CN107597076A - A kind of aminocellulose and its application - Google Patents
A kind of aminocellulose and its application Download PDFInfo
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- CN107597076A CN107597076A CN201710941320.0A CN201710941320A CN107597076A CN 107597076 A CN107597076 A CN 107597076A CN 201710941320 A CN201710941320 A CN 201710941320A CN 107597076 A CN107597076 A CN 107597076A
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Abstract
The invention discloses a kind of aminocellulose and its application, its structural formula is：Wherein X is SO3Na or SO3NH4Its amino group substitution degree DS=0.50~1.40.The present invention passes through one-step synthesis method aminocellulose, low in raw material price, wide material sources using cellulose sulfate as raw material with aminating agent, technique is simple, cost is relatively low, overcomes existing synthetic method complex manufacturing, severe reaction conditions, the shortcomings that cost of material is high, and process costs are high.Obtained aminocellulose is preferable to the heavy metal ion adsorbed effect in waste water, has higher actual application value.
Description
Technical field
The invention belongs to organic high molecular compound technical field, and in particular to a kind of aminocellulose and its application.
Background technology
Saccharide compound is a kind of reproducible organic resource, be eat, wear in people's life, one of main source,
Play the role of to the activity of sustaining life critically important.Amino sugar is a kind of nitrogen containing derivative of saccharide compound, is many biologies
The important component of the metabolite of macromolecular and microorganism, there is important biochemical action.And chitosan is as a kind of typical
Aminosugars compound, all it is widely used in fields such as agricultural, food industry, textile industry, daily-use chemical industries, especially in environment
Protection field can be used for the processing of industrial wastewater heavy metal as water treatment agent.The heavy metal wastewater thereby of high concentration is heavy by chemistry
After the processing of the conventional methods such as shallow lake, ion exchange, still containing micro heavy metal ion, though its concentration is small, harm is not allowed
Neglect, easily gathered by food chain in human body or other biological body.Natural polymer chitosan is because of ammonia on its molecular structure
Base nitrogen, hydroxyl oxygen energy and transition metal ions form coordinate bond by extremely strong coordination, effectively can adsorb or trap and be molten
Heavy metal ion in liquid, and remove the poisonous ion such as the lead in water body, mercury, chromium.But chitosan mainly passes through shrimp crab at present
Shell produces, its technological process of production very complicated, production cycle length, and " three wastes " amount is big, and yield is low, and product quality is difficult to control,
So far, fancy price hinders widely using for chitosan.
For cellulose as the polysaccharide most wide, quantity is most is distributed in nature, its inexpensive thing is rich, structure and chitosan class
Seemingly, and structure is easily modified, therefore amino can be introduced into cellulosic molecule, prepares class chitosan, is used with reaching with chitosan
Way similar purpose.
CN103554510A discloses a kind of preparation method of Amino End Group modified cellulose, will first pass through cleaning-drying to perseverance
The bagasse raw material of weight is dipped to more than 10 hours in concentrated base, washing, is filtered, is obtained alkali sugarcane fiber after drying, then will
Alkali sugarcane fiber occurs oxidation reaction with strong oxidizer under the conditions of lucifuge and obtains dialdehyde bagasse cellulose；Then with metering system
Sour methyl esters and ethylenediamine are raw material, in organic solvent under the conditions of lucifuge oxygen barrier stirring occur polymerisation obtain it is amine-terminated hyperbranced
Fluidized polymer, carry out flowing back instead after finally dissolving dialdehyde bagasse cellulose and Hyperbranched Polymer with Terminal Amido in organic solvent
Should be that can obtain amine-terminated hyperbrancedization grafting dialdehyde cellulose.This method complex manufacturing, time-consuming, and reaction condition requirement
Height, process costs are high, are unfavorable for industrialized production and application.
CN101027324A is disclosed using cellulose and is had general formula X-(CH2)n-NR1R2Alkylating reagent (X represent
Leaving group, such as chlorine, bromine, iodine or sulfonic group R ' SO3) it is raw material, prepared in the basic conditions by condensation reaction containing amino
The method of cellulose derivative.Although this method technique is relatively simple, used alkylating reagent X- (CH2)n-NR1R2No
Easily obtain, it is expensive, it is unfavorable for industrialized production and application.
The content of the invention
It is an object of the invention to provide a kind of aminocellulose.
Another object of the present invention is to provide the application of above-mentioned aminocellulose.
Technical scheme is as follows：
A kind of aminocellulose, its structural formula are：
Wherein X is-SO3Na or-SO3NH4Its
Amino group substitution degree DS=0.50~1.40；
Its synthetic method includes：Cellulose sulfate and excess of ammonia reagent are added in autoclave, 100~
Utilized under 200 DEG C of constant temperature and naturally cool to room temperature from 6~48h of booster reaction, reaction after terminating, then carry out separation of solid and liquid, i.e.,
；Above-mentioned aminating agent is water, methanol or the ethanol solution of ammonia.
The reaction equation of its synthetic method is as follows：
In a preferred embodiment of the invention, the mol ratio of the ammonia in the cellulose sulfate and aminating agent
For 1: 2~10.
Another technical scheme of the present invention is as follows：
Application of the above-mentioned aminocellulose in heavy metal ion is adsorbed.
In a preferred embodiment of the invention, the heavy metal ion include copper ion, lead ion, chromium ion,
At least one of cadmium ion and nickel ion.
Beneficial effects of the present invention：
1st, the present invention passes through one-step synthesis method aminocellulose, raw material using cellulose sulfate as raw material with aminating agent
Cheap, wide material sources, technique is simple, cost is relatively low, overcomes existing synthetic method complex manufacturing, and reaction condition is severe
Carve, the shortcomings that cost of material is high, and process costs are high, it is preferable to the heavy metal ion adsorbed effect in waste water, have higher
Actual application value.
2nd, the structure of aminocellulose of the invention is similar with chitosan, has good chelation with a variety of metals,
Amino, hydroxyl on its macromolecular chain can form stable chelate with a variety of toxic metal ions, so as to remove in waste water
Heavy metal ion, thus the processing of heavy metal ions in wastewater can be used it for.Advantages of good adsorption effect, efficiency high, adsorb heavy metal
Ionic species is more, and can adsorb contents of many kinds of heavy metal ion simultaneously.Adsorb the separating process of the aminocellulose of heavy metal ion
Simply, it can recycle, work well after desorption.
Brief description of the drawings
Fig. 1 is the nuclear-magnetism comparison diagram of the cellulose sodium sulfate in the present invention and obtained aminocellulose.
Embodiment
Technical scheme is further detailed and described below by way of embodiment combination accompanying drawing.
Embodiment 1
Cellulose sodium sulfate and 25% ammoniacal liquor are added in autoclave with mol ratio 1: 5, rapid sealing, 180 DEG C
It is lower to utilize boosting constant temperature stirring reaction 24h certainly.After reaction terminates, room temperature is naturally cooled to, reaction has solid generation, separation of solid and liquid
Go out filter cake, dried at 80 DEG C to constant weight.Product finds occur new peak at δ=41ppm by nmr analysis, through consult be-
CH2- N- chemical shift；N content is obtained by elementary analysis and determines DS=1.31.The nuclear magnetic resonance C spectrums and N of comprehensive analysis product
Content, it may be determined that amino is carried out for cellulose sodium sulfate using the method in this research and substituted successfully.
Embodiment 2
Cellulose sodium sulfate and 25% ammoniacal liquor are added in autoclave with mol ratio 1: 5, it is rapid closed, 180 DEG C
It is lower to utilize boosting constant temperature stirring reaction 6h certainly.After reaction terminates, room temperature is naturally cooled to, reaction has solid generation, separation of solid and liquid
Go out filter cake, dried at 80 DEG C to constant weight.Product finds occur new peak at δ=41ppm by nmr analysis, through consult be-
CH2- N- chemical shift；N content is obtained by elementary analysis and determines DS=1.09.The nuclear magnetic resonance C spectrums and N of comprehensive analysis product
Content, it may be determined that amino is carried out for cellulose sodium sulfate using the method in this research and substituted successfully.
The cellulose derivative containing amino being prepared is carried out to the adsorption applications of heavy metal ion：
Embodiment 3
Aminocellulose (DS=1.31) made from the embodiment of the present invention 1 is added in lead ion solution, stirring and adsorbing,
After reaching adsorption equilibrium, the concentration of heavy metal in solution before and after adsorbing is analyzed, measures aminocellulose effects of ion adsorption rate
For 81.6%.The aminocellulose of adsorpting lead ion is desorbed, concrete technology is as follows：The adsorpting lead ion that will be filtrated to get
Aminocellulose with a small amount of 1% HCl soak 30min, filtering, filter cake again with a small amount of 1% NaOH soak 30min after mistake
Filter, filter cake is then washed till neutrality with distilled water, at 60 DEG C drying can recycled, adsorption effect is good.
Embodiment 4
Aminocellulose (DS=1.09) made from the embodiment of the present invention 2 is added in copper ion solution, stirring and adsorbing,
After reaching adsorption equilibrium, the concentration of heavy metal in solution before and after adsorbing is analyzed, measures aminocellulose effects of ion adsorption rate
For 74.3%.The aminocellulose for adsorbing copper ion is desorbed, concrete technology is as follows：The absorption copper ion that will be filtrated to get
Aminocellulose with a small amount of 1% HCl soak 30min, filtering, filter cake again with a small amount of 1% NaOH soak 30min after mistake
Filter, filter cake is then washed till neutrality with distilled water, at 60 DEG C drying can recycled, adsorption effect is good.
Aminocellulose made from embodiments of the invention 1 and 2 carries out qualitative analysis by nuclear magnetic resonance C spectrograms, compares
The nuclear-magnetism figure of reactant cellulose sulfate and product, is as a result shown in Fig. 1；Contrasted from spectrogram, reaction product is in δ=41ppm
There is new peak in place, is-CH through consulting2- N- chemical shift.N content is obtained by elementary analysis and determines DS 0.50~1.40, is received
Rate is 40%-60%.The nuclear magnetic resonance C spectrums and N content of comprehensive analysis synthetic product, it may be determined that using the method in this research
Amino is carried out for cellulose sulfate to substitute successfully.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still it belong in the range of the present invention covers.
Claims (4)
- A kind of 1. aminocellulose, it is characterised in that：Its structural formula is：Wherein X is-SO3Na or-SO3NH4Its amino Substitution value DS=0.50~1.40；Its synthetic method includes：Cellulose sulfate and excess of ammonia reagent are added in autoclave, 100~200 Utilized under DEG C constant temperature and naturally cool to room temperature from 6~48h of booster reaction, reaction after terminating, then carry out separation of solid and liquid, produce； Above-mentioned aminating agent is water, methanol or the ethanol solution of ammonia.
- A kind of 2. aminocellulose as claimed in claim 1, it is characterised in that：In the cellulose sulfate and aminating agent Ammonia mol ratio be 1: 2~10.
- A kind of 3. application of aminocellulose in heavy metal ion is adsorbed described in claim 1 or 2.
- 4. application as claimed in claim 3, it is characterised in that：The heavy metal ion include copper ion, lead ion, chromium from At least one of son, cadmium ion and nickel ion.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530546A (en) * | 2018-04-20 | 2018-09-14 | 厦门大学 | The synthesis and application of quasi- chitosan and its derivative |
| CN110773132A (en) * | 2019-11-04 | 2020-02-11 | 齐鲁工业大学 | Preparation method and application of aminated nanocrystalline cellulose chromium efficient desorbent |
| CN112175096A (en) * | 2020-10-09 | 2021-01-05 | 厦门大学 | Carboxymethyl-like chitosan and one-step synthesis process |
| CN116655812A (en) * | 2023-05-23 | 2023-08-29 | 苏州博睿特环保科技有限公司 | Lead ion adsorption material in battery recovery feed liquid and preparation method thereof |
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| CN103360499A (en) * | 2012-04-11 | 2013-10-23 | 厦门大学 | Simple synthesis process of cellulose sulfate |
| CN103987733A (en) * | 2011-10-14 | 2014-08-13 | 巴斯夫欧洲公司 | Preparation of oligosaccharides containing amine groups |
| CN105013447A (en) * | 2015-07-01 | 2015-11-04 | 南通大学 | Preparation method of modified cellulose heavy metal adsorbent |
| CN107056955A (en) * | 2017-05-26 | 2017-08-18 | 厦门大学 | A kind of exploitation for the synthesis and green surfactant for intending chitosan soap |
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| CN103987733A (en) * | 2011-10-14 | 2014-08-13 | 巴斯夫欧洲公司 | Preparation of oligosaccharides containing amine groups |
| CN103360499A (en) * | 2012-04-11 | 2013-10-23 | 厦门大学 | Simple synthesis process of cellulose sulfate |
| CN105013447A (en) * | 2015-07-01 | 2015-11-04 | 南通大学 | Preparation method of modified cellulose heavy metal adsorbent |
| CN107056955A (en) * | 2017-05-26 | 2017-08-18 | 厦门大学 | A kind of exploitation for the synthesis and green surfactant for intending chitosan soap |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530546A (en) * | 2018-04-20 | 2018-09-14 | 厦门大学 | The synthesis and application of quasi- chitosan and its derivative |
| CN110773132A (en) * | 2019-11-04 | 2020-02-11 | 齐鲁工业大学 | Preparation method and application of aminated nanocrystalline cellulose chromium efficient desorbent |
| CN110773132B (en) * | 2019-11-04 | 2022-09-13 | 齐鲁工业大学 | Preparation method and application of aminated nanocrystalline cellulose chromium efficient desorbent |
| CN112175096A (en) * | 2020-10-09 | 2021-01-05 | 厦门大学 | Carboxymethyl-like chitosan and one-step synthesis process |
| CN112175096B (en) * | 2020-10-09 | 2022-04-26 | 厦门大学 | Carboxymethyl-like chitosan and one-step synthesis process |
| CN116655812A (en) * | 2023-05-23 | 2023-08-29 | 苏州博睿特环保科技有限公司 | Lead ion adsorption material in battery recovery feed liquid and preparation method thereof |
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Application publication date: 20180119 |