CN102391521B - Modified alkali lignin and preparation method thereof - Google Patents
Modified alkali lignin and preparation method thereof Download PDFInfo
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- CN102391521B CN102391521B CN 201110181503 CN201110181503A CN102391521B CN 102391521 B CN102391521 B CN 102391521B CN 201110181503 CN201110181503 CN 201110181503 CN 201110181503 A CN201110181503 A CN 201110181503A CN 102391521 B CN102391521 B CN 102391521B
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- alkali lignin
- deionized water
- methylene dichloride
- preparation
- iodotrimethylsilane
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Abstract
The invention relates to a modified alkali lignin and a preparation method thereof. In the invention, trimethyliodosilane and alkali lignin react to obtain the modified alkali lignin, and the phenolic hydroxyl group content of the prepared modified alkali lignin is greater than or equal to 1.8. In addition, the preparation method of the modified alkali lignin is simple, and does not destroy the structure of the alkali lignin.
Description
Technical field
The present invention relates to the chemical industry field, be specifically related to a kind of modification alkali lignin and preparation method thereof.
Background technology
Pulp and paper industry will be isolated about 1.4 hundred million t Mierocrystalline celluloses every year from plant, obtain the xylogen byproduct about 5,000 ten thousand t simultaneously.The lignin molecule amount that extracts from pulping waste liquor to millions of, and has significant polymolecularity at hundreds of, and is water insoluble, has good physics, chemical property, as fire-retardant, solvent resistance and good thermal stability.Industrial lignin generally exists with the alkali lignin form, and alkali lignin is important chemical material, carries out the chemistry comprehensive utilization, and is significant to middle-size and small-size paper mill black liquor treatment.The discharging of black liquid not only causes the significant wastage of resource, serious environment pollution again simultaneously, thereby it is carried out comprehensive development and utilization Economic development and environment protection all are of great immediate significance.
The industrial soda xylogen is actually the little fragment of alkali lignin macromolecules degradation formation and a kind of mixture of various fragment condensess, remains with macromolecular skeleton and the basic functions group of xylogen originally.As contain multiple functional group or chemical bonds such as phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl, carboxyl, methoxyl group, conjugated double bond, and have the aromatic nucleus of phenol type and non-phenol type, its side chain and aromatic proton all can carry out number of chemical reactions such as grafting.These character make alkali lignin have huge potential using value in modern chemistry industry.Along with the serious day by day of shortage of resources and enhancing day by day that human environment is realized, people pay close attention to the higher value application of the waste resource of this natural reproducible of alkali lignin more and more.The reactive behavior of alkali lignin itself is little, and the alkali lignin of non-modified is because performance is general, and its purposes generally is restricted, and is very little in industrial direct range of application.
Summary of the invention
In order to address the above problem, the invention provides the modification alkali lignin that a kind of preparation method is simple, content of phenolic hydroxyl groups is higher.
The content of phenolic hydroxyl groups of modification alkali lignin of the present invention 〉=1.8.
Further be described content of phenolic hydroxyl groups 〉=5.9.
The present invention also provides a kind of method for preparing described modification alkali lignin, and it comprises the steps:
(1) alkali lignin is dissolved in the solvent, makes alkali lignin solution;
(2) nitrogen deoxygenation adds Iodotrimethylsilane in alkali lignin solution, the mass ratio that makes alkali lignin and Iodotrimethylsilane is 1: 10～20;
(3) under temperature is 70～100 ℃ condition, reacted 1～2 hour, make the modification alkali lignin.
Wherein, solvent is methylene dichloride or water described in the step (1).
In addition, the alkali lignin strength of solution is 0.05～1g/ml described in the step (1).
In addition, the mass ratio of alkali lignin and Iodotrimethylsilane is 1: 12～16 described in the step (2).
In addition, the temperature in the step (3) is 90 ℃.
In addition, the reaction times in the step (3) is 2 hours.
The present invention utilizes demethylating reaction, the methoxyl group in the alkali lignin is removed the methyl modification become hydroxyl, prepares a kind of modification alkali lignin.Can carry out purifying to the raw material alkali lignin before preparation modification alkali lignin, purification process does not have particular restriction.
In addition, used Iodotrimethylsilane both can use the commercially available prod among the present invention, also can pass through at the laboratory sintetics.When synthetic in the laboratory, excessive slightly hexamethyldisilane and Iod R can be made, its preparation method mild condition, the time is short, and corrodibility is low relatively.
The present invention prepares the modification alkali lignin by the demethylation modification, and method is simple, and the structure of alkali lignin be there is no destruction, can be used as the industrial reaction raw material and further reacts, and its prospects for commercial application is extensive.
And modification alkali lignin preparation method of the present invention is simple, content of phenolic hydroxyl groups is higher, do not destroy the structure of alkali lignin, can realize the higher value application to waste resource.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Agents useful for same is as follows among the embodiment:
Alkali lignin: Tianjin is contained rich river chemical industry and is sold company limited
Sodium hydroxide: analytical pure, Beijing Chemical Plant
Sulfuric acid: 95%～98%, analytical pure, Beijing Chemical Plant
Iodotrimethylsilane: 99%, sunshine Li Deshi chemical industry company limited
Methylene dichloride: analytical pure, Beijing Chemical Plant
Embodiment 1
1, get the raw materials ready according to following proportioning:
Alkali lignin 5g
Methylene dichloride 50ml
Iodotrimethylsilane 50ml
2, preparation mixed solution
Alkali lignin and methylene dichloride are added in the three-necked flask, stir and make the alkali lignin dissolving, obtain alkali lignin-methylene dichloride mixed solution.
3, demethylating reaction
Feed nitrogen, drain air after, add the Iodotrimethylsilane of 50ml, 90 ℃ of following stirring reaction 2h, condensing reflux.
4, product is handled
1) at first stop heating, be cooled to room temperature, self-condensation mouth of pipe place adds deionized water;
2) close nitrogen, stop mechanical stirring, reacted material is carried out suction filtration, use the deionized water wash reactor, continue suction filtration;
3) use the deionized water wash filter cake, be colourless until filtrate;
4) with the filter cake oven dry, porphyrize namely gets product of the present invention.
Measure the content of phenolic hydroxyl groups of the modification alkali lignin material of present embodiment preparation according to Folin-Ciocalteu reagent method, detected result sees Table 1.
Embodiment 2
1, get the raw materials ready according to following proportioning:
Alkali lignin 5g
Water 100ml
Iodotrimethylsilane 35ml
2, preparation mixed solution
Alkali lignin and water are added in the three-necked flask, stir and make the alkali lignin dissolving, obtain the alkali lignin aqueous solution.
3, demethylating reaction
Feed nitrogen, drain air after, add the Iodotrimethylsilane of 35ml, 100 ℃ of following stirring reaction 1h, condensing reflux.
4, product is handled
1) at first stop heating, be cooled to room temperature, self-condensation mouth of pipe place adds deionized water;
2) close nitrogen, stop mechanical stirring, reacted material is carried out suction filtration, use the deionized water wash reactor, continue suction filtration;
3) use the deionized water wash filter cake, be colourless until filtrate;
4) with the filter cake oven dry, porphyrize namely gets product of the present invention.
Measure the content of phenolic hydroxyl groups of the modification alkali lignin material of present embodiment preparation according to Folin-Ciocalteu reagent method, detected result sees Table 1.
Embodiment 3
1, get the raw materials ready according to following proportioning:
Alkali lignin 5g
Methylene dichloride 100ml
Iodotrimethylsilane 70ml
2, preparation mixed solution
Alkali lignin and methylene dichloride are added three-necked flask, stir and make the alkali lignin dissolving, obtain alkali lignin-methylene dichloride mixed solution.
3, demethylating reaction
Feed nitrogen, drain air after, add the Iodotrimethylsilane of 70ml, 70 ℃ of following stirring reaction 2h, condensing reflux.
4, product is handled
1) at first stop heating, be cooled to room temperature, self-condensation mouth of pipe place adds deionized water;
2) close nitrogen, stop mechanical stirring, reacted material is carried out suction filtration, use the deionized water wash reactor, continue suction filtration;
3) use the deionized water wash filter cake, be colourless until filtrate;
4) with the filter cake oven dry, porphyrize namely gets product of the present invention.
Measure the content of phenolic hydroxyl groups of the modification alkali lignin material of present embodiment preparation according to Folin-Ciocalteu reagent method, detected result sees Table 1.
Table 1 modification alkali lignin phenol hydroxy value measuring result
The detected result of table 1 shows: the modification alkali lignin material of patent preparation of the present invention has higher content of phenolic hydroxyl groups, be 13 times of alkali lignin, illustrate that the Iodotrimethylsilane method makes content of phenolic hydroxyl groups obtain significant raising, further specify methoxyl group and remove relatively thoroughly that side reaction is less.
The modification alkali lignin of the present invention's preparation can prepare phenol-aldehyde tackiness agent with resin alloy, and the xylogen glue that makes has stronger crosslinking curing; Alkali lignin after the modification has phenol type building stone, can generate the product of similar resol with formaldehyde reaction, can be used as high temp profile control agent, is used in the steam recover petroleum; In addition, also can be used as tensio-active agent, flocculation agent, packing strengthening agent, antifreezing agent etc., can be widely used in agricultural, petroleum industry, water treatment, biochemical medicine, plastics industry and the building materials auxiliary agent, its application prospect is very wide.
Claims (2)
1. a modification alkali lignin is characterized in that, the content of phenolic hydroxyl groups of described modification alkali lignin is 5.920mmol/g;
The preparation method of described modification alkali lignin comprises the steps:
(1) get the raw materials ready according to following proportioning:
Alkali lignin 5g
Methylene dichloride 50ml
Iodotrimethylsilane 50ml;
(2) preparation mixed solution
Alkali lignin and methylene dichloride are added in the three-necked flask, stir and make the alkali lignin dissolving, obtain alkali lignin-methylene dichloride mixed solution;
(3) demethylating reaction
Feed nitrogen, drain air after, add the Iodotrimethylsilane of 50ml, 90 ℃ of following stirring reaction 2h, condensing reflux;
(4) product is handled
At first stop heating, be cooled to room temperature, self-condensation mouth of pipe place adds deionized water; Close nitrogen then, stop mechanical stirring, reacted material is carried out suction filtration, use the deionized water wash reactor, continue suction filtration; Use the deionized water wash filter cake again, be colourless until filtrate; With the filter cake oven dry, porphyrize namely gets described modification alkali lignin at last.
2. a method for preparing the described modification alkali lignin of claim 1 is characterized in that, comprises the steps:
The preparation method of described modification alkali lignin comprises the steps:
(1) get the raw materials ready according to following proportioning:
Alkali lignin 5g
Methylene dichloride 50ml
Iodotrimethylsilane 50ml;
(2) preparation mixed solution
Alkali lignin and methylene dichloride are added in the three-necked flask, stir and make the alkali lignin dissolving, obtain alkali lignin-methylene dichloride mixed solution;
(3) demethylating reaction
Feed nitrogen, drain air after, add the Iodotrimethylsilane of 50ml, 90 ℃ of following stirring reaction 2h, condensing reflux;
(4) product is handled
At first stop heating, be cooled to room temperature, self-condensation mouth of pipe place adds deionized water; Close nitrogen then, stop mechanical stirring, reacted material is carried out suction filtration, use the deionized water wash reactor, continue suction filtration; Use the deionized water wash filter cake again, be colourless until filtrate; With the filter cake oven dry, porphyrize namely gets described modification alkali lignin at last.
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| CN 201110181503 CN102391521B (en) | 2011-06-30 | 2011-06-30 | Modified alkali lignin and preparation method thereof |
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| CN 201110181503 CN102391521B (en) | 2011-06-30 | 2011-06-30 | Modified alkali lignin and preparation method thereof |
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| CN102391521A CN102391521A (en) | 2012-03-28 |
| CN102391521B true CN102391521B (en) | 2013-08-21 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104530444B (en) * | 2014-11-21 | 2017-02-22 | 东北林业大学 | Modification method for improving industrial lignin activity |
| CN106590555A (en) * | 2016-12-01 | 2017-04-26 | 东莞市联洲知识产权运营管理有限公司 | Nano anhydrous propylene glycol type automobile engine anti-freezing liquid and preparation method |
| CN115418002B (en) * | 2022-09-26 | 2024-03-29 | 江西师范大学 | Hydroxyl-rich lignin, preparation method and application thereof in selective adsorption separation of ammonia gas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250088A (en) * | 1979-08-20 | 1981-02-10 | American Can Company | Demethylated lignin and process |
| CN1148386A (en) * | 1994-04-11 | 1997-04-23 | 中外制药株式会社 | 4,6-di-5-butyl-2,3-dihydrobenzothiophene derivative |
-
2011
- 2011-06-30 CN CN 201110181503 patent/CN102391521B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250088A (en) * | 1979-08-20 | 1981-02-10 | American Can Company | Demethylated lignin and process |
| CN1148386A (en) * | 1994-04-11 | 1997-04-23 | 中外制药株式会社 | 4,6-di-5-butyl-2,3-dihydrobenzothiophene derivative |
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