CN115449053B - Method for preparing lignin epoxy resin and toughening modification through chemical reaction - Google Patents
Method for preparing lignin epoxy resin and toughening modification through chemical reaction Download PDFInfo
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- CN115449053B CN115449053B CN202110641879.8A CN202110641879A CN115449053B CN 115449053 B CN115449053 B CN 115449053B CN 202110641879 A CN202110641879 A CN 202110641879A CN 115449053 B CN115449053 B CN 115449053B
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- 229920005610 lignin Polymers 0.000 title claims abstract description 113
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 88
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000004048 modification Effects 0.000 title abstract description 10
- 238000012986 modification Methods 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 23
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 22
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000012046 mixed solvent Substances 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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 24
- 239000003960 organic solvent Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005452 bending Methods 0.000 abstract description 4
- 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 13
- 239000011259 mixed solution Substances 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
- 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 8
- 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
- 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 7
- 239000000243 solution Substances 0.000 description 7
- 230000005587 bubbling Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 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 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 3
- 238000003306 harvesting Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 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
- 239000002253 acid Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
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- 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
- 241000218378 Magnolia Species 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
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- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 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
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- 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
- 238000005538 encapsulation Methods 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
- 238000007676 flexural strength test Methods 0.000 description 1
- -1 forest harvest Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000009776 industrial production 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 230000035939 shock Effects 0.000 description 1
- 238000010025 steaming Methods 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
Landscapes
- Chemical & Material Sciences (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 method for preparing lignin epoxy resin and toughening modification through chemical reaction. A method for preparing lignin epoxy resin and toughening modification 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 mixture after the reaction, adding sodium hydroxide at constant temperature for reaction, distilling under reduced pressure after the reaction is finished to recover water and excessive epoxy chloropropane, adding phthalic anhydride and a catalyst into the recovered water and excessive epoxy chloropropane for reflux reaction, and removing the water generated by the reaction under reduced pressure after the reaction is finished to obtain the toughened lignin-based epoxy resin. According to the invention, the phthalate toughening lignin-based epoxy resin directly synthesized by chemical reaction is adopted, so that the toughness of the thermosetting lignin-based epoxy resin is remarkably improved, 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 and toughening and modifying the lignin epoxy resin through chemical reaction.
Background
The epoxy resin has the advantages of good thermal stability, insulativity, adhesiveness, good mechanical property, molding process performance, low cost and the like, and is widely applied to the fields of adhesion, encapsulation of electronic components, manufacture 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 along with the use of bisphenol A epoxy resin, researches and discovers that bisphenol A can cause endocrine dyscrasia, threaten the health of fetuses and children, and reports that obesity caused by cancers and metabolic disorder is related to bisphenol A.
Lignin is a biomass resource with a rich reserve. 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 hundred million cubic meters. The eucalyptus planting area in the two broad areas is up to 3400 ten thousand acres by the year 2010. Based on statistics, 100m of harvesting 3 Wood, which can generate 30m 3 Is a harvest residue of (2). During wood production, the processing residues account for about 20% of the raw material. About 1.5 hundred million tons of byproducts such as forest harvest, wood processing and the like are expected to exist in 2020 China each year, and a large part of forestry residues are directly burnt or idle to be discarded, so that not only is the resource wasted, but also the environment is seriously polluted, and the forestry residues are rich in lignin resources. The output of the waste paper-making liquid in China per year is up to 500 ten thousand tons, which accounts for one sixth of the waste paper-making liquid worldwide, and the waste paper-making liquid is an important source of lignin. There has been a century interest in the rational use of lignin resources, but only a small fraction of lignin and its derivatives have been reasonably used. Lignin is a natural biopolymer with a three-dimensional structure, has a large number of aromatic groups, methoxy groups, ether bonds, conjugated double bonds and the like, and has good flame retardant property and 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 is similar to that of bisphenol A, and the epoxy resin can be prepared by directly reacting with epichlorohydrin for epoxidation. The utilization rate of waste lignin can be improved by using lignin to produce epoxy resin, the high added value of lignin is increased, and 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 cured pure epoxy resin has the defects of high crosslinking density, three-dimensional crosslinked network structure, brittle quality, fatigue resistance, poor impact toughness and the like, and is easy to generate stress cracking phenomenon when being subjected to external impact stress. In addition, the epoxy resin generates internal stress due to volume shrinkage and the like in the curing process, so that the materials are difficult to meet the requirements of increasingly developed engineering technologies, 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, it is necessary to toughen and modify the epoxy resin. The way to toughen the epoxy resin is to introduce as much flexible chain segments as possible into the molecular structure of the epoxy resin under the condition that the base body reaches a certain heat deformation temperature, so as to improve the yield deformation capability of the epoxy base body.
There are two main approaches to toughening epoxy resins:
1. structurally improved, as is well known as diglycidyl 1, 2-epoxycyclohexane-4, 5-dicarboxylate (TDE-85). Zheng Yaping et al studied the application properties of TDE-85 and aromatic amine curing agents after curing, found that for TDE-85/MPD systems, the modulus after curing was as high as 5.3GPa, which is significantly improved compared with the modulus of 2.3 GPa-3.0 GPa of the general bisphenol A epoxy resin, and the elongation at break was about 1.6-2.5%; whereas the TDE-85/DDS system has an impact strength of up to 17.1 MPa. Chen Weijian and the like, which are prepared from high-boiling alcohol (HBS) lignin as a raw material. The reaction process is as follows: firstly, fully dissolving HBS lignin in glycol, and reacting with maleic anhydride to generate HBS lignin-polymeric acid with the formation of a byproduct glycol polymer. And then the polymeric acid reacts with ethylene glycol diglycidyl ether to obtain lignin-based polyester epoxy resin, and the impact strength, the tensile strength and the bending strength are all improved. The effect of the structural change is remarkable, but the implementation is difficult.
2. Blending modification: the toughening agent has the main functions of increasing the toughness of the epoxy resin and improving the bending strength and the shock resistance. The existing toughening method has less research and is carried out by a mixed compounding mode. The toughening substances mainly adopted are roughly classified into rubber elastomer, liquid crystal polymer, thermoplastic resin, core-shell structure polymer, hyperbranched polymer, inorganic nano particles and the like. The toughening methods often bring corresponding problems while achieving the toughening purpose. For example, the epoxy resin is initially toughened with a rubber elastomer such as nitrile rubber, but since the rubber contains unsaturated bonds, degradation and aging easily occur under high temperature and aerobic conditions, which in turn reduces the heat resistance and medium resistance of the epoxy resin. Some modified epoxy resins are modified by using thermoplastic resins with high modulus and good heat resistance, but the modified epoxy resins have poor modification effect due to poor compatibility of two phases of the cured epoxy resin system and weak interfacial force, so that a new method is required to improve the toughness of the epoxy resins.
Disclosure of Invention
The invention solves the problems in the prior art, and aims to provide the lignin-based epoxy resin prepared by chemical reaction and the toughening modification method.
In order to achieve the above purpose, the invention adopts the following technical scheme: a method for preparing lignin epoxy resin and toughening modification 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 mixture after the reaction, adding sodium hydroxide at constant temperature for reaction, distilling under reduced pressure after the reaction is finished to recover water and excessive epoxy chloropropane, adding phthalic anhydride and a catalyst into the recovered water and excessive epoxy chloropropane for reflux reaction, and removing the 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 sources: (1) The lignin particles are the remainder extract of the forestry of the artificial forest, and mainly comprise eucalyptus, poplar, larch, masson pine and the like. Extracting biomass residues by using ionic liquid, and carrying out mixed enzyme hydrolysis treatment on cellulose and pectase for 72 hours to obtain lignin raw materials suitable for preparing lignin-based epoxy resin; (2) The lignin particles are papermaking black liquor extract, and crude lignin is subjected to enzymolysis treatment by cellulase and pectase for 72 hours. Washing, drying and crushing lignin obtained in the two places by deionized water, and taking the lignin with the particle size less than or equal to 0.1 mu m for use.
Preferably, the method for preparing lignin epoxy resin and toughening modification through chemical reaction specifically comprises the following steps: adding the pretreated lignin particles and a mixed solvent into a reaction vessel, heating to 180-220 ℃ for stirring reaction, adding epoxy chloropropane into the mixture after the reaction, adding sodium hydroxide at a constant temperature of 70-90 ℃ for reaction, distilling under reduced pressure after the reaction is finished to recover water and excessive epoxy chloropropane, adding phthalic anhydride and a catalyst into the recovered water and 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 specific steps of adding sodium hydroxide at the constant temperature of 70-90 ℃ for reaction are as follows: adding 20% sodium hydroxide at a constant temperature of 70-90 ℃ to react for 2-4h, wherein the solid-liquid ratio of lignin particles to sodium hydroxide solution is 2:5-10g/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 1-3:1, and the alcohol is selected from one or two of ethylene glycol, glycerol, butanol, 1, 3-butanediol, 1, 4-butanediol and octanol.
The invention adopts chemical reaction to prepare lignin-based epoxy resin and a toughening method, the added alcohol just serves as a solvent, then becomes a reactant, the method is continuous and finished at 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 alcohol organic solvent is 1:2-1:4.
Further 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 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 placing the lignin particles with the particle size smaller than 0.1 mu m into a 105 ℃ drying box to dry for 7-8 hours to constant weight to obtain the pretreated lignin particles.
Preferably, the solid-to-liquid ratio of the lignin particles to the mixed solvent is 1:20-1:40g/mL, and the solid-to-liquid ratio of the lignin particles to the epichlorohydrin is 1:10-1:20g/mL.
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. according to the invention, the phthalate toughening lignin-based epoxy resin directly synthesized by chemical reaction is adopted, so that the toughness of the thermosetting lignin-based epoxy resin is remarkably improved, and the prepared toughened thermosetting epoxy resin has excellent impact strength, bending strength and elongation at break.
2. The method for toughening lignin-based epoxy resin by directly synthesizing phthalate by chemical reaction ensures that the plasticizer is uniformly dispersed in the epoxy resin by a method of fusion while reaction, so that the solubility is improved, and meanwhile, the branched hydroxyl groups of some alcohol solvents can also chemically react with the epoxy resin, so that the toughness of the epoxy resin is improved.
3. The lignin-based epoxy resin and the toughening method are prepared by adopting chemical reaction, and the lignin raw material is a bio-based material, so that the lignin-based epoxy resin has complete biodegradability, the dependence on fossil resources is reduced to a certain extent, and the problem of white pollution is relieved.
4. The invention adopts chemical reaction to prepare lignin-based epoxy resin and a toughening method, the added alcohol just serves as a solvent, then becomes a reactant, the method is continuous and finished at 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.
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are conventional commercially available products in the art, unless specifically indicated.
The materials used are as follows:
lignin particles (papermaking black liquor extract, particle diameter less than or equal to 0.1 μm, purity 91.6%);
epichlorohydrin (specification: 99.5% (GC), shanghai Ala Biochemical technology Co., ltd.);
1, 3-butanediol (specification: 98%), shanghai Ala Biochemical technologies Co., ltd.;
ethylene glycol (specification: >99% (GC), shanghai Ala Biochemical technology Co., ltd.);
phthalic anhydride (specification: 500g, saen chemical technology (Shanghai) limited);
curing agent (methyl nadic anhydride, specification: not less than 95.0%, shanghai Michelin Biochemical technology Co., ltd.);
curing reaction accelerator (2-ethylimidazole, specification: 99% or more, shanghai Michelia Biochemical technology Co., ltd.).
A toughened lignin-based epoxy resin, the preparation reaction comprising the steps of:
(1) Adding the pretreated lignin particles and the mixed solvent into a reaction kettle at the temperature of 180-220 ℃ and fully stirring and reacting for 1-3 hours while dissolving;
(2) Adding a certain amount of epichlorohydrin into the mixed solution after the reaction in the step (1), dripping a NaOH catalyst with the mass fraction of 20% at a constant speed at the constant temperature of 70-90 ℃, reacting for a period of time, and distilling under reduced pressure to recover the mixed solution of the dripped water and the excessive epichlorohydrin;
(3) Adding phthalic anhydride and a catalyst into the recycled mixed solution of 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, decompressing and removing water generated by the reaction, adding dichloromethane, mixing and uniformly extracting, adding a certain amount of purified water to wash residual alcohol solvent and catalyst, standing and separating a water layer, heating to 80 ℃ and decompressing and steaming to remove the residual water, thereby obtaining the toughened lignin-based epoxy resin.
In the invention, the pretreatment step of the lignin particles pretreated in the step (1) is as follows: and (3) crushing the lignin solid by using a crusher to obtain lignin particles, and placing the lignin particles with the particle size smaller than 0.1 mu m into a 105 ℃ drying box to dry for 7-8 hours to constant weight to obtain the pretreated lignin particles.
In the following embodiments, the mixed solvent is a mixed solvent of epichlorohydrin and an alcohol organic solvent, the volume ratio of the epichlorohydrin to the alcohol is 1-3:1, and the alcohol is one or two selected from ethylene glycol, glycerol, butanol, 1, 3-butanediol, 1, 4-butanediol and octanol. The solid-to-liquid ratio of the lignin particles to the mixed solvent is 1:20-1:40g/mL.
In the following example, in the step (2), sodium hydroxide with mass fraction of 20% is added at constant temperature of 70-90 ℃ to react for 2-4 hours, and the solid-liquid ratio of lignin particles to sodium hydroxide solution is 2:5-10g/mL. The solid-to-liquid ratio of the lignin particles to the epichlorohydrin is 1:10-1:20g/mL.
In the following examples, the molar ratio of phthalic anhydride to alcohol organic solvent in step (3) is 1:2-1:4. 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 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 resins prepared in each of the examples and comparative examples were: epoxy groups of methyl nadic anhydride and lignin-based epoxy resin were mixed at 0.85:1, then adding 2-ethylimidazole with the mass fraction of 1.0wt% of epoxy resin as a curing reaction accelerator, vacuumizing and bubbling for 15min at 80 ℃, pouring the mixture into a stainless steel mold while the mixture is hot for curing, wherein the specific curing conditions are as follows: curing at 85 ℃ for 4 hours, curing at 120 ℃ for 12 hours, and curing at 150 ℃ for 12 hours.
The lignin-based epoxy resins prepared in each example and comparative example were tested for performance as follows:
1. tensile strength tests were carried out according to ASTM D638, type I, sample size (mm): 130X 13X 4, the stretching speed is 2mm/min.
2. The impact strength of the cantilever beam is tested according to ISO 180/1A standard, the type of the sample is type I, and the size (mm) of the sample is: 130 x 13 x 4, pendulum nominal energy: 5.5J.
3. Flexural strength test was carried out according to GB/T6569-86 standard, sample type I, sample size (mm): 130X 13X 4, the stretching speed is 2mm/min.
Example 1
A toughened lignin-based epoxy resin, the preparation reaction comprising the steps of:
(1) The lignin solid extracted from the papermaking black liquor is crushed by a universal crusher, and is sieved by a stainless steel screen, lignin powder with the particle size smaller than 0.1 mu m is taken and placed in a 105 ℃ drying box to be dried for 7 hours to constant weight, and the dried lignin particles are obtained. 4g of dried lignin particles were added to a magnetic stirring autoclave in a solid to liquid ratio of lignin particles to 1, 3-butanediol of 1:40 mL of 1, 3-butanediol is added into 10g/mL, and the volume ratio of 1, 3-butanediol to epichlorohydrin is 1:2 80mL of epichlorohydrin was added and the reaction mixture was taken out under electric heating at 180℃for 1 hour.
(2) Taking out the prepared mixture into a three-neck flask, adding 60mL of epichlorohydrin, stirring and mixing uniformly under the constant-temperature oil bath heating condition of 80 ℃, dropwise adding 15mL of NaOH solution with the mass fraction of 20% at a constant speed by adopting 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 layer oil layer under reduced pressure at the temperature of 80 ℃ to recover excessive epichlorohydrin and removing the mixed solution consisting of residual water.
(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 catalyst is 0.6% of the total mass of 1,3 butanediol and phthalic anhydride, and the reaction is carried out for 3 hours under reflux at 130 ℃. After the reaction is finished, cooling to room temperature, adding 100mL of dichloromethane extractant, fully and uniformly mixing, and then adding purified water with the total volume of 40% for fully mixing. Standing until the upper layer oil layer and the lower layer water layer are completely separated, slowly heating the oil layer to 80 ℃, and performing reduced pressure rotary evaporation to obtain dichloromethane and residual water, thereby obtaining the toughened lignin-based epoxy resin.
The epoxy value of the toughened lignin-based epoxy resin is determined and the required curing dose is calculated from the epoxy value. Epoxy groups of methyl nadic anhydride and lignin-based epoxy resin were mixed at 0.85:1, then adding 2-ethylimidazole with the mass fraction of 1.0wt% of epoxy resin as a curing reaction accelerator, vacuumizing and bubbling for 15min at 80 ℃, pouring the mixture into a stainless steel mold while the mixture is hot, wherein the specific curing conditions are as follows: and (3) curing for 4 hours at 85 ℃, curing for 12 hours at 120 ℃ and curing for 12 hours at 150 ℃ to obtain the epoxy resin spline to be tested.
Example 2
A toughened lignin-based epoxy resin, the preparation reaction comprising the steps of:
(1) The lignin solid extracted from the papermaking black liquor is crushed by a universal crusher, and is sieved by a stainless steel screen, lignin powder with the particle size smaller than 0.1 mu m is taken and placed in a 105 ℃ drying box to be dried for 7 hours to constant weight, and the dried lignin particles are obtained. 2g of the dried lignin particles were added to a magnetic stirring autoclave in a solid-to-liquid ratio of lignin particles to ethylene glycol of 1:20 mL of ethylene glycol is added into 10g/mL, and the volume ratio of the ethylene glycol to the epichlorohydrin is 1:2 to the mixture was added 40mL of epichlorohydrin, and the mixture was allowed to react at 180℃under electric heating for 1 hour.
(2) Taking out the prepared mixture into a three-neck flask, adding 30mL of epichlorohydrin, stirring and mixing uniformly under the constant-temperature oil bath heating condition of 80 ℃, dropwise adding 7.5mL of NaOH solution with the mass fraction of 20% at a constant speed by adopting 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 layer oil layer under reduced pressure at the temperature of 80 ℃ to recover excessive epichlorohydrin and removing the mixed solution consisting of residual water.
(3) Adding phthalic anhydride into the mixed solution obtained in the step (2), wherein the molar ratio of the phthalic anhydride to the glycol is 1:2, adding NaHSO 4 Catalyst, naHSO 4 The mass of the catalyst is 0.6% of the total mass of the glycol and the phthalic anhydride, and the mixture is subjected to reflux reaction for 3 hours at the temperature of 130 ℃. After the reaction is finished, cooling to room temperature, adding 80mL of dichloromethane extractant, fully and uniformly mixing, and then adding purified water with the total volume of 40% for fully mixing. Standing until the upper layer oil layer and the lower layer water layer are completely separated, slowly heating the oil layer to 80 ℃, and performing reduced pressure rotary evaporation to obtain dichloromethane and residual water to obtain the toughened lignin-based epoxy resin.
The epoxy value of the toughened lignin epoxy resin is determined and the required curing dose is calculated from the epoxy value. Epoxy groups of methyl nadic anhydride and lignin-based epoxy resin were mixed at 0.85:1, then adding 2-ethylimidazole with the mass fraction of 1.0wt% of epoxy resin as a curing reaction accelerator, vacuumizing and bubbling for 15min at 80 ℃, and pouring the mixture into a stainless steel mold while the mixture is hot. The specific curing conditions are as follows: and (3) curing for 4 hours at 85 ℃, curing for 12 hours at 120 ℃ and curing for 12 hours at 150 ℃ to obtain the epoxy resin spline 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 1:1, the volume ratio of the epichlorohydrin to the alcohol organic solvent in the mixed solvent is 1:1, and the solid-liquid ratio of the lignin particles to the mixed solvent is 1:40g/mL; the reaction time of the stirred reaction was 1h with heating to 200 ℃.
In the step (2), 40mL of epichlorohydrin is added into the mixed solution in the step (1), 35mL of 20% sodium hydroxide solution is dripped at a constant temperature of 70 ℃ for reaction for 4 hours. After the reaction, the lower aqueous layer was separated by standing. And (3) distilling the upper layer oil layer under reduced pressure at the temperature of 80 ℃ to recover excessive epichlorohydrin and removing the mixed solution consisting of residual water.
In the step (3), the molar ratio of phthalic anhydride to the alcohol organic solvent is 1:2.NaHSO (NaHSO) 4 The mass of the catalyst is 0.9 percent of the total mass of the alcohol organic solvent and phthalic anhydride. The reflux reaction temperature was 130℃and the reflux reaction time was 5 hours. After the reaction is finished, cooling to room temperature, adding 100mL of dichloromethane extractant, fully and uniformly mixing, and then adding purified water with the total volume of 60% for fully mixing. Standing until the upper layer oil layer and the lower layer water layer are completely separated, slowly heating the oil layer to 80 ℃, and performing reduced pressure rotary evaporation to obtain dichloromethane and residual water to obtain the toughened lignin-based epoxy resin.
The epoxy value of the toughened lignin epoxy resin is determined and the required curing dose is calculated from the epoxy value. Epoxy groups of methyl nadic anhydride and lignin-based epoxy resin were mixed at 0.85:1, then adding 2-ethylimidazole with the mass fraction of 1.0wt% of epoxy resin as a curing reaction accelerator, vacuumizing and bubbling for 15min at 80 ℃, and pouring the mixture into a stainless steel mold while the mixture is hot. The specific curing conditions are as follows: and (3) curing for 4 hours at 85 ℃, curing for 12 hours at 120 ℃ and curing for 12 hours at 150 ℃ to obtain the epoxy resin spline to be tested.
Example 4
The same as in example 1, except that: in the step (1), the volume ratio of the alcohol organic solvent is 1, 4-butanediol to octanol, the volume ratio of the 1, 4-butanediol to the octanol is 1:1, the volume ratio of the epichlorohydrin in the mixed solvent to the alcohol organic solvent is 3:1, and the solid-liquid ratio of lignin particles to the mixed solvent is 1:20g/mL; the reaction time of the stirred reaction was 1h with heating to 220 ℃.
In the step (2), 40mL of epichlorohydrin is added into the mixed solution in the step (1), 45mL of 20% sodium hydroxide solution is added dropwise at a constant temperature of 90 ℃ for reaction for 2h. After the reaction, the lower aqueous layer was separated by standing. And (3) distilling the upper layer oil layer under reduced pressure at the temperature of 80 ℃ to recover excessive epichlorohydrin and removing the mixed solution consisting of residual water.
In the step (3), the molar ratio of phthalic anhydride to the alcohol organic solvent is 1:4.NaHSO (NaHSO) 4 The mass of the catalyst is 1.2 percent of the total mass of the alcohol organic solvent and phthalic anhydride. The reflux reaction temperature was 150℃and the reflux reaction time was 3 hours. After the reaction is finished, cooling to room temperature, adding 100mL of dichloromethane extractant, fully and uniformly mixing, and then adding purified water with the total volume of 60% for fully mixing. Standing until the upper layer oil layer and the lower layer water layer are completely separated, slowly heating the oil layer to 80 ℃, and performing reduced pressure rotary evaporation to obtain dichloromethane and residual water to obtain the toughened lignin-based epoxy resin.
The epoxy value of the toughened lignin epoxy resin is determined and the required curing dose is calculated from the epoxy value. Epoxy groups of methyl nadic anhydride and lignin-based epoxy resin were mixed at 0.85:1, then adding 2-ethylimidazole with the mass fraction of 1.0wt% of epoxy resin as a curing reaction accelerator, vacuumizing and bubbling for 15min at 80 ℃, and pouring the mixture into a stainless steel mold while the mixture is hot. The specific curing conditions are as follows: and (3) curing for 4 hours at 85 ℃, curing for 12 hours at 120 ℃ and curing for 12 hours at 150 ℃ to obtain the epoxy resin spline to be tested.
Comparative example 1
The lignin solid extracted from the papermaking black liquor is crushed by a universal crusher, and is sieved by a stainless steel screen, lignin powder with the particle size smaller than 0.1 mu m is taken and placed in a 105 ℃ drying box to be dried for 7 hours to constant weight, and the dried lignin particles are obtained. 4g of dried lignin particles were added to a magnetic stirring autoclave in a solid to liquid ratio of lignin particles to 1, 3-butanediol of 1:40 mL of 1, 3-butanediol is added into 10g/mL, and the volume ratio of 1, 3-butanediol to epichlorohydrin is 1:2 80mL of epichlorohydrin was added and the reaction mixture was taken out under electric heating at 180℃for 1 hour. Taking out the prepared mixture into a three-neck flask, adding 60mL of epichlorohydrin, stirring and mixing uniformly under the constant-temperature oil bath heating condition of 80 ℃, dropwise adding 15mL of NaOH solution with the mass fraction of 20% at a constant speed by adopting 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 layer oil layer under reduced pressure at the temperature of 80 ℃ to recover excessive epichlorohydrin and removing the mixed solution consisting of residual water.
The epoxy value of the lignin epoxy resin is determined and the required curing dose is calculated from the epoxy value. Epoxy groups of methyl nadic anhydride and lignin-based epoxy resin were mixed at 0.85:1, then adding 2-ethylimidazole with the mass fraction of 1.0wt% of epoxy resin as a curing reaction accelerator, vacuumizing and bubbling for 15min at 80 ℃, and pouring the mixture into a stainless steel mold while the mixture is hot. The specific curing conditions are as follows: and (3) curing for 4 hours at 85 ℃, curing for 12 hours at 120 ℃ and curing for 12 hours at 150 ℃ to obtain the epoxy resin spline to be tested.
The mechanical properties of the epoxy resin bars obtained in examples 1-4 and comparative example 1 were tested to obtain the mechanical properties of the toughened lignin epoxy resin as shown in Table 1 below:
TABLE 1
As can be seen from the above table, the test performance of the epoxy resin bars of examples 1-4 is greatly improved in terms of elongation at break and impact strength, which show toughness, relative to comparative example 1, and still has higher tensile strength values and flexural strength values. The application range of the toughened lignin epoxy resin is greatly increased, and the epoxy resin has extremely high innovation value.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended 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 such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (7)
1. The method for toughening and modifying 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, heating to 180-220 ℃ and stirring for reaction, adding epichlorohydrin into the mixture after reaction, adding sodium hydroxide at a constant temperature of 70-90 ℃ for reaction, distilling under reduced pressure after the reaction is finished to recover water and excessive epichlorohydrin, adding phthalic anhydride and a catalyst into the mixture of the recovered water and the excessive epichlorohydrin for reflux reaction, and removing the water generated by the reaction under reduced pressure after the reaction is finished to obtain toughened lignin-based epoxy resin; 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 1-3:1, and the alcohol organic solvent is one or two selected from ethylene glycol, glycerol, butanol, 1, 3-butanediol, 1, 4-butanediol and octanol; 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 phthalic anhydride.
2. The method according to claim 1, wherein the molar ratio of phthalic anhydride to alcohol organic solvent is 1:2-1:4.
3. The method according to claim 1, characterized in that the pretreatment step of the pretreated lignin particles is: and (3) crushing the lignin solid by using a crusher to obtain lignin particles, and placing the lignin particles with the particle size of less than 0.1 mu m into a 105 ℃ drying box to dry for 7-8 hours to constant weight to obtain the pretreated lignin particles.
4. The method of claim 1, wherein the solid to liquid ratio of lignin particles to mixed solvent is 1:20 to 1:40g/mL.
5. The method of claim 1, wherein the solid to liquid ratio of lignin particles to epichlorohydrin is from 1:10 to 1:20g/mL.
6. The method of claim 1, wherein the reflux reaction temperature is 130 ℃ to 150 ℃ and the reflux reaction time is 3 to 5h.
7. The method of claim 1, wherein the reaction time of the stirring reaction at 180 ℃ to 220 ℃ is 1-3h.
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| 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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| 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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