CN102875698B - Method for synthesizing bagasse xylan sulfate by sodium aminotrisulfonate water-phase esterification process - Google Patents
Method for synthesizing bagasse xylan sulfate by sodium aminotrisulfonate water-phase esterification process Download PDFInfo
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- CN102875698B CN102875698B CN201210421832.1A CN201210421832A CN102875698B CN 102875698 B CN102875698 B CN 102875698B CN 201210421832 A CN201210421832 A CN 201210421832A CN 102875698 B CN102875698 B CN 102875698B
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Abstract
The invention discloses a method for synthesizing bagasse xylan sulfate by a sodium aminotrisulfonate water-phase esterification process, which comprises the following steps: reacting an NaHSO3 solution and a NaNO2 solution to obtain an esterifying agent sodium aminotrisulfonate (N(SO3Na)3) solution with sulfo-group; and by using bagasse xylan as the main raw material, sodium aminotrisulfonate as the esterifying agent and 12-tungstophosphoric acid as a catalyst, carrying out catalytic reaction on the bagasse xylan and the esterifying agent sodium aminotrisulfonate in a water phase to generate bagasse xylan sodium sulfonate, acidifying, washing with acetone, carrying out vacuum filtration, and drying to obtain the bagasse xylan sulfate. The method disclosed by the invention has the advantages of high degree of substitution, low cost, simple technological operation, environmental protection, easy after-treatment and the like, and overcomes some defects in the organic phase process.
Description
Technical field
The present invention relates to the method for the synthetic bagasse xylan sulfuric ester of a kind of amino sodium trisulfonate esterification in aqueous phase method.
Background technology
Xylan is the main component that is extensively present in hemicellulose in natural vegetable fibre, has unique biological activity, biodegradable, nontoxicity and good biocompatibility.Due to the defect of xylan self performance, its modification is subject to the attention of increasing Chinese scholars.At present, the modification technology of xylan mainly comprises the etherificate, esterification, oxidation of xylan and crosslinked etc.Research discovery, xylan can effectively suppress HIV to CD after sulphating
4infecting of cell, and there is the effect of anticoagulation, thrombus dissolving.At present, the reaction of synthetic xylan sulfuric ester both at home and abroad generally adopts organic reagent reaction system, as xylan is reacted in DMSO with piperidines-N-sulfonate, can prepare the piperidines of substitution value between 0.2～1.6-
n-sulfonic group xylan; Also available chlorine sulfonic acid-pyridine method is that chlorsulfonic acid is esterifying reagent, and anhydrous pyridine and methane amide etc. are the synthetic corn cob of reaction solvent or bagasse xylan sulfuric ester.Why the synthetic solvents of organic reagents as reaction system that adopt of xylan sulfuric ester, are to be mostly strongly-acid reagent because prepare the esterifying agent of xylan sulfuric ester more, the degraded of making solvent and can avoiding or alleviate xylan chain with organic reagent.But the technique of the synthetic xylan sulfuric ester of solvent method using organic reagent as reaction system is loaded down with trivial details, environmental pollution serious, cost is relatively high, aftertreatment trouble etc.
The present invention, taking bagasse xylan as main raw material, adopts a kind of relatively mild esterifying agent to substitute strongly-acid esterifying agent, and reaction system changes water into from organic phase, thereby avoids the degraded of xylan chain in reaction process.
Summary of the invention
The object of the invention is to prepare in order to overcome current organic solvent method the problem such as environmental protection that bagasse xylan sulfuric ester exists, the method for a kind of amino sodium trisulfonate esterification in aqueous phase legal system for bagasse xylan sulfuric ester is provided.
Concrete steps are:
(1) by 6 ~ 8g solid NaHSO
3adding successively volume with 25 ~ 30mL distilled water is in the four-necked bottle of 250mL, the even NaHSO that obtains of stirring and dissolving under room temperature
3solution.
(2) NaHSO of heating steps (1) gained under agitation
3solution to temperature is 80 ~ 90 DEG C, evenly drips massfraction and be 20% NaNO
2solution 4 ~ 7mL, controls and dropwises for 20 ~ 30 minutes, continues to stir 10 ~ 15 minutes, obtains the amino sodium trisulfonate solution of esterifying agent.
(3) take 3 ~ 6g bagasse xylan and join in the amino sodium trisulfonate solution of step (2) gained, then add 0.03 ~ 0.2g catalyzer 12-tungstophosphoric acid; Controlling temperature of reaction is 40 ~ 60 DEG C, and adopting massfraction is that 5% sodium hydroxide solution adjustment reaction system pH is 7～10, under agitation reacts 4～6 hours.
(4) to the analytical pure acetone that adds 30 ~ 50mL in step (3) gained reaction solution, precipitate 15 ~ 20 minutes; Suction filtration, and with 15 ~ 20mL analytical pure washing with acetone throw out filter cake 3 times.
(5) throw out after step (4) gained washing is placed in to the four-necked bottle of 250mL, adds 40 ~ 50mL distilled water, under agitation drip 2 ~ 5mL massfraction and be 38% hydrochloric acid soln, dropwise rear continuation and stir 10 ~ 15 minutes.
(6) gained solution in step (5) is transferred in the beaker of 500mL, under glass stick stirs, added 25 ~ 30mL analytical pure acetone, separate out the rear suction filtration of precipitation, obtain the thick product of bagasse xylan sulfuric ester.
(7) by 10 ~ 15mL analytical pure washing with acetone 3 times for the thick product of gained in step (6), suction filtration, obtains throw out.
(8) throw out of gained in step (7) is placed in to the thermostatic drying chamber of 50 DEG C and is dried to constant weight, obtain product bagasse xylan sulfuric ester.
(9) adopt BaCl
2the substitution value of products obtained therefrom in-Turbidity of Gelatin method determination step (8).Substitution value
dScalculation formula be:
DS=(132×
S%)/(32－102×
S%)
In formula:
s%---the quality percentage composition of sulphur in sample;
132---the relative molecular mass of wood sugar unit in xylan molecule;
102---become-OSO after 1 hydroxyl in polysaccharide molecule is substituted
3na, the increased value of relative molecular mass is 102;
32---the relative atomic mass of S.
NaHSO
3and NaNO
2reaction under certain conditions can generate the amino sodium trisulfonate (N (SO with sulfonic acid group
3na)
3), amino sodium trisulfonate can be used as esterifying agent and bagasse xylan and reacts and generate bagasse xylan sulfonate sodium, then can obtain bagasse xylan sulfuric ester through acidifying.The advantages such as the method for the synthetic bagasse xylan sulfuric ester of the amino sodium trisulfonate esterification in aqueous phase method that the present invention relates to has that substitution value is high, cost is low, technological operation is easy, environmental protection, aftertreatment are easy, have overcome the some shortcomings of organic phase method.
Brief description of the drawings
Fig. 1 is bagasse xylan IR figure.
Fig. 2 is bagasse xylan sulfuric ester IR figure prepared by the embodiment of the present invention 2.
Fig. 3 is former tapioca (flour) SEM figure.
Fig. 4 is bagasse xylan sulfuric ester SEM figure prepared by the embodiment of the present invention 2.
Embodiment
Embodiment 1:
(1) by 7.2gNaHSO
3solid and 30mL distilled water add in four-necked bottle, and NaHSO at room temperature stirs to obtain
3solution.
(2) NaHSO of heating steps (1) gained under agitation
3solution to temperature is 82 ± 2 DEG C, evenly drips massfraction and be 20% NaNO
2solution 5mL, after controlling and dropwising for 25 minutes, continues to stir 10 minutes, obtains the amino sodium trisulfonate solution of esterifying agent.
(3) take 3.50g bagasse xylan and join in the amino sodium trisulfonate solution of step (2) gained, then add 0.1g catalyzer 12-tungstophosphoric acid; Controlling temperature of reaction is 50 DEG C, and adopting massfraction is that 5% sodium hydroxide solution adjustment reaction system pH is 9.0, under agitation reacts 5 hours.
(4) to the analytical pure acetone that adds 35mL in step (3) gained reaction solution, precipitate 20 minutes; Suction filtration, and with 15mL analytical pure washing with acetone throw out filter cake 3 times.
(5) throw out after step (4) gained washing is placed in to the four-necked bottle of 250mL, adds 45mL distilled water, under agitation drip 3mL massfraction and be 38% hydrochloric acid soln, dropwise rear continuation and stir 15 minutes.
(6) gained solution in step (5) is transferred in the beaker of 500mL, under glass stick stirs, added 30mL analytical pure acetone, separate out the rear suction filtration of precipitation, obtain the thick product of bagasse xylan sulfuric ester.
(7) by 15mL analytical pure washing with acetone 3 times of the thick product of gained in step (6), suction filtration, obtains throw out.
(8) throw out of gained in step (7) is placed in to the thermostatic drying chamber of 50 DEG C and is dried to constant weight, obtain product.
(9) use BaCl
2the substitution value of products obtained therefrom in-Turbidity of Gelatin method determination step (8), obtaining its substitution value is 1.22.
Embodiment 2:
(1) by 5.0gNaHSO
3solid and 25mL distilled water add in four-necked bottle, and NaHSO at room temperature stirs to obtain
3solution.
(2) NaHSO of heating steps (1) gained under agitation
3solution to temperature is 85 ± 2 DEG C, evenly drips massfraction and be 20% NaNO
2solution 4mL, after controlling and dropwising for 20 ~ 25 minutes, continues to stir 10 minutes, obtains the amino sodium trisulfonate solution of esterifying agent.
(3) take 3.00g bagasse xylan and join in the amino sodium trisulfonate solution of step (2) gained, then add 0.08g catalyzer 12-tungstophosphoric acid; Controlling temperature of reaction is 40 DEG C, and adopting massfraction is that 5% sodium hydroxide solution adjustment reaction system pH is 10.0, under agitation reacts 4 hours.
4) to the analytical pure acetone that adds 30mL in step (3) gained reaction solution, precipitate 15 minutes; Suction filtration, and with 13mL analytical pure washing with acetone throw out filter cake 3 times.
(5) throw out after step (4) gained washing is placed in to the four-necked bottle of 250mL, adds 35mL distilled water, under agitation drip 2mL massfraction and be 38% hydrochloric acid soln, dropwise rear continuation and stir 15 minutes.
(6) gained solution in step (5) is transferred in the beaker of 500mL, under glass stick stirs, added 25mL analytical pure acetone, separate out the rear suction filtration of precipitation, obtain the thick product of bagasse xylan sulfuric ester.
(7) by thick product 15mL washing with acetone 3 times of gained in step (6), suction filtration, obtains throw out.
(8) throw out of gained in step (7) is placed in to the thermostatic drying chamber of 50 DEG C and is dried to constant weight, obtain product.
(9) use BaCl
2the substitution value of products obtained therefrom in-Turbidity of Gelatin method determination step (8), obtaining its substitution value is 0.51.
Product is analyzed through IR, and spectrogram is at 1122.78cm
-1place is the feature stretching vibration absorption peak of S=O, 803.52cm
-1place is the feature stretching vibration absorption peak of S-O; In the IR of bagasse xylan figure, do not observe these absorption peaks, illustrate bagasse xylan successfully on keyed jointing sulfate groups.Sem analysis result has shown the particle surface pattern before and after bagasse xylan modification, can find out bagasse xylan rough, is amorphous state; And bagasse xylan sulfuric ester particle surface has obvious damaged rill and space, maximum diameter of hole reaches 4.8 μ m, and its structure originally is damaged, form and structure generation considerable change.
Claims (1)
1. a method for the synthetic bagasse xylan sulfuric ester of amino sodium trisulfonate esterification in aqueous phase method, is characterized in that concrete steps are:
(1) by 6 ~ 8g solid NaHSO
3adding successively volume with 25 ~ 30mL distilled water is in the four-necked bottle of 250mL, the even NaHSO that obtains of stirring and dissolving under room temperature
3solution;
(2) NaHSO of heating steps (1) gained under agitation
3solution to temperature is 80 ~ 90 DEG C, evenly drips massfraction and be 20% NaNO
2solution 4 ~ 7mL, controls and dropwises for 20 ~ 30 minutes, continues to stir 10 ~ 15 minutes, obtains the amino sodium trisulfonate solution of esterifying agent;
(3) take 3 ~ 6g bagasse xylan and join in the amino sodium trisulfonate solution of step (2) gained, then add 0.03 ~ 0.2g catalyzer 12-tungstophosphoric acid; Controlling temperature of reaction is 40 ~ 60 DEG C, and adopting massfraction is that 5% sodium hydroxide solution adjustment reaction system pH is 7～10, under agitation reacts 4～6 hours;
(4) to the analytical pure acetone that adds 30 ~ 50mL in step (3) gained reaction solution, precipitate 15 ~ 20 minutes; Suction filtration, and with 15 ~ 20mL analytical pure washing with acetone throw out filter cake 3 times;
(5) throw out after step (4) gained washing is placed in to the four-necked bottle of 250mL, adds 40 ~ 50mL distilled water, under agitation drip 2 ~ 5mL massfraction and be 38% hydrochloric acid soln, dropwise rear continuation and stir 10 ~ 15 minutes;
(6) gained solution in step (5) is transferred in the beaker of 500mL, under glass stick stirs, added 25 ~ 30mL analytical pure acetone, separate out the rear suction filtration of precipitation, obtain the thick product of bagasse xylan sulfuric ester;
(7) by 10 ~ 15mL analytical pure washing with acetone 3 times for the thick product of gained in step (6), suction filtration, obtains throw out;
(8) throw out of gained in step (7) is placed in to the thermostatic drying chamber of 50 DEG C and is dried to constant weight, obtain product bagasse xylan sulfuric ester.
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| CN103130917A (en) * | 2013-03-21 | 2013-06-05 | 苏州鸿洋医药科技有限公司 | Preparation method of pentosan polysulfuric acid and salt thereof |
| CN104119452B (en) * | 2014-07-16 | 2016-10-05 | 北京化工大学 | The method that one class polyacid catalyzes and synthesizes cellulose esters |
| CN104530263B (en) * | 2014-12-17 | 2016-09-28 | 桂林理工大学 | A kind of preparation method of gallic acid bagasse xylan ester |
| CN104628882B (en) * | 2015-03-08 | 2017-04-12 | 桂林理工大学 | Synthetic method of sulfo bagasse xylan phthalate |
| CN104610469A (en) * | 2015-03-08 | 2015-05-13 | 桂林理工大学 | Synthesis method for anti-staphylococcus aureus double-activity gallic acid-sulfated bagasse xylan |
| CN106519079A (en) * | 2016-10-26 | 2017-03-22 | 桂林理工大学 | Synthetic method of anti-HIV-activity sulfonyl bagasse xylan polyethylene terephthalate |
| CN106366216B (en) * | 2016-10-26 | 2019-11-26 | 桂林理工大学 | A kind of synthetic method of double activated sulfonic group bagasse xylan sulfosalicylic acid ester |
| CN106565857A (en) * | 2016-10-26 | 2017-04-19 | 桂林理工大学 | Method for synthesizing double-active sulfo bagasse xylan isophthalate |
| CN106366215A (en) * | 2016-10-26 | 2017-02-01 | 桂林理工大学 | Preparation method of double-esterification active sulfo bagasse xylan paraben |
| CN107556405A (en) * | 2017-09-15 | 2018-01-09 | 桂林理工大学 | A kind of preparation method of double activated sulfonic group bagasse xylan to hydroxyl salicylate |
| CN107417810B (en) * | 2017-09-15 | 2019-11-26 | 桂林理工大学 | The synthetic method of AntiHIV1 RT activity double activated sulfonic group bagasse xylan ferrocenecarboxylic acid ester |
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Non-Patent Citations (2)
| Title |
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| H.Sisler.Potassium Nitrilosulfonate.《Journal of the american chemical society》.1938,第60卷(第8期), * |
| Potassium Nitrilosulfonate;H.Sisler;《Journal of the american chemical society》;19380831;第60卷(第8期);第1947页第2栏 * |
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Effective date of registration: 20201224 Address after: 224700 Industrial Park, Jianyang Town, Jianhu County, Yancheng City, Jiangsu Province Patentee after: JIANGSU SHUANGXIN GROUP Co.,Ltd. Address before: Unit 2414-2416, main building, no.371, Wushan Road, Tianhe District, Guangzhou City, Guangdong Province Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20201224 Address after: Unit 2414-2416, main building, no.371, Wushan Road, Tianhe District, Guangzhou City, Guangdong Province Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: 541004 the Guangxi Zhuang Autonomous Region Guilin Construction Road No. 12 Patentee before: GUILIN University OF TECHNOLOGY |