CN111763304A - Lignin oligomer epoxy resin and preparation method thereof - Google Patents
Lignin oligomer epoxy resin and preparation method thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 112
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 64
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 230000002829 reductive effect Effects 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 13
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 16
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000007363 ring formation reaction Methods 0.000 claims description 12
- 238000007142 ring opening reaction Methods 0.000 claims description 12
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003495 polar organic solvent Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 4
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 4
- 239000012074 organic phase Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 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 4
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 2
- 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 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- 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 lignin oligomer epoxy resin and a preparation method thereof. The method comprises the steps of carrying out open-loop reaction on lignin reductive degradation oligomer and epoxy chloropropane under the action of a phase transfer catalyst, and carrying out closed-loop reaction in the presence of alkali to prepare the lignin oligomer epoxy resin. The preparation method is simple and convenient, and the prepared lignin oligomer epoxy resin has the cured product mechanical property equivalent to that of bisphenol A epoxy resin and has excellent thermal stability.
Description
Technical Field
The invention relates to lignin oligomer epoxy resin and a preparation method thereof, in particular to a method for preparing epoxy resin by reacting partially reduced and degraded lignin oligomer with epichlorohydrin, belonging to the field of bio-based high polymer materials.
Technical Field
The lignin is used as a natural phenolic high-molecular compound with abundant reserves in the nature, has wide sources and low price, contains a plurality of active groups such as phenolic hydroxyl, alcoholic hydroxyl, carboxyl and the like in a molecular structure, can replace the traditional fossil resources to synthesize the epoxy resin, particularly a macromolecular rigid framework thereof, and can endow the epoxy resin with good mechanical property and thermal stability. However, lignin is difficult to be dissolved in most organic solvents due to its complex chemical structure and composition, low reactivity, and thus, development and utilization in the field of epoxy resins are restricted.
Currently, there are three main ways to apply lignin in epoxy resin: (1) blending lignin directly with epoxy resin in the form of additives, modifiers, etc. (Green Chemistry,2018,20(7): 1459-; (2) the lignin is pretreated and modified by demethylation, phenolization, hydroxymethylation, amination and the like, and then replaces bisphenol A to synthesize epoxy resin (Progress in Polymer Science 2014,39(7): 1266-1290); (3) the lignin is degraded into oligomers to replace bisphenol A synthetic epoxy resin (Biomacromolecules,2017,18(8): 2640-2648). Compared with the former two methods, the method for synthesizing the epoxy resin by degrading the oligomer with the lignin has the outstanding advantages of good compatibility, high lignin substitution rate and the like, and is an effective way for high-valued utilization of the lignin in the field of epoxy resin materials.
The patent CN 201910934089.1 reports a lignin oligomer and a preparation method thereof, the lignin reductive degradation oligomer obtained by the method not only has high phenolic hydroxyl content (more than or equal to 362mg/g), high reactivity and good organic solvent solubility, but also better retains the rigid structural characteristics of lignin, and is an ideal raw material for effectively replacing lignin to synthesize epoxy resin.
The method is simple and convenient, and the obtained epoxy resin has the cured product mechanical property equivalent to that of bisphenol A epoxy resin, has excellent thermal stability, and can be used for replacing bisphenol A epoxy resin to be applied to the fields of coatings, adhesives, composite materials, road traffic and the like.
Disclosure of Invention
The invention aims to provide a lignin-based partially reductive degradation oligomer epoxy resin and a preparation method thereof.
The invention adopts the following technical scheme: lignin oligomerEpoxy resin, namely performing open-loop reaction on lignin oligomer and epoxy chloropropane under the action of a phase transfer catalyst, and performing closed-loop reaction in the presence of alkali to prepare the lignin oligomer epoxy resin, wherein the structural formula is as follows:
wherein lignin is lignin.
The preparation method of the lignin oligomer epoxy resin comprises the following steps of performing open-loop reaction on lignin oligomer and epoxy chloropropane under the action of a phase transfer catalyst, and performing closed-loop reaction in the presence of alkali to prepare the lignin oligomer epoxy resin, wherein the synthetic reaction formula is as follows:
the lignin oligomer is a lignin partial reduction degradation oligomer prepared according to a patent CN 201910934089.1 method and a solvent separation oligomer thereof, and has a molecular weight of 500 g/mol-2000 g/mol and a phenolic hydroxyl group content of 0.35mol/100 g-0.90 mol/100 g.
The solvent separation oligomer is prepared by the following method: and dissolving the lignin partial reductive degradation oligomer in a polar organic solvent, adding a non-polar organic solvent, and distilling insoluble substances under reduced pressure to obtain a solvent separation oligomer.
The polar organic solvent is any one or a mixture of more than two of dichloromethane, ethyl acetate, acetone and chloroform; the non-polar solvent is any one of petroleum ether, normal hexane and n-pentane, and the dosage of the non-polar solvent is 1-10 times of the volume of the polar organic solvent.
The phase transfer catalyst is any one or a mixture of more than two of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride, and the dosage of the phase transfer catalyst is 1-5% of the mass of the lignin oligomer.
The dosage of the epichlorohydrin is 4 to 30 times of the quality of the lignin oligomer.
The alkali is any one or a mixture of more than two of sodium hydroxide, potassium hydroxide and calcium hydroxide, and the ratio of the alkali to the amount of phenolic hydroxyl substances in the lignin oligomer is 0.5-2.5: 1.
The ring-opening reaction temperature is 70-120 ℃, the ring-opening reaction time is 2-10 h, the ring-closing reaction temperature is 40-80 ℃, and the ring-closing reaction time is 1-5 h.
The optimal preparation reaction conditions are as follows: the dosage of the phase transfer catalyst is 2.0 percent of the mass of the lignin oligomer, the ring-opening reaction temperature is 100 ℃, the ring-opening reaction time is 8 hours, the mass ratio of alkali to phenolic hydroxyl substances in the lignin oligomer is 2:1, the ring-closing reaction temperature is 70 ℃, and the ring-closing reaction time is 3 hours; under the reaction condition, the obtained epoxy resin is in a liquid state or a solid state according to the molecular weight of the lignin oligomer.
Has the advantages that:
1. the invention prepares the novel bio-based epoxy resin by partially reducing and degrading the oligomer by the lignin, effectively solves the key problems that the chemical structure and the composition of the lignin are complex, the reaction activity is low, the solubility of an organic solvent is poor and the like, which influence the high-valued application of the lignin, and has important significance for realizing the high-efficient and high-valued utilization of the lignin resource and expanding the application of the lignin resource in high polymer materials such as epoxy resin and the like.
2. The method for preparing the lignin oligomer epoxy resin is simple and convenient, and the obtained lignin oligomer epoxy resin has the cured product mechanical property equivalent to that of bisphenol A epoxy resin and has excellent thermal stability.
Drawings
FIG. 1 is an infrared spectrum of a lignin oligomer epoxy resin.
FIG. 2 of lignin oligomer epoxy resin1H NMR chart.
FIG. 3 of lignin oligomer epoxy resin13C NMR chart.
3490cm in the infrared spectrum of the lignin oligomer epoxy resin (FIG. 1)-1The broad peak is-OH characteristic absorption peak, 2928cm-1Is in the form of-OCH3And in the side chain-CH3、–CH2C-H of (A-C)A stretching vibration absorption peak. 1589cm-1、1506cm-1、1454cm-1Is located at 907cm which is a characteristic absorption peak of a lignin phenylpropane skeleton-1And the absorption peak is the characteristic absorption peak of the epoxy group.
Of lignin oligomers with epoxy resins1In the H NMR spectrum (FIG. 2), the characteristic peak of epoxy group methylene hydrogen at the chemical shift of 3.67 ppm-3.86 ppm, the chemical shift of 2.61 ppm-2.83 ppm and13the C NMR spectrum (FIG. 3) shows a characteristic peak of an epoxy group at a chemical shift of 44.6ppm to 56.0 ppm.
Detailed Description
A lignin oligomer epoxy resin and a preparation method thereof. The synthesis reaction formula of the epoxy resin is as follows:
the method is realized by the following steps:
firstly, performing ring opening reaction on lignin oligomer and epoxy chloropropane for 2 to 10 hours at 70 to 120 ℃ under the action of a phase transfer catalyst;
and secondly, cooling the reaction system to 40-80 ℃, adding a certain amount of alkali in batches, carrying out ring-closing reaction for 1-5 h, washing with water, and carrying out reduced pressure distillation on an organic phase to obtain the lignin oligomer epoxy resin.
The lignin oligomer in the first step is lignin partial reduction degradation oligomer prepared according to a method disclosed in patent CN 201910934089.1 and solvent separation oligomer thereof (the molecular weight is 500 g/mol-2000 g/mol, and the content of phenolic hydroxyl groups is 0.35mol/100 g-0.90 mol/100 g);
the solvent separation oligomer is prepared by the following method: dissolving the lignin partial reduction degradation oligomer in one or more than two of polar organic solvents such as dichloromethane, ethyl acetate, acetone, chloroform and the like, adding non-polar organic solvents such as petroleum ether, normal hexane, n-pentane and the like with the dosage of 1-10 times of the volume of the polar organic solvents, and distilling insoluble substances under reduced pressure to obtain the solvent separation oligomer.
The dosage of the epichlorohydrin is 4 to 30 times of the quality of the lignin oligomer;
the phase transfer catalyst is any one or a mixture of more than two of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride, and the optimal dosage is 2% of the mass of the lignin oligomer;
the ring-opening reaction temperature is optimally 100 ℃, and the ring-opening reaction time is optimally 8 h.
The alkali in the second step is any one or a mixture of more than two of sodium hydroxide, potassium hydroxide and calcium hydroxide, and the optimal ratio of the alkali to the amount of phenolic hydroxyl substances in the lignin oligomer is 2: 1;
the optimal ring-closing reaction temperature is 70 ℃, and the optimal ring-closing reaction time is 3 h.
Example 1
8.0g of lignin oligomer (molecular weight of 998g/mol, phenolic hydroxyl group content of 0.65mol/100g) and 115g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 0.16g of benzyltriethylammonium chloride is added, and the temperature is raised to 70 ℃ for reaction for 8 hours. The temperature is reduced to 50 ℃, 4.11g of sodium hydroxide is added in batches, and the temperature is raised to 70 ℃ for reaction for 3 hours. After the reaction is finished, washing for 3-4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.26mol/100 g.
Example 2
10.2g of lignin oligomer (molecular weight: 998g/mol, phenolic hydroxyl group content: 0.65mol/100g) and 145g of epichlorohydrin were added to a four-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser, and dissolved by stirring, 0.10g of tetrabutylammonium bromide was added, and the mixture was heated to 100 ℃ to react for 4 hours. The temperature is reduced to 50 ℃, 2.61g of sodium hydroxide is added in batches, and the temperature is raised to 60 ℃ for reaction for 3 hours. After the reaction is finished, washing for 3 to 4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.27mol/100 g.
Example 3
10.3g of lignin oligomer (molecular weight of 998g/mol, phenolic hydroxyl group content of 0.65mol/100g) and 147g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 0.20g of benzyltrimethylammonium chloride is added, and the temperature is raised to 110 ℃ for reaction for 2 hours. The temperature is reduced to 50 ℃, 2.64g of sodium hydroxide is added in batches, and the temperature is increased to 80 ℃ for reaction for 2 hours. After the reaction is finished, washing for 3 to 4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.33mol/100 g.
Example 4
40g of lignin oligomer (molecular weight of 998g/mol, phenolic hydroxyl content of 0.65mol/100g) and 560g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 0.80g of benzyltriethylammonium chloride is added, and the temperature is raised to 100 ℃ for reaction for 8 hours. The temperature is reduced to 50 ℃, 20.6g of sodium hydroxide is added in batches, and the temperature is raised to 70 ℃ for reaction for 3 hours. After the reaction is finished, washing for 3-4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.40mol/100 g.
Example 5
75g of lignin oligomer (with the molecular weight of 1489g/mol and the phenolic hydroxyl group content of 0.56mol/100g) and 900g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 1.50g of tetrabutylammonium chloride is added, and the temperature is raised to 90 ℃ for reaction for 8 hours. The temperature is reduced to 50 ℃, 33.8g of sodium hydroxide is added in batches, and the temperature is raised to 70 ℃ for reaction for 3 hours. After the reaction is finished, washing for 3 to 4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.39mol/100 g.
Example 6
93g of lignin oligomer (with the molecular weight of 2056g/mol and the phenolic hydroxyl group content of 0.46mol/100g) and 825g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 2.79g of benzyltriethylammonium chloride is added, and the temperature is raised to 110 ℃ for reaction for 8 hours. The temperature is reduced to 50 ℃, 34.4g of sodium hydroxide is added in batches, and the temperature is raised to 70 ℃ for reaction for 3 hours. After the reaction is finished, washing for 3 to 4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.37mol/100 g.
Example 7
152g of lignin oligomer (molecular weight of 1451g/mol, content of phenolic hydroxyl group of 0.43mol/100g) and 800g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 6.10g of benzyltriethylammonium chloride is added, and the temperature is raised to 110 ℃ for reaction for 5 hours. The temperature is reduced to 50 ℃, 32.3g of sodium hydroxide is added in batches, and the temperature is raised to 60 ℃ for reaction for 2 hours. After the reaction is finished, washing for 3-4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.32mol/100 g.
The cured epoxy resin and methyltetrahydrophthalic anhydride has bending strength of 54.5MPa, tensile strength of 40.5MPa and impact strength of 8.70kJ/m2，Td(5％)324.0℃。
Example 8
161g of lignin partially reduced and degraded oligomer (molecular weight 1137g/mol, phenolic hydroxyl group content 0.53mol/100g) and 800g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 8.10g of benzyltriethylammonium chloride is added, and the temperature is raised to 110 ℃ for reaction for 3 hours. The temperature is reduced to 50 ℃, 20.8g of sodium hydroxide is added in batches, and the temperature is raised to 60 ℃ for reaction for 3 hours. After the reaction is finished, washing for 3-4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.34mol/100 g.
The cured epoxy resin and methyltetrahydrophthalic anhydride has bending strength of 55.1MPa, tensile strength of 42.0MPa, and impact strength of 9.30kJ/m2，Td(5％)322.9℃。
Example 9
172g of lignin partially reduced and degraded oligomer (molecular weight of 915g/mol, phenolic hydroxyl group content of 0.61mol/100g) and 1000g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 3.50g of dodecyl trimethyl ammonium chloride is added, and the temperature is raised to 110 ℃ for reaction for 8 hours. The temperature is reduced to 50 ℃, 52.4g of sodium hydroxide is added in batches, and the temperature is raised to 60 ℃ for reaction for 5 hours. After the reaction is finished, washing for 3-4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.32mol/100 g.
The cured epoxy resin and methyltetrahydrophthalic anhydride have a flexural strength of 18.4MPa and an impact strength of 4.10kJ/m2，Td(5％)287.5℃。
Example 10
345g of a lignin partially reductively degraded oligomer (molecular weight of 1451g/mol, phenolic hydroxyl group content of 0.43mol/100g) was dissolved in 500mL of methylene chloride, 700mL of petroleum ether was added, and the insoluble matter was distilled under reduced pressure to obtain 301g of a solvent-separated lignin oligomer (molecular weight of 1718g/mol, phenolic hydroxyl group content of 0.50mol/100 g).
290g of lignin solvent separation oligomer and 1200g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser pipe, stirred and dissolved, 5.80g of tetrabutylammonium chloride is added, and the temperature is raised to 100 ℃ for reaction for 3 hours. The temperature is reduced to 50 ℃, 97.2g of potassium hydroxide is added in batches, and the temperature is raised to 60 ℃ for reaction for 3 hours. After the reaction is finished, washing for 3-4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.32mol/100 g.
The cured epoxy resin and methyltetrahydrophthalic anhydride has bending strength of 74.3MPa, tensile strength of 46.8MPa and impact strength of 11.1kJ/m2，Td(5％)327.4℃。
Example 11
238g of lignin partially reduced and degraded oligomer (molecular weight of 631g/mol, phenolic hydroxyl group content 0.63mol/100g) was dissolved in 300mL of ethyl acetate, 600mL of petroleum ether was added, and the insoluble matter was distilled under reduced pressure to obtain 197g of solvent-separated lignin oligomer (molecular weight of 836g/mol, phenolic hydroxyl group content 0.58mol/100 g).
197g of lignin solvent separation oligomer and 600g of epichlorohydrin are added into a four-neck round-bottom flask with a stirrer, a thermometer and a reflux condenser, stirred and dissolved, 3.90g of tetrabutylammonium chloride is added, and the temperature is raised to 100 ℃ for reaction for 3 hours. The temperature is reduced to 50 ℃, 45.7g of sodium hydroxide is added in batches, and the temperature is raised to 60 ℃ for reaction for 3 hours. After the reaction is finished, washing for 3-4 times, and distilling the organic phase under reduced pressure to obtain the lignin oligomer epoxy resin with the epoxy value of 0.32mol/100 g.
The cured epoxy resin and methyltetrahydrophthalic anhydride have bending strength of 112.0MPa and tensile strengthDegree of 59.8MPa and impact strength of 11.1kJ/m2，Td(5％)325.1℃。
Claims (10)
1. A lignin oligomer epoxy resin characterized by: the lignin oligomer and epoxy chloropropane are subjected to open-loop reaction under the action of a phase transfer catalyst, and then subjected to close-loop reaction in the presence of alkali to prepare the lignin oligomer epoxy resin, wherein the structural formula is as follows:
wherein lignin is lignin.
2. The preparation method of lignin oligomer epoxy resin as claimed in claim 1, characterized in that, the lignin oligomer and epichlorohydrin are subjected to ring opening reaction under the action of phase transfer catalyst, and then subjected to ring closing reaction in the presence of alkali to prepare lignin oligomer epoxy resin, wherein the synthetic reaction formula is as follows:
3. the method of producing a lignin oligomer epoxy resin according to claim 2, wherein: the lignin oligomer is a lignin partial reduction degradation oligomer prepared according to a patent CN 201910934089.1 method and a solvent separation oligomer thereof, and has a molecular weight of 500 g/mol-2000 g/mol and a phenolic hydroxyl group content of 0.35mol/100 g-0.90 mol/100 g.
4. The method of preparing a lignin oligomer epoxy resin according to claim 3, wherein: the solvent separation oligomer is prepared by the following method: and dissolving the lignin partial reductive degradation oligomer in a polar organic solvent, adding a non-polar organic solvent, and distilling insoluble substances under reduced pressure to obtain a solvent separation oligomer.
5. The method of producing a lignin oligomer epoxy resin according to claim 4, wherein: the polar organic solvent is any one or a mixture of more than two of dichloromethane, ethyl acetate, acetone and chloroform; the non-polar solvent is any one of petroleum ether, normal hexane and n-pentane, and the dosage of the non-polar solvent is 1-10 times of the volume of the polar organic solvent.
6. The method of producing a lignin oligomer epoxy resin according to claim 2, wherein: the phase transfer catalyst is any one or a mixture of more than two of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride, and the dosage of the phase transfer catalyst is 1-5% of the mass of the lignin oligomer.
7. The method of producing a lignin oligomer epoxy resin according to claim 2, wherein: the dosage of the epichlorohydrin is 4 to 30 times of the quality of the lignin oligomer.
8. The method of producing a lignin oligomer epoxy resin according to claim 2, wherein: the alkali is any one or a mixture of more than two of sodium hydroxide, potassium hydroxide and calcium hydroxide, and the ratio of the alkali to the amount of phenolic hydroxyl substances in the lignin oligomer is 0.5-2.5: 1.
9. The method of producing a lignin oligomer epoxy resin according to claim 2, wherein: the ring-opening reaction temperature is 70-120 ℃, the ring-opening reaction time is 2-10 h, the ring-closing reaction temperature is 40-80 ℃, and the ring-closing reaction time is 1-5 h.
10. The method for preparing lignin oligomer epoxy resin according to claim 2, wherein the optimal preparation reaction conditions are: the dosage of the phase transfer catalyst is 2.0 percent of the mass of the lignin oligomer, the ring-opening reaction temperature is 100 ℃, the ring-opening reaction time is 8 hours, the mass ratio of alkali to phenolic hydroxyl substances in the lignin oligomer is 2:1, the ring-closing reaction temperature is 70 ℃, and the ring-closing reaction time is 3 hours; under the reaction condition, the obtained epoxy resin is in a liquid state or a solid state according to the molecular weight of the lignin oligomer.
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