CN101735324B - Carboxymethyl cellulose nitrate and preparation method thereof - Google Patents
Carboxymethyl cellulose nitrate and preparation method thereof Download PDFInfo
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- CN101735324B CN101735324B CN201010000551XA CN201010000551A CN101735324B CN 101735324 B CN101735324 B CN 101735324B CN 201010000551X A CN201010000551X A CN 201010000551XA CN 201010000551 A CN201010000551 A CN 201010000551A CN 101735324 B CN101735324 B CN 101735324B
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Abstract
The invention relates to carboxymethyl cellulose nitrate and a preparation method thereof, belonging to the high molecular material field. The structure of carboxymethyl cellulose nitrate of the invention is shown below, wherein R represents H, CH2COOH or NO2, the average degree of substitution of catboxymethyl group in each glucose unit is 0.2-0.6, and the average degree of substitution of nitrate group is 2.1-2.8. The preparation method comprises the following two steps: 1. using cellulose to perform alkalization, carboxymethylation and after-treatment and obtain carboxymethyl cellulose; 2. using carboxymethyl cellulose as raw material to perform esterification reaction with a nitrifying solution and prepare carboxymethyl cellulose nitrate. The material of the invention has as good film-forming property as that of cellulose nitrate and good mechanical property and can be dispersed in water; and when the material is used into waterborne coating, the dosage of organic solvent needed to be sprayed can be reduced, and the toxicity of the coating and environmental pollution can be reduced. The production method of the invention is easy to realize and can be completed by using the current production devices and methods.
Description
Technical field
The present invention relates to a kind of carboxymethyl cellulose nitrate and preparation method thereof, this material has important use and is worth on fields such as coating, medicine, sensitive materials, sensing material, belong to polymeric material field.
Background technology
Cellulose nitrate is one of the widest cellulose esters of purposes.The solubility of cellulose nitrate in common solvent, good film-forming properties and become high-mechanical property of goods etc., make this ester class can be used in the manufacturing of coating, plastics etc.
With cellulose nitrate is that the pyroxylin(e)finish of main base material is easy to spraying, and good adhesiveproperties, excellent drying property and dispersing of pigments performance are arranged, and is widely used as the coating of automobile and wood furniture.Identical with traditional solvent based coating, the solvent in the pyroxylin(e)finish is high, and the solvent when construction can be up to 80%, and these volatile organic compoundss (VOC) get into atmosphere, cause the pollution of environment, and human body is damaged.According to statistics, about 1/3 white blood disease children are relevant with the pollution that decoration design for residence is caused.
In order to protect environment and human health, national governments have all put into effect the Abgasgesetz of restriction coating VOC, and under the environmental requirement of strict limiting emission amount impelled, particularly American-European countries greatly developed environmentally friendly coating in the world.Environmentally friendly coating is low VOC and hypotoxic coating, and main kind has water-borne coatings, powder coating, high solid coating and radiation curable coating at present.The application of water-borne coatings does not generally receive the restriction of occasion, do not need special-purpose Painting tool and equipment, so water-borne coatings will become the leading product of coating yet.
The present invention is intended to prepare the excellent mechanical properties that had both had good film-forming properties of cellulose nitrate and goods, can in water, disperse again, and the usage quantity of organic solvent when reducing paint spay-coating can be used for the cellulose-based material of water-borne coatings.
This product can be used as slow, controlled release preparation use at field of medicaments.
Summary of the invention
The objective of the invention is provides a kind of carboxymethyl cellulose nitrate that can be used for water-borne coatings and preparation method thereof for the toxicity that reduces coating with to the pollution of environment.This method is on Mierocrystalline cellulose, to introduce the itrate group and the hydrophilic ether group of organic dissolubility simultaneously, obtains containing the Mierocrystalline cellulose mixing ether-ether of itrate group.
A kind of carboxymethyl cellulose nitrate of the present invention has following structure:
Wherein, R=H, CH
2COOH or NO
2, the average substitution degree of ethyloic is 0.2-0.6 on each glucose unit ring, the average substitution degree of itrate group is 2.1-2.8.
The preparation method of a kind of carboxymethyl cellulose nitrate of the present invention comprises two parts: the nitric acid esterification of the preparation of CMC 99.5 and CMC 99.5.
(1) preparation of CMC 99.5.Be divided into cellulosic alkalization, carboxymethylation and aftertreatment three phases:
Cellulosic alkalization: organic medium is mixed with aqueous sodium hydroxide solution with sodium hydroxide or organic medium,, obtain soda cellulose at 5-35 ℃ of following and fibrin reaction.Wherein Mierocrystalline cellulose and organic medium mass ratio are 1: 2-15, and the mass concentration of organic medium is not less than 85%; The mass ratio of Mierocrystalline cellulose and sodium hydroxide is 1: 0.20-0.7; Reaction times is 0.5-3.0 hour.
Carboxymethylation reaction: quaternization finishes the back and adds etherifying agent-organic medium solution, and temperature of reaction is 45～80 ℃, 30～180 minutes reaction times.Wherein used etherifying agent is Mono Chloro Acetic Acid or sodium chloroacetate or chloracetate, etherifying agent-organic medium solution quality concentration 40%～60%; Mierocrystalline cellulose and etherifying agent mol ratio be 1: 0.34～1.37.
Aftertreatment: after carboxymethylation reaction finishes, add neutralization reagent and neutralize, wash then, centrifugal, dry, pulverize afterwards for use.Employed neutralization reagent is hydrochloric acid/organic medium or Glacial acetic acid min. 99.5/organic medium mixed system.
Cellulosic degree of polymerization is at 800-1300.
Organic medium comprises a kind of in Virahol, ethanol, Virahol/ethanol, acetone, toluene, ethanol/toluene, iso-propanol/toluene, the isopropylcarbinol.
(2) the nitric acid esterification of CMC 99.5
With CMC 99.5 be dispersed in carry out in the nitrification liquid nitrated.Temperature is controlled at 20-27 ℃, and nitrification liquid and CMC 99.5 mass ratio are 30-50, reaction times 30-45min.After reaction finishes, stir down reaction solution is poured in the container that 6-20 times of water of nitric acid volume is housed, wait not have the pale brown look smoke of gunpowder back suction filtration of emerging, resulting solid matter is a filter cake behind the suction filtration.
Filter cake is put into water and is washed, and promptly gets carboxymethyl cellulose nitrate after removing remaining nitrification liquid and impurity.
Nitrification liquid is nitric acid-methylene dichloride mixed solution or nitric acid-sulfuric acid mixture liquid.Nitric acid and methylene dichloride mass ratio are 30～70: 30～70, nitric acid: sulfuric acid: the mass ratio of water is 20～32: 59～69: 6～16.
A kind of carboxymethyl cellulose nitrate of the present invention can be used for coating, medicine, sensitive materials or sensing material.
Beneficial effect
Carboxymethyl cellulose nitrate of the present invention had both had the good film-forming properties of cellulose nitrate and had given the ability of goods excellent mechanical properties; Can in water, disperse again; When being used for water-borne coatings, the usage quantity of organic solvent in the time of can reducing paint spay-coating reduces toxicity and to the pollution of environment.This product can be used as slow, controlled release preparation use at field of medicaments.This material also has important use and is worth on fields such as sensitive materials, sensing material.
Working method of the present invention is easy to realize that CMC 99.5 and nitric acid esterification thereof can use current production devices and means to accomplish.
Embodiment
Followingly the present invention at length is described, but the present invention is not limited to embodiment according to embodiment.
Embodiment 1
Under agitation condition, it is in 90% the isopropanol that 22g sodium hydroxide is joined the 750g mass concentration, adds gossypin 75g then, in 20 ℃ of reactions 60 minutes down; Add 50g and contain 50% chloroacetic Mono Chloro Acetic Acid/isopropyl alcohol mixture, be warming up to 60 ℃ of reactions 150 minutes; After reacting end, with Glacial acetic acid min. 99.5/aqueous isopropanol neutralization, washing is centrifugal then, and drying is pulverized, and gets CMC 99.5.
Get the 10g CMC 99.5 and join and carry out nitratedly in nitric acid-methylene dichloride system of 50/50, bath raio 50 is carried out about 23 ℃; Reaction times 40min stirs down reaction solution is carefully poured in the container that 1000mL zero(ppm) water is housed, and filters; The solid materials that obtains is poured in the zero(ppm) water and is washed 1 time; Join after the filtration in the hot water, boiling 15min boils behind the 5min with cold water washing 2 times with ammoniacal liquor again.
The substitution value of CMC 99.5 is according to the GB2005 test, and nitrogen content is measured with elemental analyser, and the itrate group substitution value calculates through nitrogen content.The product degree of substitution by carboxymethyl is 0.3, nitrogen content 12.05%, and the itrate group substitution value is 2.52.
Embodiment 2
Cool off kneader in advance, add the ethanol of 6g sodium hydroxide and 15mL 95%, stirred 5 minutes.The 120g Mierocrystalline cellulose is joined in the kneader; (wherein sodium hydroxide concentration is 50.5% for 360mL sodium hydroxide and alcoholic acid mixing solutions; Add-on is 70mL) join in the kneader through the alkali wine shower of pinching in the machine, under the stirring of kneader, fully contact with Mierocrystalline cellulose, 20 ℃ were reacted 45 minutes down; Drive anti-car twice during this time, each 1-5 minute.After quaternization finishes, add Mono Chloro Acetic Acid/ethanolic soln of 85mL 50% (wt), be warming up to 78 ℃ of reactions 60 minutes.After reaction finishes, discharging in and still, neutralize with hydrochloric acid/ethanolic soln, wash then, centrifugal, drying.
The 10g CMC 99.5 joins in 45mL nitric acid-sulfuric acid mixture liquid, and 20 ℃ were reacted 25 minutes down.Nitric acid: sulfuric acid: water=29: 60: 12.After reaction finishes, stir down reaction solution is carefully poured in the container that 1200mL zero(ppm) water is housed.Filter, the solid materials that obtains is poured in the zero(ppm) water washing into 1 time, joins after the filtration in the hot water, and boiling 15min boils behind the 5min with cold water washing 2 times with ammoniacal liquor again.
The substitution value of CMC 99.5 is according to the GB2005 test, and nitrogen content is measured with elemental analyser, and the itrate group substitution value calculates through nitrogen content.The product degree of substitution by carboxymethyl is 0.25, nitrogen content 11.50%, and the itrate group substitution value is 2.30.
Embodiment 3
Under agitation condition; It is in Virahol/ethanolic soln of 90% that 38g sodium hydroxide is joined the 1150g mass concentration; Add wood pulp cypress 95g then; Reacted 90 minutes down in 30 ℃, add 82g and contain 58% chloroacetic Mono Chloro Acetic Acid/Virahol/alcohol mixed solution, be warming up to 75 ℃ of reactions 80 minutes; After reaction finishes, with Glacial acetic acid min. 99.5/ethanolic soln neutralization, wash then, centrifugal, drying is pulverized, and gets CMC 99.5.
Get the 10g CMC 99.5 and join and carry out nitratedly in nitric acid-methylene dichloride system of 55/45, bath raio 50 is carried out about 20 ℃; Reaction times 40min stirs down reaction solution is carefully poured in the container that 400mL zero(ppm) water is housed, and filters; The solid materials that obtains is poured in the zero(ppm) water and is washed 1 time; Join after the filtration in the hot water, boiling 15min boils behind the 5min with cold water washing 2 times with ammoniacal liquor again.
The substitution value of CMC 99.5 is according to the GB2005 test, and nitrogen content is measured with elemental analyser, and the itrate group substitution value calculates through nitrogen content.The product degree of substitution by carboxymethyl is 0.5, nitrogen content 10.65%, and the itrate group substitution value is 2.21.
Embodiment 4
The preparation of CMC 99.5 is with embodiment 1.
Get the 10g CMC 99.5 and join and carry out nitratedly in nitric acid-methylene dichloride system of 40/60, bath raio 50 is carried out about 20 ℃; Reaction times 40min stirs down reaction solution is carefully poured in the container that 400mL zero(ppm) water is housed, and filters; The solid materials that obtains is poured in the zero(ppm) water and is washed 1 time; Join after the filtration in the hot water, boiling 15min boils behind the 5min with cold water washing 2 times with ammoniacal liquor again.
The substitution value of CMC 99.5 is according to the GB2005 test, and nitrogen content is measured with elemental analyser, and the itrate group substitution value calculates through nitrogen content.The product degree of substitution by carboxymethyl is 0.3, nitrogen content 11.92%, and the itrate group substitution value is 2.48.
Claims (7)
1. the preparation method of a carboxymethyl cellulose nitrate is characterized in that comprising the preparation of CMC 99.5 and the nitric acid esterification of CMC 99.5;
One. the preparation of CMC 99.5 is divided into cellulosic alkalization, carboxymethylation and aftertreatment three phases
(1) cellulosic alkalization
Organic medium is mixed with aqueous sodium hydroxide solution with sodium hydroxide or organic medium,, obtain soda cellulose at 5-35 ℃ of following and fibrin reaction; Wherein Mierocrystalline cellulose and organic medium mass ratio are 1: 2-15, and the mass concentration of organic medium is not less than 85%; The mass ratio of Mierocrystalline cellulose and sodium hydroxide is 1: 0.20-0.7, and the concentration of aqueous sodium hydroxide solution is 20%-51%; Reaction times is 0.5-3.0 hour;
(2) carboxymethylation reaction
Quaternization finishes the back and adds etherifying agent-organic medium solution, and promptly etherifying agent is dissolved in the solution that obtains behind the organic medium, and temperature of reaction is 45-80 ℃, reaction times 30-180 minute; Wherein used etherifying agent is Mono Chloro Acetic Acid or sodium chloroacetate or chloracetate, etherifying agent-organic medium solution quality concentration 40%-60%; Mierocrystalline cellulose and etherifying agent mol ratio be 1: 0.34-1.37;
(3) aftertreatment
After carboxymethylation reaction finishes, add neutralization reagent and neutralize, wash then, centrifugal, dry, pulverize afterwards for use;
Two. the nitric acid esterification of CMC 99.5
With CMC 99.5 be dispersed in carry out in the nitrification liquid nitrated; Temperature is controlled at 20-27 ℃, and nitrification liquid and CMC 99.5 mass ratio are 30-50, reaction times 30-45min; After reaction finishes; Stir down reaction solution is poured in the container that 6-20 times of water of nitric acid volume is housed, wait not have the pale brown look smoke of gunpowder back suction filtration of emerging, resulting solid matter is a filter cake behind the suction filtration; Filter cake is put into water and is washed, and promptly gets carboxymethyl cellulose nitrate after removing remaining nitrification liquid and impurity, and the prepared carboxymethyl cellulose nitrate that obtains has following structure:
Wherein, R=H, CH
2COOH or NO
2, the average substitution degree of ethyloic is 0.2-0.6 on each glucose unit ring, the average substitution degree of itrate group is 2.1-2.8.
2. the preparation method of a kind of carboxymethyl cellulose nitrate according to claim 1 is characterized in that: the organic medium in said comprises a kind of in Virahol, ethanol, Virahol/ethanol, acetone, toluene, ethanol/toluene, iso-propanol/toluene, the isopropylcarbinol.
3. the preparation method of a kind of carboxymethyl cellulose nitrate according to claim 1, it is characterized in that: the said cellulosic polymerization degree is 800-1300.
4. the preparation method of a kind of carboxymethyl cellulose nitrate according to claim 2, it is characterized in that: used etherifying agent is Mono Chloro Acetic Acid, sodium chloroacetate or chloracetate in said (2) carboxymethylation reaction.
5. the preparation method of a kind of carboxymethyl cellulose nitrate according to claim 1, it is characterized in that: employed neutralization reagent is hydrochloric acid/organic medium or Glacial acetic acid min. 99.5/organic medium mixed system in aftertreatment.
6. the preparation method of a kind of carboxymethyl cellulose nitrate according to claim 1, it is characterized in that: nitrification liquid described in two is nitric acid-methylene dichloride mixed solution or nitric acid-sulfuric acid mixture liquid; The mass ratio of nitric acid and methylene dichloride is 30～70: 30～70, nitric acid: sulfuric acid: the mass ratio of water is 20～32: 59～69: 6～16.
7. the preparation method of a kind of carboxymethyl cellulose nitrate according to claim 1 is characterized in that: utilize the carboxymethyl cellulose nitrate of this method preparation to be used for coating, medicine, sensitive materials or sensing material.
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| CN201010000551XA CN101735324B (en) | 2010-01-13 | 2010-01-13 | Carboxymethyl cellulose nitrate and preparation method thereof |
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| CN201010000551XA CN101735324B (en) | 2010-01-13 | 2010-01-13 | Carboxymethyl cellulose nitrate and preparation method thereof |
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| CN101735324B true CN101735324B (en) | 2012-07-04 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104403007A (en) * | 2014-12-15 | 2015-03-11 | 江南大学 | Method for preparing sodium carboxymethyl cellulose |
| CN104744596B (en) * | 2015-02-10 | 2017-05-10 | 江苏泰格油墨有限公司 | Preparation method of water-borne nitrocotton dispersion |
| CN104892989A (en) * | 2015-05-25 | 2015-09-09 | 北京理工大学 | Aqueous carboxymethylcellulose nitrate ester resin dispersion |
| CN105418770B (en) * | 2015-11-05 | 2018-03-27 | 重庆力宏精细化工有限公司 | The production method of carboxymethyl cellulose acetate butyrate |
| CN109293784A (en) * | 2018-09-19 | 2019-02-01 | 南通泰利达化工有限公司 | A kind of process preparing carboxymethyl cellulose nitrate |
| CN109369811A (en) * | 2018-09-19 | 2019-02-22 | 南通泰利达化工有限公司 | A kind of optimization process preparing carboxymethyl cellulose nitrate |
| CN110467682B (en) * | 2019-09-24 | 2020-11-10 | 北京理工大学 | Cellulose derivative and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3638698A (en) * | 1966-09-30 | 1972-02-01 | Us Navy | Crosslinked carboxymethyl cellulose nitrates propellants |
| CN101220099A (en) * | 2008-01-31 | 2008-07-16 | 重庆力宏精细化工有限公司 | Production method for high viscosity sodium carboxymethylcellulose |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3638698A (en) * | 1966-09-30 | 1972-02-01 | Us Navy | Crosslinked carboxymethyl cellulose nitrates propellants |
| CN101220099A (en) * | 2008-01-31 | 2008-07-16 | 重庆力宏精细化工有限公司 | Production method for high viscosity sodium carboxymethylcellulose |
Non-Patent Citations (2)
| Title |
|---|
| JP平11-277450A 1999.10.12 |
| JP平7-53908A 1995.02.28 |
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