CN115449053A - Lignin epoxy resin prepared by chemical reaction and toughening modification method - Google Patents
Lignin epoxy resin prepared by chemical reaction and toughening modification method Download PDFInfo
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- CN115449053A CN115449053A CN202110641879.8A CN202110641879A CN115449053A CN 115449053 A CN115449053 A CN 115449053A CN 202110641879 A CN202110641879 A CN 202110641879A CN 115449053 A CN115449053 A CN 115449053A
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- 229920005610 lignin Polymers 0.000 title claims abstract description 126
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 106
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 95
- 238000002715 modification method Methods 0.000 title description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 30
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 24
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 22
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 238000002156 mixing Methods 0.000 description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 7
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 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 5
- 239000008213 purified water Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 244000166124 Eucalyptus globulus Species 0.000 description 2
- 108010059820 Polygalacturonase Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 108010093305 exopolygalacturonase Proteins 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 241000018650 Pinus massoniana Species 0.000 description 1
- 235000011609 Pinus massoniana Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- -1 methoxyl groups Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
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- 235000020824 obesity Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
Abstract
The invention discloses a method for preparing lignin epoxy resin and toughening and modifying the lignin epoxy resin through chemical reaction. A method for preparing lignin epoxy resin and toughening and modifying the lignin epoxy resin through chemical reaction comprises the following steps: adding the pretreated lignin particles and a mixed solvent into a reaction vessel for heating reaction, adding epoxy chloropropane into the reacted mixture, adding sodium hydroxide at constant temperature for reaction, performing reduced pressure distillation to recover water and excessive epoxy chloropropane after the reaction is finished, adding phthalic anhydride and a catalyst into the recovered water and the excessive epoxy chloropropane for reflux reaction, and removing water generated by the reaction under reduced pressure after the reaction is finished to obtain the toughened lignin-based epoxy resin. The invention adopts phthalate toughened lignin-based epoxy resin directly synthesized by chemical reaction, obviously improves the toughness of thermosetting lignin-based epoxy resin, and the prepared toughened thermosetting epoxy resin has excellent impact strength, bending strength and elongation at break.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for preparing lignin epoxy resin through chemical reaction and toughening modification.
Background
Because of having the advantages of better thermal stability, insulation property, adhesiveness, good mechanical property, molding process property, low cost and the like, the epoxy resin is widely applied to the fields of bonding and packaging of electronic components, manufacturing of printed circuit boards and the like, and becomes one of the most important electronic chemical materials at present. Currently, 80% or more of the epoxy resins are bisphenol a type epoxy resins. Bisphenol A monomer is derived from petrochemical industry, and with the use of bisphenol A type epoxy resin, researches show that bisphenol A can cause endocrine dyscrasia, threaten the health of fetuses and children, and the correlation between cancer and obesity caused by metabolic disorder and bisphenol A is reported.
Lignin is a biomass resource with abundant reserves. The artificial forest in China develops rapidly, the area reaches 6933 ten thousand hectares, and the accumulation amount of the artificial forest reaches 24.83 billion cubic meters. According to statistics, the planting area of the eucalyptus in two regions reaches 3400 ten thousand mu as long as 2010. Felling 100m according to the statistical data 3 Wood, 30m will be produced 3 The felling residue of (1). During wood production, the processing residues account for approximately 20% of the raw material. Estimated 2020 every year, about 1.5 million tons of byproducts of forest harvesting, wood processing and the like exist in China, a large part of the forestry residues are directly burned or idle and discarded, so that not only is the resource waste caused, but also the environment is seriously polluted, and the forestry residues contain abundant lignin resources. The yield of the papermaking waste liquid in China is up to 500 million tons every year, which accounts for one sixth of the papermaking waste liquid all over the world, and the papermaking waste liquid is also an important source of lignin. There has been much more than a century of interest in the rational use of lignin resources, but only a small fraction of lignin and its derivatives have gained reasonable use. The lignin is a natural biological polymer with a three-dimensional structure, has a large amount of aromatic groups, methoxyl groups, ether bonds, conjugated double bonds and the like, and has good flame retardant propertyAnd thermal stability. Meanwhile, the epoxy resin has a large number of functional groups such as phenolic hydroxyl, alcoholic hydroxyl, carbonyl and the like, and the structure of the epoxy resin is similar to that of bisphenol A, and the epoxy resin can be directly prepared by the reaction and epoxidation of the bisphenol A and epichlorohydrin. The utilization rate of the waste lignin can be improved by utilizing the lignin to produce the epoxy resin, the high added value of the lignin is increased, and the waste is changed into valuable.
Although the epoxy resin has excellent bonding strength, good dielectric property, high hardness and strong corrosion resistance, the epoxy resin is widely applied to various fields of national defense and industrial production. However, the pure epoxy resin has high crosslinking density after being cured and is in a three-dimensional crosslinking network structure, so the pure epoxy resin has the defects of brittle quality, fatigue resistance, poor impact toughness and the like, and is easy to generate stress cracking when being acted by external impact stress. In addition, in the curing process of the epoxy resin, internal stress is generated due to volume shrinkage and the like, so that the material is warped, cracked, reduced in strength and the like, the requirements of increasingly developed engineering technology are difficult to meet, and the application of the epoxy resin is limited to a certain extent. Therefore, in order to fully develop the high performance of the epoxy resin, toughening modification is required. The approach of toughening the epoxy resin is to introduce a flexible chain segment into the molecular structure of the epoxy resin as much as possible under the condition of ensuring that the matrix reaches a certain thermal deformation temperature, so that the yield deformation capability of the epoxy matrix is improved.
There are two main approaches to toughening epoxy resins:
1. improved from the structure, such as 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid diglycidyl ester (TDE-85) which is well known. Zhengzilian et al studied the application performance of TDE-85 and aromatic amine curing agent after curing, and found that the modulus after curing is up to 5.3GPa for TDE-85/MPD system, the modulus is significantly improved compared with 2.3 GPa-3.0 GPa of common bisphenol A epoxy resin, and the elongation at break is about 1.6-2.5%; while the TDE-85/DDS system has an impact strength of up to 17.1 MPa. Aging and the like, and the polyester type epoxy resin is prepared by using high boiling point alcohol (HBS) lignin as a raw material. The reaction process is as follows: firstly, fully dissolving HBS lignin in ethylene glycol, and reacting with maleic anhydride to generate HBS lignin-polymeric acid accompanied by generation of a byproduct ethylene glycol polymer. Then the polymeric acid reacts with ethylene glycol diglycidyl ether to obtain the lignin-based polyester epoxy resin, and the impact strength, the tensile strength and the bending strength are all improved. The effect of structural change is remarkable, but it is difficult to implement.
2. Blending modification: the main function of the added toughening agent is to increase the toughness of the epoxy resin and improve the bending strength and the shock resistance. The existing toughening method has less research and is carried out in a mixed compounding way. Mainly adopts toughening substances which are roughly divided into rubber elastomers, liquid crystal polymers, thermoplastic resins, core-shell structure polymers, hyperbranched polymers, inorganic nanoparticles and the like. These toughening methods often cause problems while achieving the purpose of toughening. For example, epoxy resins were first toughened with rubber elastomers such as nitrile rubber, but since the rubber contains unsaturated bonds, degradation and aging easily occur under high temperature and aerobic conditions, with a consequent decrease in the heat resistance and dielectric resistance of the epoxy resin. Some epoxy resins modified by thermoplastic resins with high modulus and good heat resistance have poor modification effect due to poor compatibility of two phases and weak interface acting force of a cured epoxy resin system, so that a new method for improving the toughness of the epoxy resin is required.
Disclosure of Invention
The invention solves the problems in the prior art, and aims to provide a lignin epoxy resin preparation method through chemical reaction and a toughening modification method.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing lignin epoxy resin and toughening and modifying the lignin epoxy resin through chemical reaction comprises the following steps: adding the pretreated lignin particles and a mixed solvent into a reaction vessel for heating reaction, adding epoxy chloropropane into the reacted mixture, adding sodium hydroxide at constant temperature for reaction, performing reduced pressure distillation to recover water and excessive epoxy chloropropane after the reaction is finished, adding phthalic anhydride and a catalyst into the recovered water and the excessive epoxy chloropropane for reflux reaction, and removing water generated by the reaction under reduced pressure after the reaction is finished to obtain the toughened lignin-based epoxy resin.
The lignin particles come from two places: (1) The lignin particles are remainder extracts of artificial forests and forestry, and mainly comprise eucalyptus, poplar, larch, masson pine and the like. Extracting the biomass residue by using ionic liquid, and carrying out mixed enzyme hydrolysis treatment on the cellulose and the pectinase for 72 hours to obtain a lignin raw material suitable for preparing the lignin-based epoxy resin; (2) The lignin particles are the extract of the papermaking black liquor, and the crude lignin is subjected to enzymolysis treatment for 72 hours by cellulase and pectinase. Washing, drying and crushing the lignin obtained at the two positions by deionized water, and taking the lignin with the particle size of less than or equal to 0.1 mu m for use.
Preferably, the method for preparing the lignin epoxy resin and toughening and modifying through the chemical reaction comprises the following steps: adding the pretreated lignin particles and a mixed solvent into a reaction vessel, heating to 180-220 ℃, stirring for reaction, adding epoxy chloropropane into the reacted mixture, adding sodium hydroxide at a constant temperature of 70-90 ℃ for reaction, performing reduced pressure distillation to recover water and excessive epoxy chloropropane after the reaction is finished, adding phthalic anhydride and a catalyst into the recovered water and the excessive epoxy chloropropane for reflux reaction, and removing water generated by the reaction under reduced pressure after the reaction is finished to obtain the toughened lignin-based epoxy resin.
The method comprises the following specific steps of adding sodium hydroxide at a constant temperature of 70-90 ℃ for reaction: sodium hydroxide with the mass fraction of 20% is added at the constant temperature of 70-90 ℃ for reaction for 2-4h, and the solid-to-liquid ratio of the lignin particles to the sodium hydroxide solution is 2-10 g/mL.
Preferably, the mixed solvent is a mixed solvent of epichlorohydrin and an alcohol organic solvent, the volume ratio of the epichlorohydrin to the alcohol organic solvent is 1-3.
The invention adopts chemical reaction to prepare lignin-based epoxy resin and a toughening method, the added alcohol is just used as a solvent, and is changed into a reactant later, the method is continuous and one-time, the preparation process is simple, other special equipment is not needed, the operation process is easy to implement, and the production cost is reduced.
Further preferably, the molar ratio of the phthalic anhydride to the alcoholic organic solvent is 1.
More preferably, the catalyst is NaHSO 4 The mass of the catalyst is 0.6-1.2% of the total mass of the alcohol organic solvent and the phthalic anhydride.
Preferably, the pretreatment step of the pretreated lignin particles is: and (3) crushing the lignin solid by using a crusher to obtain lignin particles, and drying the lignin particles with the particle size of less than 0.1 mu m in a drying oven at 105 ℃ for 7-8 hours to constant weight to obtain the pretreated lignin particles.
Preferably, the solid-liquid ratio of the lignin particles to the mixed solvent is 1.
Preferably, the reflux reaction temperature is 130-150 ℃, the reflux reaction time is 3-5h, and the reaction time of stirring reaction when heating to 180-220 ℃ is 1-3h.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts phthalate toughened lignin-based epoxy resin directly synthesized by chemical reaction, obviously improves the toughness of thermosetting lignin-based epoxy resin, and the prepared toughened thermosetting epoxy resin has excellent impact strength, bending strength and elongation at break.
2. The invention adopts the method of directly synthesizing the phthalate toughening lignin-based epoxy resin by chemical reaction, and the method of reaction and fusion ensures that the plasticizer is uniformly dispersed in the epoxy resin and the solubility is improved, and simultaneously, the branched hydroxyl of some alcohol solvents can also have chemical reaction with the epoxy resin, thereby improving the toughness of the epoxy resin.
3. The invention adopts chemical reaction to prepare lignin-based epoxy resin and a toughening method, the lignin raw material is a bio-based material, and the lignin-based epoxy resin has complete biodegradability, reduces the dependence on fossil resources to a certain extent, and relieves the problem of white pollution.
4. The invention adopts the chemical reaction to prepare the lignin-based epoxy resin and the toughening method, the added alcohol is just used as a solvent, and then is changed into a reactant, the method is continuously finished, the preparation process is simple, other special equipment is not needed, the operation process is easy to implement, and the production cost is reduced.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
The materials used were as follows:
lignin particles (papermaking black liquor extract, particle diameter is less than or equal to 0.1 mu m, purity is 91.6%);
epichlorohydrin (specification: not less than 99.5% (GC), shanghai Allantin Biotechnology Co., ltd.);
1, 3-butanediol (specification: 98%, shanghai Aladdin Biotechnology Co., ltd.);
ethylene glycol (specification: >99% (GC), shanghai alading biochem technologies, ltd);
phthalic anhydride (specification: 500g, sahn chemical technology (Shanghai) Co., ltd.);
curing agent (methyl nadic anhydride, specification: more than or equal to 95.0%, shanghai Michelin Biochemical technology Co., ltd.);
a curing reaction accelerator (2-ethylimidazole, specification: not less than 99%, shanghai Michelin Biotechnology Co., ltd.).
The preparation reaction of the toughened lignin-based epoxy resin comprises the following steps:
(1) Adding the pretreated lignin particles and the mixed solvent into a reaction kettle at the temperature of between 180 and 220 ℃, fully stirring, dissolving and reacting for 1 to 3 hours;
(2) Adding a certain amount of epoxy chloropropane into the mixed solution reacted in the step (1), dripping a NaOH catalyst with the mass fraction of 20% at a constant temperature of 70-90 ℃, reacting for a period of time, and performing reduced pressure distillation to recover the mixed solution of the dripped water and the excessive epoxy chloropropane;
(3) Adding phthalic anhydride and a catalyst into the recovered mixed solution of the excessive epichlorohydrin, carrying out reflux reaction for a period of time under a certain temperature condition, controlling the temperature at 80 ℃ after the reaction is finished, removing water generated by the reaction under reduced pressure, adding dichloromethane, mixing uniformly, extracting, adding a certain amount of purified water to wash residual alcohol solvent and the catalyst, standing, separating a water layer, heating to 80 ℃ and carrying out reduced pressure rotary evaporation to remove residual water to obtain the toughened lignin-based epoxy resin.
In the invention, the pretreatment steps of the lignin particles pretreated in the step (1) are as follows: and (3) crushing the lignin solid by using a crusher to obtain lignin particles, and drying the lignin particles with the particle size of less than 0.1 mu m in a drying oven at 105 ℃ for 7-8 hours to constant weight to obtain the pretreated lignin particles.
In the following examples, the mixed solvent is a mixed solvent of epichlorohydrin and an alcohol organic solvent, the volume ratio of epichlorohydrin to alcohol is 1-3, and the alcohol is one or two selected from ethylene glycol, glycerol, butanol, 1, 3-butanediol, 1, 4-butanediol and octanol. The solid-liquid ratio of the lignin particles to the mixed solvent is 1.
In the following embodiment, sodium hydroxide with the mass fraction of 20% is added at the constant temperature of 70-90 ℃ in the step (2) for reaction for 2-4h, and the solid-to-liquid ratio of the lignin particles to the sodium hydroxide solution is 2-10 g/mL. The solid-liquid ratio of the lignin particles to the epichlorohydrin is 1.
In the following examples, the molar ratio of the phthalic anhydride to the alcoholic organic solvent in step (3) is 1. The catalyst is NaHSO 4 The mass of the catalyst is 0.6-1.2% of the total mass of the alcohol organic solvent and the phthalic anhydride. The reflux reaction temperature is 130-150 ℃, and the reflux reaction time is 3-5h.
In the following examples, the curing conditions of the lignin-based epoxy resin prepared in each example and comparative example were as follows: mixing methyl nadic anhydride and epoxy group of lignin-based epoxy resin in a ratio of 0.85:1, then adding 2-ethylimidazole with the mass fraction of 1.0wt% of the mass of the epoxy resin as a curing reaction accelerator, carrying out vacuum air suction soaking at the temperature of 80 ℃ for 15min, pouring the mixture into a stainless steel mold while the mixture is hot, and curing, wherein the specific curing conditions are as follows: curing at 85 ℃ for 4h, curing at 120 ℃ for 12h and curing at 150 ℃ for 12h.
The lignin-based epoxy resin prepared in each example and comparative example has the following performance tests:
1. tensile strength test was conducted according to ASTM D638, type I, specimen size (mm): 130X 13X 4, and a drawing speed of 2mm/min.
2. Izod impact strength was measured according to ISO 180/1A, type I, specimen size (mm): 130 × 13 × 4, pendulum nominal energy: 5.5J.
3. The bending strength test is carried out according to the GB/T6569-86 standard, the type of the sample is type I, and the size (mm) of the sample is as follows: 130X 13X 4, and a drawing speed of 2mm/min.
Example 1
The preparation reaction of the toughened lignin-based epoxy resin comprises the following steps:
(1) Crushing the solid lignin extracted from the papermaking black liquor by using a universal crusher, sieving by using a stainless steel sieve, and placing lignin powder with the particle size of less than 0.1 mu m in a drying oven at 105 ℃ for drying for 7 hours to constant weight to obtain dried lignin particles. Adding 4g of dried lignin particles into a magnetic stirring pressure kettle, and mixing the lignin particles and 1, 3-butanediol according to a solid-to-liquid ratio of 1: 40mL of 1, 3-butanediol was added at 10g/mL, and the volume ratio of 1, 3-butanediol to epichlorohydrin was 1:2, adding 80mL of epoxy chloropropane, reacting for 1 hour under the condition of 180 ℃ electric heating, and taking out the reaction mixture.
(2) And taking the prepared mixture out of the three-neck flask, adding 60mL of epoxy chloropropane, stirring and mixing uniformly under the heating condition of a constant-temperature oil bath at 80 ℃, dropwise adding 15mL of 20% NaOH solution at a constant speed by using a peristaltic pump, and reacting for 3 hours at a constant temperature. After the reaction, the lower aqueous layer was separated by standing. And (3) distilling the upper oil layer under reduced pressure to recover excessive epichlorohydrin and remove residual water under the condition of controlling the temperature to be 80 ℃.
(3) Adding phthalic anhydride into the mixed solution obtained in the step (2), wherein the molar ratio of the phthalic anhydride to the 1, 3-butanediol is 1:2, adding NaHSO 4 Catalyst, naHSO 4 The mass of the compound (b) is 0.6 percent of the total mass of 1,3 butanediol and phthalic anhydride, and the reflux reaction is carried out for 3 hours at the temperature of 130 ℃. After the reaction is finished, cooling to room temperature, adding 100mL of dichloromethane extractant, fully mixing uniformly, adding purified water accounting for 40% of the total volume, and fully mixing. Standing until the upper oil layer and the lower water layer are completely separated, slowly heating the oil layer to 80 ℃, and carrying out reduced pressure rotary evaporation to remove dichloromethane and residual water, thereby obtaining the toughened lignin-based epoxy resin.
And measuring the epoxy value of the epoxy resin on the toughened lignin and calculating the required curing agent amount according to the epoxy value. Mixing methyl nadic anhydride and epoxy group of lignin-based epoxy resin in a ratio of 0.85:1, adding 2-ethylimidazole with the mass fraction of 1.0wt% of the mass of the epoxy resin as a curing reaction accelerator, carrying out vacuum air suction soaking at the temperature of 80 ℃ for 15min, pouring the mixture into a stainless steel mold while the mixture is hot, wherein the specific curing conditions are as follows: curing at 85 ℃ for 4h, curing at 120 ℃ for 12h and curing at 150 ℃ for 12h to obtain the epoxy resin sample strip to be tested.
Example 2
The preparation reaction of the toughened lignin-based epoxy resin comprises the following steps:
(1) Crushing lignin solid extracted from the papermaking black liquor by using a universal crusher, sieving by using a stainless steel sieve, and drying lignin powder with the particle size of less than 0.1 mu m in a drying oven at 105 ℃ for 7 hours to constant weight to obtain dried lignin particles. Adding 2g of dried lignin particles into a magnetic stirring pressure kettle, and mixing the lignin particles and ethylene glycol according to a solid-to-liquid ratio of 1: adding 20mL of glycol into 10g/mL, and mixing the mixture according to the volume ratio of the glycol to the epichlorohydrin of 1:2, adding 40mL of epoxy chloropropane, reacting for 1 hour under the condition of 180 ℃ electric heating, and taking out the reaction mixture.
(2) And taking the prepared mixture out of the three-neck flask, adding 30mL of epoxy chloropropane, stirring and mixing uniformly under the constant-temperature oil bath heating condition of 80 ℃, dropwise adding 7.5mL of 20% NaOH solution at a constant speed by using a peristaltic pump, and reacting for 3 hours at a constant temperature. After the reaction, the lower aqueous layer was separated by standing. And (3) distilling the upper oil layer under reduced pressure to recover excessive epichlorohydrin and remove residual water under the condition of controlling the temperature to be 80 ℃.
(3) Adding phthalic anhydride into the mixed solution obtained in the step (2), wherein the molar ratio of the phthalic anhydride to the ethylene glycol is 1:2, adding NaHSO 4 Catalyst, naHSO 4 The mass of the catalyst is 0.6 percent of the total mass of the glycol and the phthalic anhydride, and the reflux reaction is carried out for 3 hours at the temperature of 130 ℃. After the reaction is finished, cooling to room temperature, adding 80mL of dichloromethane extractant, fully mixing uniformly, adding purified water with the total volume of 40%, and fully mixing. Standing until the upper oil layer and the lower water layer are completely separated, slowly heating the oil layer to 80 ℃, and carrying out decompression rotary evaporation to remove dichloromethane and residual water to obtain the toughened lignin-based epoxy resin.
And measuring the epoxy value of the toughened lignin epoxy resin and calculating the required curing agent amount according to the epoxy value. Reacting methyl nadic anhydride with the epoxy groups of the lignin-based epoxy resin in a ratio of 0.85:1, adding 2-ethylimidazole with the mass fraction of 1.0wt% of the mass of the epoxy resin as a curing reaction accelerator, vacuumizing and soaking for 15min at the temperature of 80 ℃, and pouring the mixture into a stainless steel mold while the mixture is hot. The specific curing conditions are as follows: curing at 85 ℃ for 4h, curing at 120 ℃ for 12h and curing at 150 ℃ for 12h to obtain the epoxy resin sample strip to be tested.
Example 3
The same as in example 1, except that: in the step (1), the alcohol organic solvent is glycerol and butanol, the volume ratio of the glycerol to the butanol is 1; the reaction time for stirring the reaction is 1h when heating to 200 ℃.
In the step (2), 40mL of epoxy chloropropane is added into the mixed solution in the step 1, 35mL of sodium hydroxide solution with the mass fraction of 20% is dropwise added at the constant temperature of 70 ℃, and the reaction is carried out for 4 hours. After the reaction, the lower aqueous layer was separated by standing. And (3) carrying out reduced pressure distillation on the upper oil layer at the temperature of 80 ℃ to recover the mixed liquid consisting of the excessive epichlorohydrin and the removed residual water.
In the step (3), the molar ratio of the phthalic anhydride to the alcoholic organic solvent is 1. NaHSO 4 The mass of the catalyst is 0.9 percent of the total mass of the alcohol organic solvent and the phthalic anhydride. The reflux reaction temperature is 130 ℃, and the reflux reaction time is 5h. After the reaction is finished, cooling to room temperature, adding 100mL of dichloromethane extractant, fully mixing uniformly, adding purified water with the total volume of 60%, and fully mixing. Standing until the upper oil layer and the lower water layer are completely separated, slowly heating the oil layer to 80 ℃, and carrying out decompression rotary evaporation to remove dichloromethane and residual water to obtain the toughened lignin-based epoxy resin.
And measuring the epoxy value of the toughened lignin epoxy resin and calculating the required curing agent amount according to the epoxy value. Mixing methyl nadic anhydride and epoxy group of lignin-based epoxy resin in a ratio of 0.85:1, adding 2-ethylimidazole with the mass fraction of 1.0wt% of the mass of the epoxy resin as a curing reaction accelerator, vacuumizing and soaking for 15min at the temperature of 80 ℃, and pouring the mixture into a stainless steel mold while the mixture is hot. The specific curing conditions are as follows: curing at 85 ℃ for 4h, curing at 120 ℃ for 12h and curing at 150 ℃ for 12h to obtain the epoxy resin sample strip to be tested.
Example 4
The same as in example 1, except that: in the step (1), the alcohol organic solvent is 1, 4-butanediol and octanol, the volume ratio of the 1, 4-butanediol to the octanol is 1; the reaction time was 1h with stirring while heating to 220 ℃.
In the step (2), 40mL of epoxy chloropropane is added into the mixed solution in the step (1), 45mL of sodium hydroxide solution with the mass fraction of 20% is dripped at the constant temperature of 90 ℃, and the reaction is carried out for 2h. After the reaction, the lower aqueous layer was separated by standing. And (3) distilling the upper oil layer under reduced pressure to recover excessive epichlorohydrin and remove residual water under the condition of controlling the temperature to be 80 ℃.
In the step (3), the molar ratio of the phthalic anhydride to the alcohol organic solvent is 1. NaHSO 4 The mass of the catalyst is 1.2 percent of the total mass of the alcohol organic solvent and the phthalic anhydride. The reflux reaction temperature is 150 ℃, andthe flow reaction time was 3h. After the reaction is finished, cooling to room temperature, adding 100mL of dichloromethane extractant, fully mixing uniformly, adding purified water accounting for 60 percent of the total volume, and fully mixing. Standing until the upper oil layer and the lower water layer are completely separated, slowly heating the oil layer to 80 ℃, and carrying out reduced pressure rotary evaporation to remove dichloromethane and residual water to obtain the toughened lignin-based epoxy resin.
And measuring the epoxy value of the toughened lignin epoxy resin and calculating the required curing agent amount according to the epoxy value. Mixing methyl nadic anhydride and epoxy group of lignin-based epoxy resin in a ratio of 0.85:1, adding 2-ethylimidazole with the mass fraction of 1.0wt% of the mass of the epoxy resin as a curing reaction accelerator, vacuumizing and soaking for 15min at the temperature of 80 ℃, and pouring the mixture into a stainless steel mold while the mixture is hot. The specific curing conditions are as follows: curing at 85 ℃ for 4h, curing at 120 ℃ for 12h and curing at 150 ℃ for 12h to obtain the epoxy resin sample strip with the performance to be tested.
Comparative example 1
Crushing the solid lignin extracted from the papermaking black liquor by using a universal crusher, sieving by using a stainless steel sieve, and placing lignin powder with the particle size of less than 0.1 mu m in a drying oven at 105 ℃ for drying for 7 hours to constant weight to obtain dried lignin particles. Adding 4g of dried lignin particles into a magnetic stirring pressure kettle, and mixing the lignin particles and 1, 3-butanediol according to a solid-to-liquid ratio of 1: 40mL of 1, 3-butanediol was added at 10g/mL, and the volume ratio of 1, 3-butanediol to epichlorohydrin was 1:2, adding 80mL of epichlorohydrin, reacting for 1 hour under the condition of 180 ℃ electric heating, and taking out the reaction mixture. And taking the prepared mixture out of the three-neck flask, adding 60mL of epoxy chloropropane, stirring and mixing uniformly under the constant-temperature oil bath heating condition of 80 ℃, dropwise adding 15mL of 20% NaOH solution at a constant speed by using a peristaltic pump, and reacting for 3 hours at a constant temperature. After the reaction, the mixture was allowed to stand to separate a lower aqueous layer. And (3) carrying out reduced pressure distillation on the upper oil layer at the temperature of 80 ℃ to recover the mixed liquid consisting of the excessive epichlorohydrin and the removed residual water.
The epoxy value of the lignin epoxy resin is determined and the required curing agent amount is calculated according to the epoxy value. Mixing methyl nadic anhydride and epoxy group of lignin-based epoxy resin in a ratio of 0.85:1, adding 2-ethylimidazole with the mass fraction of 1.0wt% of the mass of the epoxy resin as a curing reaction accelerator, vacuumizing and soaking for 15min at the temperature of 80 ℃, and pouring the mixture into a stainless steel mold while the mixture is hot. The specific curing conditions are as follows: curing at 85 ℃ for 4h, curing at 120 ℃ for 12h and curing at 150 ℃ for 12h to obtain the epoxy resin sample strip with the performance to be tested.
The epoxy resin sample bars obtained in examples 1-4 and comparative example 1 were subjected to mechanical property test, and the mechanical property results of the toughened lignin epoxy resin were obtained as shown in table 1 below:
TABLE 1
As can be seen from the above table, the test properties of the epoxy resin bars of examples 1 to 4 are greatly improved in elongation at break and impact strength showing toughness, and still have higher tensile strength values and bending strength values, compared to comparative example 1. The application range of the toughened lignin epoxy resin is greatly increased, and the toughened lignin epoxy resin has high innovation value.
The above are only preferred embodiments of the present invention, and it should be noted that the above preferred embodiments should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A method for preparing lignin epoxy resin and toughening and modifying the lignin epoxy resin through chemical reaction is characterized by comprising the following steps: adding the pretreated lignin particles and a mixed solvent into a reaction vessel for heating reaction, adding epoxy chloropropane into the reacted mixture, adding sodium hydroxide at constant temperature for reaction, performing reduced pressure distillation to recover water and excessive epoxy chloropropane after the reaction is finished, adding phthalic anhydride and a catalyst into the recovered water and the excessive epoxy chloropropane for reflux reaction, and removing water generated by the reaction under reduced pressure after the reaction is finished to obtain the toughened lignin-based epoxy resin.
2. The method for preparing lignin epoxy resin and toughening and modifying according to claim 1, comprising the following steps: adding the pretreated lignin particles and a mixed solvent into a reaction vessel, heating to 180-220 ℃, stirring for reaction, adding epoxy chloropropane into the reacted mixture, adding sodium hydroxide at a constant temperature of 70-90 ℃ for reaction, performing reduced pressure distillation to recover water and excessive epoxy chloropropane after the reaction is finished, adding phthalic anhydride and a catalyst into the recovered water and the excessive epoxy chloropropane for reflux reaction, and removing water generated by the reaction under reduced pressure after the reaction is finished to obtain the toughened lignin-based epoxy resin.
3. The method for preparing lignin epoxy resin and toughening and modifying according to claim 1 or 2, wherein the mixed solvent is a mixed solvent of epichlorohydrin and an alcohol organic solvent, the volume ratio of epichlorohydrin to the alcohol organic solvent is 1-3, and the alcohol organic solvent is one or two selected from ethylene glycol, glycerol, butanol, 1, 3-butanediol, 1, 4-butanediol and octanol.
4. The method for preparing lignin epoxy resin and toughening and modifying according to claim 3, wherein the molar ratio of the phthalic anhydride to the alcohol organic solvent is 1.
5. The method for preparing lignin epoxy resin and toughening and modifying according to claim 3, wherein the catalyst is NaHSO 4 The catalyst is alcohol organic solvent0.6 to 1.2 percent of the total mass of the agent and the phthalic anhydride.
6. The method for preparing lignin epoxy resin and toughening and modifying according to claim 1 or 2, wherein the pretreatment of the pretreated lignin particles comprises: and (3) crushing the lignin solid by using a crusher to obtain lignin particles, and drying the lignin particles with the particle size of less than 0.1 mu m in a drying oven at 105 ℃ for 7-8 hours to constant weight to obtain the pretreated lignin particles.
7. The method for preparing the lignin epoxy resin and toughening and modifying according to claim 1, wherein the solid-to-liquid ratio of the lignin particles to the mixed solvent is 1.
8. The method for preparing the lignin epoxy resin and toughening and modifying the lignin epoxy resin through the chemical reaction according to claim 1 or 2, wherein the solid-to-liquid ratio of the lignin particles to the epichlorohydrin is 1.
9. The method for preparing the lignin epoxy resin and toughening and modifying through chemical reaction according to claim 1, wherein the reflux reaction temperature is 130-150 ℃, and the reflux reaction time is 3-5h.
10. The method for preparing lignin epoxy resin and toughening and modifying through chemical reaction according to claim 1, wherein the reaction time of the stirring reaction when the temperature is increased to 180-220 ℃ is 1-3h.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3149085A (en) * | 1958-10-20 | 1964-09-15 | West Virginia Pulp & Paper Co | Method of making synthetic resin from lignin and an epoxide and resulting product |
CN1966545A (en) * | 2006-10-21 | 2007-05-23 | 福州大学 | Enzymatic hydrolysis lignin epoxy resin material formula and its preparation method |
KR101880390B1 (en) * | 2017-02-23 | 2018-08-16 | 경희대학교 산학협력단 | customized chemical modification method using lignin |
CN110358055A (en) * | 2019-07-29 | 2019-10-22 | 南京林业大学 | The method that one kettle way prepares lignin acid anhydride curable epoxy resin |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3149085A (en) * | 1958-10-20 | 1964-09-15 | West Virginia Pulp & Paper Co | Method of making synthetic resin from lignin and an epoxide and resulting product |
CN1966545A (en) * | 2006-10-21 | 2007-05-23 | 福州大学 | Enzymatic hydrolysis lignin epoxy resin material formula and its preparation method |
KR101880390B1 (en) * | 2017-02-23 | 2018-08-16 | 경희대학교 산학협력단 | customized chemical modification method using lignin |
CN110358055A (en) * | 2019-07-29 | 2019-10-22 | 南京林业大学 | The method that one kettle way prepares lignin acid anhydride curable epoxy resin |
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