CN101914850B - Method for sulfonating surface of plant fiber - Google Patents
Method for sulfonating surface of plant fiber Download PDFInfo
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- CN101914850B CN101914850B CN2010102663754A CN201010266375A CN101914850B CN 101914850 B CN101914850 B CN 101914850B CN 2010102663754 A CN2010102663754 A CN 2010102663754A CN 201010266375 A CN201010266375 A CN 201010266375A CN 101914850 B CN101914850 B CN 101914850B
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Abstract
The invention relates to a method for sulfonating the surface of plant fiber. The method comprises the following steps of: forming an epoxy compound by using ClCH2-CH (OH)-(CH2) n-SO3Na (n is equal to be between 1 and 10) in concentrated alkaline solution; and performing a ring-opening reaction of the epoxy compound and hydroxyl on the surface of the plant fiber so as to introduce sulfoacid groups for cellulose and make the sulfonic acid group content of the surface of the sulfonated fiber reach about 0.046 mmol/g of fiber. The sulfonating method has the advantages of simple preparation method, short reaction time, no toxicity in reagent, safe experimental process and good experimental effect.
Description
Technical field
The present invention relates to a kind of method of string sulfonating surface, belong to papermaking, weaving and sponge manufacture field.
Background technology
Cellulose is a kind of reproducible natural polymer; Content is the abundantest in plant; And cellulose has cheapness, degradable, environment is not produced characteristics such as pollution; So along with the development of society and the progress of science and technology, cellulose not only is used for papermaking, textile industry, each country all attaches great importance to cellulosic research and development.Be that the product that raw material is processed also is used to aspects such as plastics, explosive, electrician and scientific research apparatus widely with the cellulose now.
But cellulosic architectural characteristic has determined the water insoluble and common organic solvents of cellulose, also lacks thermoplasticity simultaneously, is difficult to processing and forming, and this has just limited its application in every respect, so the research of cellulose being carried out the modification aspect has just been arranged.Cellulose modifiedly can be divided into multiplely, for example on cellulose, connect other active groups, cellulose is carried out esterification, etherificate etc.
Now a large amount of research is arranged both at home and abroad,, improve its suction, anti-outlet capacity, and change its surperficial chemical property to improve the compatibility of fiber and other materials to fibre modification.The research of one of them is to change plant fiber material surface electric charge character, thus improve its dyeing and finishing, absorption and with electrolytical binding ability.Carboxylated is a most popular field of research.Its method comprises the hydroxyl with TEMPO selective oxidation C6, periodate oxidation etc.It is reported to make the surface charge of broad-leaved wood sulphate pulp fiber increase by 150%, consequently use dried/wet tensile (strength) of the paper of the slurry production of handling to increase 30-200%. through the TEMPO oxidation system
The cellulose sulfonation is another approach that lets the charge property of fiber surface change, yet research in this respect is few.The cellulose sulfonation is introduced sulfonic group exactly on fiber, thereby increases cellulosic stability, and surface charge.Sulfonation can be divided into Direct Sulfonation and indirect sulfonation, and Direct Sulfonation is exactly direct and fibrin reaction with sulfonating agent, and indirect sulfonation then is before sulfonation, with alkali fiber to be carried out preliminary treatment earlier.
The people such as open when bright once to the cotton preparation feedback of sulfonation, the mechanism of enrichment, and the cotton stability of sulfonation studies, inquire into its characterization of adsorption simultaneously contents of many kinds of heavy metal ion.What his experiment was selected for use is absorbent cotton, is soaked in 95% ethanolic solution that contains 2% NaOH 40 minutes, in sintered filter funnel, does near with washing with alcohol and suction filtration, repeats twice, and the method that again absorbent cotton was soaked in the carbon disulfide 100 minutes prepares.People such as Zhang Xiangyu also once did cellulosic sulfonation experiment.The Direct Sulfonation method is adopted in their experiment, is sulfonating agent with the chlorosulfonic acid, and chloroform is a dispersant, and cellulose is a raw material, has prepared sulfonated cellulose, and it is used as oil-well cement filtrate reducer, can inquire into its filtrate-loss control.
In a word, existing string sulfonating surface method is reacted equal more complicated, and the not environmental protection of reaction reagent that has, such as the chloroform of using in carbon disulfide in the appeal first method and the second method.The method of sulfonating of fiber remains further to be researched and developed out a kind of environmental friendliness, low, the simple method of modifying of technology of cost.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of environmental friendliness, low, the simple method of modifying of technology of cost are provided.The object of the invention is realized through following technical proposals:
A kind of method of string surface modification is characterized in that comprising the steps:
(1) adopts water soluble sulfonated reagent with
(wherein n=1～10) structure;
(2) in 20～50% concentrated alkali solution, generate the material with epoxy construction, the material of said epoxidation structure and the mol ratio of alkali are 1: 1～1: 4;
(3) adding string in the solution of said sulfonating agent and alkali makes it to soak fully; The fiber that soaks is evenly distributed soup through squeezing and is convenient to quality control in fiber, the degree of squeezing be make the amount of wet string be about former string amount 2-3 doubly;
(4) open loop generation chemical reaction 10-30 minute and the generation ehter bond under the condition of 50～150 ℃ of reaction temperatures of the cellulosic hydroxyl in last and the string, thus sulfonic acid group introduced for said string.
The present invention compared with prior art, the preparation method is simple, the reaction time is short, and reaction reagent is nontoxic, experimentation safety, experiment effect is better, easy realization of industrial production.
The specific embodiment
Take by weighing the 5g cotton linter; Cotton linter is placed in the 50ml mixed liquor of the NaOH that passes through proportioning and sulfonated reagent
(
replaces with CHSAS in the narration afterwards) and soaked 20 minutes; Thereby sulfonated reagent becomes epoxy reaction at the Cl of concentrated base in easily with the H combination of adjacent hydroxyl; The hydroxyl on epoxide and string surface just can generate corresponding ehter bond in ring-opening reaction so, and the chemism of reaction is referring to accompanying drawing 1.
Removing excessive solution through squeezing, make 2-3 that the amount of wet fiber is about raw material doubly, is to make soup be penetrated into the fiber the inside more equably through squeezing one, and the another one effect can be controlled quality exactly; Then fiber 60 ℃ of preheatings 15 minutes, reacted 10-30 minute at 70-120 ℃ then, reaction finishes the back and uses the distilled water rinsing, until neutrality; Air-dry or the oven dry with the fiber of wash clean at last.The mensuration of the surface charge of fiber adopts the method for conductivity titration.
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
At first take by weighing 15g NaOH and 6.0g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 10 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0200mmol/g at last, and carboxyl is 0.0195mmol/g.
Embodiment 2
At first take by weighing 15g NaOH and 7.5g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 20 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0381mmol/g at last, and carboxyl is 0.0270mmol/g.
Embodiment 3
At first take by weighing 15g NaOH and 9.0g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 30 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0243mmol/g at last, and carboxyl is 0.0258mmol/g.
Embodiment 4
At first take by weighing 20g NaOH and 8.0g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 20 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0183mmol/g at last, and carboxyl is 0.0256mmol/g.
Embodiment 5
At first take by weighing 20g NaOH and 10g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 30 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0314mmol/g at last, and carboxyl is 0.0268mmol/g.
Embodiment 6
At first take by weighing 20g NaOH and 12g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 10 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0285mmol/g at last, and carboxyl is 0.0325mmol/g.
Embodiment 7
At first take by weighing 25g NaOH and 10g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 30 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0223mmol/g at last, and carboxyl is 0.0197mmol/g.
Embodiment 8
At first take by weighing 25g NaOH and 12.5g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 10 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0274mmol/g at last, and carboxyl is 0.0294mmol/g.
Embodiment 9
At first take by weighing 25g NaOH and 15g CHSAS preparation 50ml solution.Take by weighing the 5g cotton linter then, cotton linter is placed in the 50ml mixed liquor through the NaOH of proportioning and CHSAS soaked 20 minutes, be about 10g using pressurizing unit to send excessive its weight in wet base of solution maintenance.Putting into baking oven through the fiber of extruding, regulate 60 degrees centigrade of oven temperatures earlier, preheating 15 minutes is adjusted to 120 degrees centigrade with oven temperature then and reacted 20 minutes.Reaction finishes the back and uses the distilled water rinsing, until neutrality; Down baking 6 hours is subsequent use at 105 degrees centigrade at last the slurry of wash clean to be put into baking oven.Sulfonic group content through conductivity mensuration fiber surface is 0.0458mmol/g at last, and carboxyl is 0.0290mmol/g.
Technique effect
The present invention introduces sulfonic acid group through to the string sulfonating surface for fiber, significantly changes the surface chemistry and the charge property of string.Compare with carboxyl, the pKa value of sulfonic acid group is lower, so it has bigger pH range of application in solution.Thereby the fiber after the sulfonation will help the absorption of cationic sheet paper reinforcing agent to strengthen strength of paper, help the dyeing and finishing of string, and the absorption that increases metal ion and nano particle.And there are some researches show that sulfonated cellulose has anticoagulation and antiviral function, therefore be expected to be applied to medicine and medical and hygiene article industry.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Though the present invention discloses as above with preferred embodiment; Yet be not in order to limiting the present invention, anyly be familiar with the professional and technical personnel, in the scope that does not break away from technical scheme of the present invention; When the technology contents of above-mentioned announcement capable of using is made a little change or is modified to the equivalent embodiment of equivalent variations; In every case be not break away from technical scheme content of the present invention, to above any simple modification, equivalent variations and modification that embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (1)
1. the method for string sulfonating surface modification is characterized in that comprising the steps:
(1) adopts the water soluble sulfonated reagent with
structure, wherein n=1～10;
(2) said water soluble sulfonated reagent with
structure is generated the material with epoxidation structure in 20%～50% concentrated alkali solution, said have the material of epoxidation structure and the mol ratio of alkali is 1: 1～1: 4;
(3) adding string in the mixed solution of step (2) preparation makes it to soak fully; The fiber that soaks through squeezing the mixed solution of step (2) preparation is evenly distributed in fiber and make steady quality, the degree of squeezing be make the amount of wet string be former string amount 2-3 doubly;
(4) cellulosic hydroxyl in the last string and said material with epoxidation structure issued biochemical reaction 10-30 minute and generated ehter bond in the condition of 50～150 ℃ of reaction temperatures, thereby had introduced sulfonic acid group for said string.
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| CN2010102663754A CN101914850B (en) | 2010-08-30 | 2010-08-30 | Method for sulfonating surface of plant fiber |
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|---|---|---|---|
| CN2010102663754A CN101914850B (en) | 2010-08-30 | 2010-08-30 | Method for sulfonating surface of plant fiber |
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| Publication Number | Publication Date |
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| CN101914850A CN101914850A (en) | 2010-12-15 |
| CN101914850B true CN101914850B (en) | 2012-01-11 |
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| CN117585987B (en) * | 2024-01-18 | 2024-03-19 | 河北国亮新材料股份有限公司 | Tundish coating material and preparation method thereof |
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| JPH04146901A (en) * | 1990-10-11 | 1992-05-20 | Oji Paper Co Ltd | Fibrous, highly water-absorptive cellulosic substance |
| US6149549A (en) * | 1998-09-21 | 2000-11-21 | Syborn Chemicals, Inc. | Anionically derivatised cotton for improved comfort and care-free laundering |
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