CN117866384A - Lignin and epoxy resin copolymer film composite material and preparation method thereof - Google Patents
Lignin and epoxy resin copolymer film composite material and preparation method thereof Download PDFInfo
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- CN117866384A CN117866384A CN202310098600.5A CN202310098600A CN117866384A CN 117866384 A CN117866384 A CN 117866384A CN 202310098600 A CN202310098600 A CN 202310098600A CN 117866384 A CN117866384 A CN 117866384A
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- 229920005610 lignin Polymers 0.000 title claims abstract description 76
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000003085 diluting agent Substances 0.000 claims description 21
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000007790 scraping Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 5
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 5
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 5
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 5
- -1 cardanol phenolic amine Chemical class 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 9
- 238000004537 pulping Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000004593 Epoxy Substances 0.000 description 11
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a lignin and epoxy resin copolymer film composite material and a preparation method thereof, belonging to the technical field of lignin new materials. The method takes black liquor lignin as a raw material, and is copolymerized with E44 epoxy resin, a curing agent is added, and the lignin and epoxy resin copolymer film composite material is obtained through curing. According to the invention, black liquor lignin is used as a raw material to prepare the lignin and epoxy resin copolymer film material, and compared with an E44 film, the elongation at break is increased from 10.6% to 136.5%, and excellent toughness is shown. The invention provides a new idea for recycling pulping black liquor and has good practicability.
Description
Technical Field
The invention belongs to the technical field of new lignin materials, and particularly relates to a lignin and epoxy resin copolymer film composite material and a preparation method thereof.
Background
With the increasing global energy consumption and the severe shortage of petroleum resources, research into renewable resource utilization has attracted widespread attention. Currently, the pulping industry produces approximately 5000 ten thousand tons of industrial lignin per year, with most of these byproducts being used as fuel for alkali recovery and a small number (less than 5%) being processed into dispersants, binders, surfactants, and the like. Therefore, development of high-value utilization of black liquor lignin has important significance.
Epoxy resins (EP) have been widely used in the fields of paint, adhesive and electronics because of their good adhesive strength, superior insulation and excellent chemical corrosion resistance. The lignin has the advantages of a three-dimensional network-shaped rigid structure containing benzene rings, rich hydroxyl functional groups and the like, so that the lignin has great potential in the field of lignin-based epoxy resin composite materials. Xu et al successfully synthesized a series of lignin-based thermosetting resins with adjustable mechanical properties by one-step esterification of lignin, PEG400 and citric acid. The results showed that as the lignin usage increased, the tensile strength increased from 1.2MPa to 34.3MPa. Liu et al used anhydride as a curing agent to prepare carboxylated alkali lignin-based epoxy resin, and compared with pure epoxy resin, the critical stress intensity factor of the carboxylated alkali lignin-based epoxy resin is increased by 68%, and the critical strain energy release rate is increased by 164%. Daniel et al depolymerize the natural lignin in pine wood by hydrogenolysis to obtain an oil product that is reacted with epichlorohydrin to obtain an epoxy prepolymer. The epoxy resin after mixed curing with bisphenol a type epoxy resin or ethylene glycol type epoxy resin has higher flexural modulus and strength than bisphenol a type epoxy resin. Zhang et al modified poplar organic solvent lignin with succinic anhydride to prepare lignin-based epoxy resins having lignin content up to 20%. The tensile strength and flexural strength properties are improved compared to pure epoxy resins. The lignin-based epoxy resin has the defect of low toughness.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a lignin and epoxy resin copolymer film composite material and a preparation method thereof, which realize the resource utilization of pulping black liquor and the sustainable development of bio-based substituted petroleum base.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of lignin and epoxy resin copolymer film uses black liquor lignin as raw material, and makes them undergo the process of copolymerization reaction with E44 epoxy resin, and adds curing agent, and makes them undergo the process of curing so as to obtain the lignin and epoxy resin copolymer film composite material. The method comprises the following steps:
1) Washing the black liquor lignin with water to obtain Refined Lignin (RL);
2) E-44 and RL are added into a reactor with a mechanical stirrer, a thermometer and a condenser tube, stirred and mixed, tetrabutylammonium bromide is added for reaction, and lignin and epoxy resin copolymer (RLEP) is prepared after the reaction is finished;
3) Adding the diluent into the RLEP, stirring to uniformly mix, adding the curing agent, mixing, ultrasonically removing bubbles, coating and scraping a film by using a scraper, and curing to obtain the lignin and epoxy resin copolymer film (RLEPF).
The preparation method of the lignin and epoxy resin copolymer film comprises the steps of dissolving black liquor lignin in water with equal mass, adjusting pH to be 2 by using 2wt% sulfuric acid aqueous solution, centrifuging, washing with water, and freeze-drying the obtained solid to obtain Refined Lignin (RL).
The preparation method of the lignin and epoxy resin copolymer film comprises the steps of stirring E-44 and RL for 1h at 120 ℃; tetrabutylammonium bromide was added and reacted at 160℃for 4 hours.
The preparation method of the lignin and epoxy resin copolymer film comprises the steps that the RL mass is less than or equal to 25wt% of the E-44 mass; preferably, the RL mass is 5wt% to 25wt% of the E-44 mass; it is further preferred that the RL mass is 25 wt.% of the E-44 mass.
According to the preparation method of the lignin and epoxy resin copolymer film, the mass of tetrabutylammonium bromide is 1% of that of E44.
According to the preparation method of the lignin and epoxy resin copolymer film, the diluent is a mixed solution of dimethylbenzene and n-butyl alcohol in a mass ratio of 4:1, and the dosage of the diluent is equal to the mass of the epoxy resin; the mass ratio of RLEP to diluent is 1:1.
According to the preparation method of the lignin and epoxy resin copolymer film, the curing agent is cardanol phenolic amine, and the mass ratio of the cardanol phenolic amine to the RLEP is equal to the epoxy value of 33.49×RLEP.
The thickness of the scraper is 1000 mu m, and the scraper is cured for 17 days at room temperature.
The lignin and epoxy resin copolymer film prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
compared with an E44 film, the elongation at break of the lignin and epoxy resin copolymer film is increased from 10.6% to 136.5%, so that the lignin and epoxy resin copolymer film has excellent toughness and good practicability.
The RLEP prepared by the invention not only provides a new idea for recycling pulping black liquor, but also develops a novel lignin-based epoxy resin film composite material.
Drawings
FIG. 1 is a FTIR spectrum of RLEP.
Detailed Description
The invention is further described below in connection with specific embodiments.
Black liquor lignin generally contains a large amount of lignin. The black liquor lignin used in the examples below was derived from the new Yi city, feihuang chemical Co., ltd, and had an organic content of about 65.8wt%.
The above black liquor lignin was dissolved in water of equal mass, ph=2 was adjusted by 2wt% sulfuric acid water dissolution, and the obtained solid was centrifuged and washed with water, and freeze-dried to obtain Refined Lignin (RL).
The diluents used in the examples below were all mixed solutions of xylene and n-butanol in a mass ratio of 4:1. The curing agents are cardanol phenolic amine.
Example 1
(1) 20g E-44 were put into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser tube, stirred at 120℃for 1 hour, tetrabutylammonium bromide (mass: 1% of E44) was added, the temperature was raised to 160℃and the resulting sample was still E44 epoxy resin (RLEP-0) after 4 hours of incubation.
(2) Adding a diluent into RLEP-0 (the mass ratio of the RLEP-0 to the diluent is 1:1), stirring to uniformly mix the materials, adding a curing agent (the mass of the curing agent is 33.49 XE 44 epoxy value), mixing the materials, removing bubbles by ultrasonic, coating and scraping the film by using a scraper with the thickness of 1000 mu m, and curing the film at room temperature for 17 days to obtain the lignin and epoxy resin copolymer film (RLEPF-0).
Example 2
(1) 20. 20g E-44 and a certain amount of RL (5 wt% of E-44 mass) were put into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, stirred at 120℃for 1 hour, tetrabutylammonium bromide (1% of E44 mass) was added, the temperature was raised to 160℃and the reaction was carried out for 4 hours to obtain a lignin-epoxy resin copolymer (RLEP-5).
(2) Adding a diluent into RLEP-5 (the mass ratio of the RLEP-5 to the diluent is 1:1), stirring to uniformly mix the materials, adding a curing agent (the mass of the curing agent is 33.49 times the epoxy value of the RLEP-5), mixing, ultrasonically removing bubbles, coating and scraping a film by using a scraper with the thickness of 1000 mu m, and curing for 17 days at room temperature to obtain the lignin and epoxy resin copolymer film (RLEPF-5).
Example 3
(1) 20. 20g E-44 and a certain amount of RL (10 wt% of E-44 mass) were put into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, stirred at 120℃for 1 hour, tetrabutylammonium bromide (1% of E44 mass) was added, the temperature was raised to 160℃and the reaction was carried out for 4 hours to obtain a lignin-epoxy resin copolymer (RLEP-10).
(2) Adding a diluent into RLEP-10 (the mass ratio of the RLEP-10 to the diluent is 1:1), stirring to uniformly mix the materials, adding a curing agent (the mass of the curing agent is 33.49 times the epoxy value of the RLEP-10), mixing, ultrasonically removing bubbles, coating and scraping a film by using a scraper with the thickness of 1000 mu m, and curing for 17 days at room temperature to obtain the lignin and epoxy resin copolymer film (RLEPF-10).
Example 4
(1) 20. 20g E-44 and a certain amount of RL (15 wt% of E-44 mass) were put into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, stirred at 120℃for 1 hour, tetrabutylammonium bromide (1% of E44 mass) was added, the temperature was raised to 160℃and the reaction was carried out for 4 hours to obtain a lignin-epoxy resin copolymer (RLEP-15).
(2) Adding a diluent into RLEP-15 (the mass ratio of the RLEP-15 to the diluent is 1:1), stirring to uniformly mix the materials, adding a curing agent (the mass of the curing agent is 33.49 times the epoxy value of the RLEP-15), mixing, removing bubbles by ultrasonic, coating and scraping a film by using a scraper with the thickness of 1000 mu m, and curing for 17 days at room temperature to obtain the lignin and epoxy resin copolymer film (RLEPF-15).
Example 5
(1) 20g E-44 and a certain amount of RL (20 wt% of E-44 mass) were put into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser tube, stirred at 120℃for 1 hour, tetrabutylammonium bromide (1% of E44 mass) was added, the temperature was raised to 160℃and the reaction was carried out for 4 hours to obtain a lignin-epoxy resin copolymer (RLEP-20).
(2) Adding a diluent into RLEP-20 (the mass ratio of the RLEP-20 to the diluent is 1:1), stirring to uniformly mix, adding a curing agent (the mass of the curing agent is 33.49 times the epoxy value of the RLEP-20), mixing, ultrasonically removing bubbles, coating and scraping a film by using a scraper with the thickness of 1000 mu m, and curing for 17 days at room temperature to obtain the lignin and epoxy resin copolymer film (RLEPF-20).
Example 6
(1) 20. 20g E-44 and a certain amount of RL (25 wt% of E-44 mass) were put into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, stirred at 120℃for 1 hour, tetrabutylammonium bromide (1% of E44 mass) was added, the temperature was raised to 160℃and the reaction was carried out for 4 hours to obtain a lignin-epoxy resin copolymer (RLEP-25).
(2) Adding a diluent into RLEP-25 (the mass ratio of the RLEP-25 to the diluent is 1:1), stirring to uniformly mix the materials, adding a curing agent (the mass of the curing agent is 33.49 times the epoxy value of the RLEP-25), mixing, removing bubbles by ultrasonic, coating and scraping a film by using a scraper with the thickness of 1000 mu m, and curing for 17 days at room temperature to obtain the lignin and epoxy resin copolymer film (RLEPF-25).
Example 7
1) The tensile properties of RLEPF bars at room temperature were tested by a universal tester (TY 8000B, TYTESTEER, china) according to the GB/T1040.3-2006 standard, and the bars were made into dumbbell shapes with a length of 200mm and a gauge length of 50 mm. The load cell was 5KN, the crosshead speed was set at 20mm/min, at least three bars were measured per group, and the test results for the products prepared in each example are shown in Table 1.
TABLE 1 results of product Performance parameter testing
The results in Table 1 demonstrate that the elongation at break of lignin and epoxy resin copolymer films are both higher than that of E44 epoxy resin film (RLEPF-0). Wherein the lignin and epoxy copolymer film (RLEPF-25) exhibits excellent toughness as compared with the E44 film, with an increase in elongation at break from 10.6% to 136.5%. When the lignin content exceeds 25wt%, the lignin is difficult to react completely, exhibits a liquid-solid 2 phase, and is difficult to scrape a film. Therefore, the lignin and epoxy resin copolymer film composite material has good practicability.
As shown in FIG. 1, the samples of the relative RLEP-0, RLEP-5 to RLEP-25 were at 2756cm -1 Where 2350-2640cm -1 The O-H vibration peak on the meta-carboxyl group disappeared; the hydroxyl stretching vibration peak is 3472cm -1 Offset to 3436cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The C=O vibration peak is formed by 1762cm -1 Offset to 1729cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The EV value was reduced from 0.44 to 0.21. The above shows that the carboxyl group of E-44 is copolymerized with the hydroxyl group of lignin to form an ester. At 823cm -1 、912cm -1 、1034cm -1 The characteristic vibration peaks of the epoxy compounds are shown, and the RLEP is the epoxy compound.
Claims (10)
1. A preparation method of a lignin and epoxy resin copolymer film is characterized in that black liquor lignin is taken as a raw material, and is subjected to copolymerization reaction with E44 epoxy resin, a curing agent is added, and the lignin and epoxy resin copolymer film composite material is obtained through curing.
2. The method for preparing the lignin and epoxy resin copolymer film according to claim 1 comprising the steps of:
1) Washing black liquor lignin with water to obtain RL;
2) E-44 and RL are added into a reactor with a mechanical stirrer, a thermometer and a condenser tube, stirred and mixed, tetrabutylammonium bromide is added for reaction, and RLEP is prepared after the reaction is finished;
3) Adding the diluent into the RLEP, stirring to uniformly mix the diluent and the RLEP, adding the curing agent, mixing, removing bubbles by ultrasonic, coating and scraping a film by using a scraper, and curing to obtain the RLEPF.
3. The method for producing a lignin and epoxy resin copolymer film according to claim 1 or 2, wherein the black liquor lignin is dissolved in water of equal mass, ph=2 is adjusted with 2wt% sulfuric acid aqueous solution, and the obtained solid is freeze-dried to obtain RL.
4. The method for preparing a lignin and epoxy resin copolymer film according to claim 2 wherein E-44 and RL are stirred at 120 ℃ for 1 hour; tetrabutylammonium bromide was added and reacted at 160℃for 4 hours.
5. The method for producing a lignin and epoxy resin copolymer film according to claim 2 wherein the RL mass is 25wt% or less of the E-44 mass.
6. The method for producing a lignin and epoxy resin copolymer film according to claim 2 wherein the mass of tetrabutylammonium bromide is 1% of the mass of E44.
7. The method for preparing a lignin and epoxy resin copolymer film according to claim 2 wherein the diluent is a mixed solution of xylene and n-butanol in a mass ratio of 4:1, and the amount of the mixed solution is equal to the mass of the epoxy resin; the mass ratio of RLEP to diluent is 1:1.
8. The method for preparing the lignin and epoxy resin copolymer film according to claim 2 wherein the curing agent is cardanol phenolic amine and the mass ratio of cardanol phenolic amine to RLEP is equal to 33.49 x RLEP.
9. The method for preparing a lignin and epoxy resin copolymer film according to claim 2 wherein the doctor blade has a thickness of 1000 μm and is cured at room temperature for 17 days.
10. The lignin and epoxy resin copolymer film prepared by the method of any one of claims 1-9.
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