organic solvent lignin or lignosulfonate.
Preferably, the isocyanate in the step (1), the step (2) and the step (3) is one or a combination of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate with the functionality of more than or equal to 2; the polyethylene glycol in the step (3) is one or a combination of several of polyethylene glycols with the polymerization degree of 200-800.
Preferably, the fiber in the step (4) is one or a combination of more of cellulose fiber, bamboo fiber, hemp fiber, palm fiber, coconut fiber, glass fiber and carbon fiber, and the length-diameter ratio of the fiber is 5-35; the flame retardant is one or a combination of more of halogen-free antimony trioxide, magnesium carbonate, montmorillonite, triphenyl phosphite and trioctyl phosphate.
A lignin/fiber thermoplastic composite material obtained by the preparation method of any one of the above.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the preparation method of the lignin/fiber thermoplastic composite material comprises the steps of preparing two modified lignins through furfuryl amine, N-carbamyl maleimide and isocyanate, mixing the two modified lignins to construct Diels-Alder dynamic chemical crosslinking, and finally compounding the Diels-Alder dynamic chemical crosslinking with fiber and a flame retardant to prepare the lignin/fiber thermoplastic composite material which has thermal responsiveness and can be recycled. The Diels-Alder dynamic chemical reaction is a 4+2 cycloaddition reaction between a diene compound (furfuryl amine modified lignin) and a dienophile (N-carbamyl maleimide modified lignin) to form a cyclohexene structure. The bonding has temperature reversibility, can be solidified at 60-90 ℃ and softened or liquefied at 110-130 ℃, can be made into various shapes by virtue of the property in an injection molding mode, is convenient to process, and can be used for recovering, purifying and remolding materials in a heating mode.
(2) The lignin is rich in rigid benzene rings, and can endow the lignin/fiber thermoplastic composite material with good mechanical strength and rigidity; the lignin contains various conjugated structures taking benzene rings as centers, can effectively absorb ultraviolet rays, and can endow the lignin/fiber thermoplastic composite material with good ultraviolet aging resistance; various biomass or inorganic fiber raw materials have good mechanical strength, and the tensile resistance of the lignin/fiber thermoplastic composite material can be improved; various added flame retardants can endow the lignin/fiber thermoplastic composite material with good flame retardant performance; the lignin is mainly obtained from the papermaking waste liquid, the price is low, and the production cost of the lignin/fiber thermoplastic composite material can be effectively reduced; the lignin and various biomass fibers are renewable and degradable natural polymers, and can endow the lignin/fiber thermoplastic composite material with good biodegradability. The lignin/fiber thermoplastic composite material prepared by the method reasonably utilizes biomass resources, can replace part of petroleum-based and difficultly-degraded thermoplastic materials, thereby reducing environmental pollution, and can be applied to multiple fields of packaging, buildings, electronic and electric appliances and the like.
Drawings
FIG. 1 is a flow diagram illustrating the preparation of a lignin/fiber thermoplastic composite according to various embodiments of the present invention.
FIG. 2 is a graph showing the tensile properties of the cured lignin/fiber thermoplastic composite of example 1 at various temperatures.
FIG. 3 is a graph of the effect of different fiber addition levels on the tensile properties of a lignin/fiber thermoplastic composite of example 2.
FIG. 4 is a graph of the effect of the number of recovery remolding times on the tensile properties of a lignin/fiber thermoplastic composite of example 3.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation flow chart of the lignin/fiber thermoplastic composite material is shown in figure 1.
Example 1:
the method comprises the following steps: under the protection of nitrogen, according to the molar ratio of total hydroxyl of lignin to hexamethylene diisocyanate and furfuryl amine of 1:1.5:2.5, 10g of kraft lignin and hexamethylene diisocyanate with corresponding mass are dissolved in dimethyl sulfoxide, a dibutyltin dilaurate catalyst with 0.05% of the mass of the lignin is added, finally furfuryl amine with corresponding mass is slowly added, so that the total concentration (mass fraction) of the lignin, the hexamethylene diisocyanate and the furfuryl amine in the dimethyl sulfoxide is 30%, and heat preservation is carried out for 2 hours at 65 ℃, so that a system 1 is obtained.
Step two: under the protection of nitrogen, according to the molar ratio of total hydroxyl of lignin to hexamethylene diisocyanate and N-carbamyl maleimide of 1:1:0.8, 10g of kraft lignin and hexamethylene diisocyanate with corresponding mass are dissolved in dimethyl sulfoxide, a dibutyltin dilaurate catalyst with 0.08% of the mass of the lignin is added, finally, N-carbamyl maleimide with corresponding mass is slowly added, so that the total concentration (mass fraction) of the lignin, the hexamethylene diisocyanate and the N-carbamyl maleimide in the dimethyl sulfoxide is 45%, and the system 2 is obtained by keeping the temperature at 80 ℃ for 3 hours.
Step three: under the protection of nitrogen, 50ml of the system 1 and the system 2 are mixed according to the mass ratio of 1:1, polyethylene glycol (PEG-400) and hexamethylene diisocyanate are added according to the molar ratio of 1:1.15, wherein the adding amount of the PEG-400 is 10 percent of the total mass of lignin in the system 1 and the system 2, and the stirring is continued at 50 ℃ to obtain the system 3.
Step four: and (3) mixing ramie fibers accounting for 0.8% of the total mass of the system 3 and triphenyl phosphite accounting for 7.5% of the total mass of the system 3, pouring the mixture into a mold after fully mixing the mixture with the system 3, and curing the mixture for 24 hours at 75 ℃ for molding.
Step five: and (3) preserving the heat of the lignin/fiber thermoplastic composite material obtained in the fourth step for 30min at the temperature of 130 ℃, recovering the solid composite material into a liquid state, and separating mechanical impurities mixed in the using process by filtering. And after separation, injecting the mixture into the mold again, and curing the mixture at 75 ℃ for 24h for molding, wherein the material can be recycled repeatedly.
As shown in fig. 2, the change of the stretching performance of the cured lignin/fiber thermoplastic composite material at different temperatures is shown. The tensile property of the lignin/fiber thermoplastic composite material is basically stable at the temperature of 10-90 ℃; when the temperature is reduced, the brittleness of the composite material is enhanced, so that the tensile strength is reduced, but at the temperature of-15 ℃, the lignin/fiber thermoplastic composite material still can keep better tensile strength; when the temperature is increased to 110 ℃, the Diels-Alder dynamic chemical bond starts to generate a reversible reaction, the composite material is softened and gradually becomes liquid along with the continuous increase of the temperature, and the mechanical property is obviously reduced at the moment.
Example 2:
the method comprises the following steps: under the protection of nitrogen, 10g of alkali lignin and isophorone diisocyanate with the corresponding mass are dissolved in dimethyl sulfoxide according to the molar ratio of total lignin hydroxyl to isophorone diisocyanate and furfuryl amine of 1:1.25:1.65, a dibutyltin dilaurate catalyst with the mass of 0.08% of the lignin is added, finally furfuryl amine with the corresponding mass is slowly added, the total concentration (mass fraction) of the lignin, isophorone diisocyanate and furfuryl amine in the dimethyl sulfoxide is 30%, and heat preservation is carried out for 1h at 50 ℃ to obtain a system 1.
Step two: under the protection of nitrogen, 10g of alkali lignin and isophorone diisocyanate and N-carbamyl maleimide are dissolved in dimethyl sulfoxide according to the molar ratio of total hydroxyl of lignin to isophorone diisocyanate to N-carbamyl maleimide of 1:1.25:1.65, a dibutyltin dilaurate catalyst accounting for 0.02% of the mass of the lignin is added, finally, N-carbamyl maleimide of the corresponding mass is slowly added, so that the total concentration (mass fraction) of the lignin, isophorone diisocyanate and the N-carbamyl maleimide in the dimethyl sulfoxide is 30%, and the temperature is kept at 50 ℃ for 2 hours to obtain a system 2.
Step three: under the protection of nitrogen, 50ml of system 1 and system 2 are mixed according to the mass ratio of 1:1, polyethylene glycol (PEG-200) and isophorone diisocyanate are added according to the molar ratio of 1:1.5, wherein the adding amount of the PEG-200 is 15% of the total mass of lignin in the system 1 and the system 2, and the system 3 is obtained by continuously stirring at 50 ℃.
Step four: and (3) mixing the glass fiber accounting for 0.5 percent of the total mass of the system 3 and trioctyl phosphate accounting for 5 percent of the total mass of the system 3, pouring the mixture into a mold, and curing for 20 hours at 60 ℃ for molding.
Step five: and (3) preserving the heat of the lignin/fiber thermoplastic composite material obtained in the fourth step for 40min at 120 ℃, recovering the solid composite material into a liquid state, and separating mechanical impurities mixed in the using process by filtering. And after separation, injecting the mixture into the mold again, and curing the mixture at 70 ℃ for 20h for molding, wherein the material can be recycled repeatedly.
As shown in fig. 3, is the effect of different fiber addition levels on the tensile properties of the lignin/fiber thermoplastic composite. Within a certain range, the tensile strength of the lignin/fiber thermoplastic composite material is continuously improved along with the increase of the addition amount of the fiber, and when the addition amount is higher than 1.2%, the uniform distribution of the fiber in the composite material is difficult, the mechanical property of the composite material is difficult to be continuously improved, and even the mechanical property of the material is reduced.
Example 3:
the method comprises the following steps: under the protection of nitrogen, 10g of acetic acid solvent lignin and toluene diisocyanate with corresponding mass are dissolved in dimethyl sulfoxide according to the molar ratio of total lignin hydroxyl to toluene diisocyanate to furfuryl amine of 1:1.5:1.6, a dibutyltin dilaurate catalyst with 0.08% of lignin mass is added, finally furfuryl amine with corresponding mass is slowly added, so that the total concentration (mass fraction) of the lignin, the toluene diisocyanate and the furfuryl amine in the dimethyl sulfoxide is 25%, and the system 1 is obtained by keeping the temperature at 60 ℃ for 2 hours.
Step two: under the protection of nitrogen, dissolving 10g of acetic acid solvent lignin and toluene diisocyanate with the corresponding mass in dimethyl sulfoxide according to the molar ratio of total hydroxyl of lignin to toluene diisocyanate and N-carbamyl maleimide of 1:1.5:1.6, adding dibutyltin dilaurate catalyst with the mass of 0.08% of lignin, and finally slowly adding N-carbamyl maleimide with the corresponding mass to ensure that the total concentration (mass fraction) of the lignin, the toluene diisocyanate and the N-carbamyl maleimide in the dimethyl sulfoxide is 25%, and preserving heat for 2h at 60 ℃ to obtain a system 2.
Step three: under the protection of nitrogen, 50ml of the system 1 and the system 2 are mixed according to the mass ratio of 1:1, polyethylene glycol (PEG-800) and toluene diisocyanate are added according to the molar ratio of 1:0.8, wherein the adding amount of the PEG-800 is 15 percent of the total mass of lignin in the system 1 and the system 2, and the stirring is continued at 60 ℃ to obtain the system 3.
Step four: and (3) mixing the nano cellulose fiber accounting for 0.1 percent of the total mass of the system 3 and the antimony trioxide accounting for 10 percent of the total mass of the system 3, pouring the mixture into a mold after fully mixing the mixture with the system 3, and curing for 36 hours at 75 ℃ for molding.
Step five: and (3) preserving the heat of the lignin/fiber thermoplastic composite material obtained in the fourth step for 30min at 110 ℃, recovering the solid composite material into a liquid state, and separating mechanical impurities mixed in the using process by filtering. And after separation, injecting the mixture into the mold again, and curing the mixture at 75 ℃ for 36h for molding, wherein the material can be recycled repeatedly.
As shown in fig. 4, the effect on the tensile properties of the lignin/fiber thermoplastic composite for recovery of the number of remolding times. After the first curing, the lignin/fiber thermoplastic composite material has excellent tensile property, the tensile strength of the composite material is gradually reduced along with the increase of the recycling and remodeling times, and after 8 times of recycling, the tensile strength of the lignin/fiber thermoplastic composite material can still be maintained above 20 MPa.
Example 4:
the method comprises the following steps: under the protection of nitrogen, 10g of enzymatic hydrolysis lignin and diphenylmethane diisocyanate with the corresponding mass are dissolved in dimethyl sulfoxide according to the molar ratio of the total hydroxyl of the lignin to the diphenylmethane diisocyanate and the furfuryl amine of 1:1.3:1.8, a dibutyltin dilaurate catalyst with the mass of 0.06% of the lignin is added, finally, furfuryl amine with the corresponding mass is slowly added, so that the total concentration (mass fraction) of the lignin, the diphenylmethane diisocyanate and the furfuryl amine in the dimethyl sulfoxide is 35%, and the system 1 is obtained by keeping the temperature at 60 ℃ for 3 hours.
Step two: under the protection of nitrogen, 10g of enzymatic hydrolysis lignin and diphenylmethane diisocyanate and N-carbamyl maleimide are dissolved in dimethyl sulfoxide according to the molar ratio of the total hydroxyl of the lignin to the diphenylmethane diisocyanate and the N-carbamyl maleimide of 1:1.3:1.8, a dibutyltin dilaurate catalyst accounting for 0.06% of the mass of the lignin is added, finally, the N-carbamyl maleimide of the corresponding mass is slowly added, so that the total concentration (mass fraction) of the lignin, the diphenylmethane diisocyanate and the N-carbamyl maleimide in the dimethyl sulfoxide is 35%, and the temperature is maintained at 60 ℃ for 3 hours to obtain a system 2.
Step three: under the protection of nitrogen, 50ml of system 1 and system 2 are mixed according to the mass ratio of 1:1, polyethylene glycol (PEG-800) and diphenylmethane diisocyanate are added according to the molar ratio of 1:1.1, wherein the adding amount of the PEG-800 is 18 percent of the total mass of lignin in the system 1 and the system 2, and the stirring is continued at 60 ℃ to obtain a system 3.
Step four: taking the palm fiber accounting for 0.6 percent of the total mass of the system 3 and trioctyl phosphate accounting for 8 percent of the total mass of the system 3, fully mixing with the system 3, pouring into a mold, and curing for 20 hours at 90 ℃ for molding.
Step five: and (3) preserving the heat of the lignin/fiber thermoplastic composite material obtained in the fourth step for 25min at the temperature of 130 ℃, recovering the solid composite material into a liquid state, and separating mechanical impurities mixed in the using process by filtering. And after separation, injecting the mixture into the mold again, and curing the mixture at 80 ℃ for 20h for molding, wherein the material can be recycled repeatedly.
The invention is not limited to the examples, and any equivalent changes that can be made by one skilled in the art through reading the technical scheme of the invention in the specification of the invention are covered by the claims of the invention.
Claims (10)
1. A preparation method of a lignin/fiber thermoplastic composite material is characterized by comprising the following steps:
(1) under the protection of nitrogen, fully mixing lignin and isocyanate, dissolving the lignin and the isocyanate in dimethyl sulfoxide, adding a catalyst dibutyltin dilaurate, and finally adding furfuryl amine to react to obtain a system 1;
(2) under the protection of nitrogen, fully mixing lignin and isocyanate, dissolving the lignin and the isocyanate in dimethyl sulfoxide, adding a catalyst dibutyltin dilaurate, and finally adding N-carbamyl maleimide to react to obtain a system 2;
(3) under the protection of nitrogen, mixing the system 1 and the system 2, adding polyethylene glycol for full dissolution, adding isocyanate, and continuously stirring to obtain a system 3;
(4) and uniformly dispersing the fiber and the flame retardant in the system 3, transferring the mixture into a mold, and curing the mixture into the lignin/fiber thermoplastic composite material.
2. The preparation method according to claim 1, wherein in the step (1), the reaction temperature is 50-80 ℃, and the reaction time is 1-3 h; the molar ratio of the total hydroxyl groups of the lignin to isocyanate and furfuryl amine is 1 (1-1.5) to 0.8-2.5; the addition amount of the dibutyltin dilaurate is 0.02-0.08 percent of the total mass of the lignin; the sum of the mass fractions of the lignin, the isocyanate and the furfuryl amine in the dimethyl sulfoxide is 15-45%.
3. The preparation method according to claim 1, wherein in the step (2), the reaction temperature is 50-80 ℃, and the reaction time is 1-3 h; the molar ratio of the total hydroxyl groups of the lignin to isocyanate and N-carbamyl maleimide is 1 (1-1.5) to 0.8-2.5; the addition amount of the dibutyltin dilaurate is 0.02-0.08 percent of the total mass of the lignin; the sum of the mass fractions of the lignin, the isocyanate and the N-carbamyl maleimide in the dimethyl sulfoxide is 15-45%.
4. The preparation method according to claim 1, wherein in the step (3), when the system 1 and the system 2 are mixed, the mass ratio of the lignin in the system 1 and the system 2 is 1 (0.8-1.2); the molar ratio of hydroxyl of the polyethylene glycol to the complementary isocyanate is 1 (0.8-1.5).
5. The preparation method according to claim 1, wherein in the step (4), the addition amount of the fiber is 0.1-1.5% of the mass of the system 3; the addition amount of the flame retardant is 5-10% of the mass of the system 3; the curing temperature is 60-90 ℃.
6. The preparation method according to claim 1, wherein the lignin/fiber thermoplastic composite material obtained in the step (4) is softened or liquefied at high temperature, and then subjected to impurity separation, remodeling and recycling; the softening or liquefying temperature of the lignin/fiber thermoplastic composite material is 110-130 ℃.
7. The preparation method according to claim 1, wherein in the step (1) and the step (2), the lignin is one or more of enzymatic lignin, papermaking lignin, alkali lignin, organic solvent lignin, lignosulfonate, and lignin modified by acylation, esterification, etherification, phenolization, alkylation or demethylation of the enzymatic lignin, the papermaking lignin, the alkali lignin, the organic solvent lignin or the lignosulfonate.
8. The preparation method of claim 1, wherein the isocyanate in the step (1), the step (2) and the step (3) is one or a combination of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate with a functionality of more than or equal to 2; the polyethylene glycol in the step (3) is one or a combination of several of polyethylene glycols with the polymerization degree of 200-800.
9. The preparation method according to claim 1, wherein the fiber in the step (4) is one or a combination of more of cellulose fiber, bamboo fiber, hemp fiber, palm fiber, coconut fiber, glass fiber and carbon fiber, and the aspect ratio of the fiber is 5-35; the flame retardant is one or a combination of more of halogen-free antimony trioxide, magnesium carbonate, montmorillonite, triphenyl phosphite and trioctyl phosphate.
10. A lignin/fiber thermoplastic composite obtainable by the method of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111945462A (en) * | 2020-07-21 | 2020-11-17 | 华南理工大学 | Lignin/tannin composite polyurethane coating and preparation method thereof |
| WO2022041614A1 (en) * | 2020-08-26 | 2022-03-03 | 何建雄 | Microporous repairable tpu thin film material and preparation method therefor |
| CN114874472A (en) * | 2021-02-05 | 2022-08-09 | 武汉大学 | Production method and application of biodegradable lignocellulose bioplastic |
| CN114874472B (en) * | 2021-02-05 | 2023-07-18 | 武汉大学 | Production method and application of biodegradable lignocellulose bioplastic |
| CN114656654A (en) * | 2022-03-26 | 2022-06-24 | 江苏理工学院 | Modified lignin self-repairing conductive hydrogel and preparation method and application thereof |
| CN114656654B (en) * | 2022-03-26 | 2023-07-11 | 江苏理工学院 | Modified lignin self-repairing conductive hydrogel and preparation method and application thereof |
| CN115521481A (en) * | 2022-11-07 | 2022-12-27 | 南京工业大学 | Novel anti-cutting resin, preparation method thereof and application thereof in preparation of rubber composite material |
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