CN104892897A - Method for preparing epoxy resin by utilizing lignin - Google Patents
Method for preparing epoxy resin by utilizing lignin Download PDFInfo
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- CN104892897A CN104892897A CN201510297639.5A CN201510297639A CN104892897A CN 104892897 A CN104892897 A CN 104892897A CN 201510297639 A CN201510297639 A CN 201510297639A CN 104892897 A CN104892897 A CN 104892897A
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Abstract
The invention relates to a method for preparing epoxy resin by utilizing lignin. The method for preparing epoxy resin by utilizing lignin comprises the following steps: (1) smashing lignin, and then removing inorganic salt impurities in lignin; (2) adding pretreated lignin and H2O2 solution into ionic liquid [BMIm]Cl, regulating the pH value to be 8-10, then carrying out oxidation reaction for 2-4 hours at the temperature of 50-90 DEG C, and finally carrying out standing and solid-liquid separation on the mixture obtained through the oxidation reaction, wherein the obtained solid matter is namely oxidized and modified lignin; and (3) adding 35-60 parts by weight of 10-20% NaOH solution and 45-90 parts by weight of epoxy chloropropane into the oxidized and modified lignin, then carrying out epoxidation reaction for 2-5 hours at the temperature of 70-100 DEG C, and finally standing and removing unreacted raw materials from the mixture obtained through the epoxidation reaction, so that the epoxy resin is obtained. The method for preparing epoxy resin by utilizing lignin is economic and environmental-friendly and is strong in operability, and the obtained epoxy resin product has good performance and has a very good commercial application prospect.
Description
Technical field
The present invention relates to epoxy resin synthesis field, relate in particular to a kind of method utilizing xylogen to prepare epoxy resin.
Background technology
Xylogen is that occurring in nature content is only second to cellulosic second largest renewable resources, every year with 5 × 10
10the speed regeneration of t is a kind of organic raw material being rich in industrial value.In the Mierocrystalline cellulose related industrieies such as plant hydrolyzed and pulp and paper industry, xylogen a large amount of output as a by-product usually, as in black liquid containing xylogen about 20 ~ 30%.But up to the present, the separating lignin more than 95% reclaims to be burnt after concentrated, and cause the significant wastage of resource on the one hand, the discharge on the other hand containing xylogen trade effluent also can cause serious detrimentally affect to environment.Xylogen is effectively utilized, is had positive meaning to China environmental protection and Economic development.
Epoxy resin is the organic compound containing two or more epoxide groups in general reference molecule, and except indivedual, their relative molecular mass is not high.The molecular structure of epoxy resin be with in molecular chain containing active epoxide group for its feature, epoxide group can be positioned at the end of molecular chain, centre or structure circlewise.Due in molecular structure containing active epoxide group, make they can with polytype solidifying agent generation crosslinking reaction and formed and insoluble there is the cancellated superpolymer of three-dimensional.Macromolecular compound containing epoxide group in all molecular structures is referred to as epoxy resin.Epoxy resin after solidification has good physics, chemical property, it has excellent bonding strength to the surface of metal and non-metallic material, and dielectric properties are good, set shrinking percentage is little, product size good stability, and hardness is high, snappiness is better, to alkali and most of solvent-stable, be thus widely used in national defence, each department of national economy, pour into a mould, flood, the purposes such as lamination material, caking agent, coating.Current epoxy resin product mostly on the market is by the traditional technology gained of dihydroxyphenyl propane epoxy resin, and its product performance are higher, and for commercially available E-44 model epoxy resin, its oxirane value can reach 0.4 ~ 0.45, and product viscosity is 25000 ~ 40000mPa.S.
But the dihydroxyphenyl propane that the above-mentioned traditional technology preparing epoxy resin uses is expensive and have toxicity, therefore finds other environmental protection, the preparation method of epoxy resin of low cost is study hotspot always.
There are at present these two kinds of synthesis techniques of resynthesis epoxy resin after people's research and utilization xylogen Direct Epoxidation Reactive Synthesis epoxy resin and lignin modification, also had research by lignin derivative and Blending Modification of Epoxy Resin in addition.But utilize xylogen directly to carry out epoxidation reaction acquisition epoxy resin and there is product component complexity, oxirane value is lower, the shortcoming that product performance are not high, as a rule, Direct Epoxidation reaction wood quality utilization ratio is below 50%, and react wayward, final product epoxy resin epoxy value, between 0.2 ~ 0.3, does not have utility value substantially, and the method for resynthesis epoxy resin after utilizing lignin modification, generally that phenolate or sulfonation modifying are carried out to xylogen, by the xylogen that phenolate is modified, modified lignin resin product phenolic hydroxyl group promotes to some extent, its epoxy resin epoxy value of finally synthesizing can reach about 0.4, but due to the normally expensive and highly toxic substance of modifying agent in modifying process, so its alternative dihydroxyphenyl propane be there is no practical significance, and Sulphonation of Lignin modification is very harsh to the control of reaction conditions, and normally carry out under the high temperature of 150 ~ 200 DEG C, there is certain operational safety hidden danger, and final synthetic product epoxy resin epoxy value is about 0.3, resin viscosity is lower than 20000mPa.S.It can thus be appreciated that the performance of the epoxy resin of the method gained of these two kinds of modified resynthesis is not also effectively improved.Therefore, the existing method utilizing xylogen to prepare epoxy resin due to the limitation of its preparation method and in product performance well below traditional technology, therefore cannot really realize commercialization utilize.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of economic environmental protection, the xylogen that utilizes of strong operability prepares the method for epoxy resin, and by the excellent property of epoxy resin product obtained by the method, with the performance of Commercial epoxy resins product and outward appearance very nearly the same.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme: utilize xylogen to prepare the method for epoxy resin, comprise the following steps:
(1) pre-treatment of xylogen
Xylogen is pulverized, then removes the inorganic salt impurities in xylogen;
(2) oxidation modification of xylogen
The massfraction of the pretreated xylogen and 35 ~ 90 weight parts of getting 1 ~ 3 weight part is the H of 30%
2o
2the massfraction that solution joins 30 ~ 50 weight parts is greater than in ionic liquid [BMIm] Cl of 99%, adjust ph to 8 ~ 10, then oxidizing reaction 2 ~ 4h under the condition of 50 ~ 90 DEG C, finally the mixture of oxidizing reaction gained is left standstill, solid-liquid separation process, gained solid substance is the xylogen after oxidation modification;
(3) synthesis of epoxy resin
The massfraction adding 35 ~ 60 weight parts in the xylogen after oxidation modification is the NaOH solution of 10 ~ 20% and the epoxy chloropropane of 45 ~ 90 weight parts, then epoxidation reaction 2 ~ 5h under 70 ~ 100 DEG C of conditions, finally the mixture of epoxidation reaction gained left standstill, remove unreacted Feedstock treating, obtain described epoxy resin.
Further, the detailed process of step (1) is: lignin powder is broken to more than 80 orders, then under lower than the condition of 110 DEG C, is dried to constant weight, to be more fully dissolved in concentration be 0.5 ~ 2mol ﹒ L
-1naOH solution in, then carry out filtration treatment, then be 0.5 ~ 2molL by concentration
-1hCl solution the pH value of gained filtrate is adjusted to 2 ~ 3, finally filtrate to be left standstill, solid-liquid separation process, then by after gained solid substance washing to neutral, drying process.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1. the excellent property of epoxy resin product that obtains of the present invention, its oxirane value can reach 0.36, and viscosity can reach 30000mPa.S, can meet the demand in market completely;
2. present invention uses H
2o
2, [BMIm] Cl two kinds of modifying agents, the cooperation of these two kinds of modifying agents can not only improve the viscosity of epoxy resin and H
2o
2what have is Bleachability, can make the epoxy resin product of the final gained of the present invention in appearance in faint yellow, and the epoxy resin product comparing the modification such as phenolate, sulfonation obtained is more pure transparent;
3. raw material economics environmental protection used in the present invention, effectively can avoid the harm to environment, and technique is simple, little, the strong operability of reaction conditions restriction, is applicable to industrialization scale operation;
4. the present invention can carry out utilization of waste material to the xylogen in papermaking wastewater, and utilization ratio is very high, thus can reduce because papermaking wastewater discharges the problem of environmental pollution brought in a large number, has the social benefit of Sustainable development.
To sum up, the economic environmental protection of the present invention, strong operability, and the excellent property of obtained epoxy resin product, with the performance of Commercial epoxy resins product and outward appearance very nearly the same, there is extraordinary commercial application prospect.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
Utilize xylogen to prepare the method for epoxy resin, comprise the following steps:
(1) pre-treatment of xylogen
Alkali lignin is crushed to 80 orders, then under the condition of 109 DEG C, is dried to constant weight, to be more fully dissolved in concentration be 1.2mol ﹒ L
-1naOH solution in, then carry out filtration treatment, then be 1.2molL by concentration
-1hCl solution the pH value of gained filtrate is adjusted to 2, finally (2h), solid-liquid separation process are left standstill to filtrate, then by the washing of gained solid substance to neutral, after 40 DEG C of vacuum drying treatment;
(2) oxidation modification of xylogen
The massfraction of the pretreated xylogen and 62 weight parts of getting 2 weight parts is the H of 30%
2o
2the massfraction that solution joins 30 weight parts is in ionic liquid [BMIm] Cl of 99.2%, by NaOH solution adjust ph to 8, then oxidizing reaction 2h under the condition of 90 DEG C, finally leave standstill (2h), solid-liquid separation process to the mixture of oxidizing reaction gained, gained solid substance is the xylogen after oxidation modification;
(3) synthesis of epoxy resin
The massfraction adding 48 weight parts in the xylogen after oxidation modification is the NaOH solution of 15% and the epoxy chloropropane of 67 weight parts, then epoxidation reaction 5h under 70 DEG C of conditions, finally (2h) left standstill to the mixture of epoxidation reaction gained, remove unreacted Feedstock treating, obtain described epoxy resin.
The epoxy resin of the present embodiment gained is faint yellow, and its oxirane value is 0.33 after tested, and viscosity is 32000mPa.S, and tensile strength is 15MPa, and xylogen utilization ratio is 85%.
Embodiment 2
Utilize xylogen to prepare the method for epoxy resin, comprise the following steps:
(1) pre-treatment of xylogen
Alkali lignin is crushed to 90 orders, then under the condition of 90 DEG C, is dried to constant weight, to be more fully dissolved in concentration be 0.5mol ﹒ L
-1naOH solution in, then carry out filtration treatment, then be 0.5molL by concentration
-1hCl solution the pH value of gained filtrate is adjusted to 2.5, finally (2h), solid-liquid separation process are left standstill to filtrate, then by the washing of gained solid substance to neutral, after 40 DEG C of vacuum drying treatment;
(2) oxidation modification of xylogen
The massfraction of the pretreated xylogen and 35 weight parts of getting 1 weight part is the H of 30%
2o
2the massfraction that solution joins 40 weight parts is in ionic liquid [BMIm] Cl of 99.5%, by NaOH solution adjust ph to 9, then oxidizing reaction 4h under the condition of 50 DEG C, finally leave standstill (2h), solid-liquid separation process to the mixture of oxidizing reaction gained, gained solid substance is the xylogen after oxidation modification;
(3) synthesis of epoxy resin
The massfraction adding 60 weight parts in the xylogen after oxidation modification is the NaOH solution of 10% and the epoxy chloropropane of 45 weight parts, then epoxidation reaction 3.5h under 85 DEG C of conditions, finally (2h) left standstill to the mixture of epoxidation reaction gained, remove unreacted Feedstock treating, obtain described epoxy resin.
The epoxy resin of the present embodiment gained is faint yellow, and its oxirane value is 0.34 after tested, and viscosity is 32500mPa.S, and tensile strength is 15MPa, and xylogen utilization ratio is 85%.
Embodiment 3
Utilize xylogen to prepare the method for epoxy resin, comprise the following steps:
(1) pre-treatment of xylogen
Alkali lignin is crushed to 100 orders, then under the condition of 100 DEG C, is dried to constant weight, to be more fully dissolved in concentration be 2mol ﹒ L
-1naOH solution in, then carry out filtration treatment, then be 2molL by concentration
-1hCl solution the pH value of gained filtrate is adjusted to 3, finally (2h), solid-liquid separation process are left standstill to filtrate, then by the washing of gained solid substance to neutral, after 40 DEG C of vacuum drying treatment;
(2) oxidation modification of xylogen
The massfraction of the pretreated xylogen and 90 weight parts of getting 3 weight parts is the H of 30%
2o
2the massfraction that solution joins 50 weight parts is in ionic liquid [BMIm] Cl of 99.5%, by NaOH solution adjust ph to 10, then oxidizing reaction 3h under the condition of 70 DEG C, finally leave standstill (2h), solid-liquid separation process to the mixture of oxidizing reaction gained, gained solid substance is the xylogen after oxidation modification;
(3) synthesis of epoxy resin
The massfraction adding 35 weight parts in the xylogen after oxidation modification is the NaOH solution of 20% and the epoxy chloropropane of 90 weight parts, then epoxidation reaction 2h under 100 DEG C of conditions, finally (2h) left standstill to the mixture of epoxidation reaction gained, remove unreacted Feedstock treating, obtain described epoxy resin.
The epoxy resin of the present embodiment gained is faint yellow, and its oxirane value is 0.34 after tested, and viscosity is 33000mPa.S, and tensile strength is 15MPa, and xylogen utilization ratio is 87%.
The concrete operations of removing unreacted Feedstock treating in the step (3) of above-described embodiment 1 to embodiment 3 are: first solid-liquid separation removes xylogen, then rotary evaporation removes other unreacted raw material.
Be to be understood that example as herein described and embodiment only in order to illustrate, those skilled in the art can make various amendment or change according to it, when not departing from spirit of the present invention, all belong to protection scope of the present invention.
Claims (2)
1. utilize xylogen to prepare the method for epoxy resin, it is characterized in that, comprise the following steps:
(1) pre-treatment of xylogen
Xylogen is pulverized, then removes the inorganic salt impurities in xylogen;
(2) oxidation modification of xylogen
The massfraction of the pretreated xylogen and 35 ~ 90 weight parts of getting 1 ~ 3 weight part is the H of 30%
2o
2the massfraction that solution joins 30 ~ 50 weight parts is greater than in ionic liquid [BMIm] Cl of 99%, adjust ph to 8 ~ 10, then oxidizing reaction 2 ~ 4h under the condition of 50 ~ 90 DEG C, finally the mixture of oxidizing reaction gained is left standstill, solid-liquid separation process, gained solid substance is the xylogen after oxidation modification;
(3) synthesis of epoxy resin
The massfraction adding 35 ~ 60 weight parts in the xylogen after oxidation modification is the NaOH solution of 10 ~ 20% and the epoxy chloropropane of 45 ~ 90 weight parts, then epoxidation reaction 2 ~ 5h under 70 ~ 100 DEG C of conditions, finally the mixture of epoxidation reaction gained left standstill, remove unreacted Feedstock treating, obtain described epoxy resin.
2. utilize xylogen to prepare the method for epoxy resin as claimed in claim 1, it is characterized in that: the detailed process of step (1) is: lignin powder is broken to more than 80 orders, then under lower than the condition of 110 DEG C, be dried to constant weight, to be more fully dissolved in concentration be 0.5 ~ 2mol ﹒ L
-1naOH solution in, then carry out filtration treatment, then be 0.5 ~ 2molL by concentration
-1hCl solution the pH value of gained filtrate is adjusted to 2 ~ 3, finally filtrate to be left standstill, solid-liquid separation process, then by after gained solid substance washing to neutral, drying process.
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Cited By (3)
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| CN106243324A (en) * | 2016-08-02 | 2016-12-21 | 黄山市徽州天马化工有限公司 | A kind of fire-retardant epoxy resin and preparation method thereof |
| CN108420751A (en) * | 2018-04-12 | 2018-08-21 | 北京林业大学 | A kind of preparation method of the nano lignin particle with uvioresistant effect |
| CN109467716A (en) * | 2018-11-06 | 2019-03-15 | 安徽理工大学 | A kind of method of modifying of lignin and the preparation method of Lignin-based epoxy resin |
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| CN102675592A (en) * | 2012-06-08 | 2012-09-19 | 吉林大学 | Synthesizing method of epoxy resin by autocatalysis of lignin |
| CN103524709A (en) * | 2013-10-14 | 2014-01-22 | 南京林业大学 | Preparation method for epoxy resin |
| CN104193962A (en) * | 2014-08-29 | 2014-12-10 | 黄山市恒泰化工有限公司 | Lignin-based polyphenol glycidol ether epoxy resin and preparation method thereof |
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2015
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Patent Citations (3)
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| CN102675592A (en) * | 2012-06-08 | 2012-09-19 | 吉林大学 | Synthesizing method of epoxy resin by autocatalysis of lignin |
| CN103524709A (en) * | 2013-10-14 | 2014-01-22 | 南京林业大学 | Preparation method for epoxy resin |
| CN104193962A (en) * | 2014-08-29 | 2014-12-10 | 黄山市恒泰化工有限公司 | Lignin-based polyphenol glycidol ether epoxy resin and preparation method thereof |
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| 杨忠连等: "离子液体［BMIm］Cl中H2O2改性碱木质素的结构及热稳定性", 《化学工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243324A (en) * | 2016-08-02 | 2016-12-21 | 黄山市徽州天马化工有限公司 | A kind of fire-retardant epoxy resin and preparation method thereof |
| CN108420751A (en) * | 2018-04-12 | 2018-08-21 | 北京林业大学 | A kind of preparation method of the nano lignin particle with uvioresistant effect |
| CN109467716A (en) * | 2018-11-06 | 2019-03-15 | 安徽理工大学 | A kind of method of modifying of lignin and the preparation method of Lignin-based epoxy resin |
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Application publication date: 20150909 |