CN106167532A - A kind of preparation method of chitosan quaternary ammonium salt - Google Patents
A kind of preparation method of chitosan quaternary ammonium salt Download PDFInfo
- Publication number
- CN106167532A CN106167532A CN201610855194.2A CN201610855194A CN106167532A CN 106167532 A CN106167532 A CN 106167532A CN 201610855194 A CN201610855194 A CN 201610855194A CN 106167532 A CN106167532 A CN 106167532A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- dimethyl
- quaternary ammonium
- solution
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention relates to the preparation method of a kind of chitosan quaternary ammonium salt, belong to high molecular technical field of modification.First chitosan is obtained N, N dimethyl chitosan by Eschweiler Clarke reaction by it;Then, under ionic liquid environment, quaternizing agent dimethyl carbonate is added by N, N dimethyl chitosan quaternary ammonium;Finally will be dried after reaction product solution organic solvent washing, gained solid is N, N, N N-trimethyl chitosan TMC.The quaternizing agent dimethyl carbonate that the present invention uses is nontoxic, and the product of reaction is carbon dioxide and methanol, and methanol reusable edible prepares dimethyl carbonate, environmental protection again.Meanwhile, compared with dimethyl sulfate, dimethyl carbonate and amine carry out having during methylation reaction preferable selectivity.
Description
Technical field
The present invention relates to the preparation method of a kind of chitosan quaternary ammonium salt, belong to high molecular technical field of modification.
Background technology
Chitosan (chitosan), also known as chitosan, is to be obtained through deacetylation by chitin (chitin)
's.Owing to forming substantial amounts of hydrogen bond, the in addition regularity in structure with intermolecular in chitosan molecule so that molecule is easily tied
Crystalline substance, solubility property is poor, is dissolved only in diluted acid under generic condition, significantly limit the application of chitosan.N, N, N-front three base enclosure is gathered
Sugar (TMC) is the chitosan alkylating product of C2 bit amino, and chitosan positively charged increase after quaternized modification, more
Big pH scope is respectively provided with preferable water solublity.Product is in fields such as pharmaceutical synthesis, pharmaceutical carrier, antibacterial, food fresh keepings
All there is extensive application.
From document reported first in 1985, chitosan prepared N, the technique of N, N-N-trimethyl chitosan TMC, research with iodomethane
Personnel start to turn to sight the quaternized research of chitosan.Dimethyl sulfate as alkylating reagent modification of chitosan,
Relatively carry out methylated method with iodomethane more effective, and low price.At present, the preparation process of TMC all with iodomethane or
Dimethyl sulfate makees methylating reagent, obtains chitosan quaternary ammonium salt with chitosan reaction.Two kinds of reagent are the most quaternized, and activity is relatively
By force, and simple to operation, but iodomethane volatility is big, and toxicity is relatively big, needs shading freezen protective, expensive,
It is difficult to industrial applications, and dimethyl sulfate effect is similar to mustard gas, severe toxicity, belong to control reagent.Comparatively speaking, carbonic acid two
Methyl ester receives significant attention as a kind of green non-poisonous methylating reagent, is widely used in organic synthesis, and lot of documents
Prove that dimethyl carbonate can be using replacement sulfur dimethyl phthalate and iodomethane as methylating reagent.
Patent publication No. is that CN 101624347 B discloses one dimethyl carbonate, tertiary amine and inorganic acid reaction and prepares
The method of quaternary ammonium salt;Patent publication No. is that CN 102816075 A discloses a kind of dimethyl carbonate and the tertiary amine less than carbon 20
The method of quaternary surfactant is prepared in reaction;Patent publication No. is that CN 1948268 A discloses by dimethyl carbonate short
Streptamine (ammonia) salt carries out quaternized technique.
Relate to the use of dimethyl carbonate disclosed in existing and prepare the patent of quaternary ammonium salt, be by dimethyl carbonate short chain uncle
Amine, ester-amine series carry out quaternized, but the existing data such as document and patent all shows, but dimethyl carbonate is as the examination that methylates
Agent reactivity is low, it usually needs High Temperature High Pressure and the common effect of catalyst;Simultaneously because chitosan belongs to natural polymer,
Water solublity is poor, directly carries out N position quaternized more difficult.
To sum up, present invention employs ionic liquid as solvent and catalyst, make whole reaction normal pressure under homogeneous system
Preparation N, N, N-N-trimethyl chitosan TMC quaternary ammonium salt, not only increase the safety of production operation, reduce environmental pollution, and greatly
Improve reaction efficiency and productivity, and not yet find and by dimethyl carbonate, the macromolecule of chitosan or similar chitosan entered
The technique that row is quaternized.
Summary of the invention
It is an object of the invention to overcome above-mentioned weak point, it is provided that the preparation method of a kind of chitosan quaternary ammonium salt.
The technical scheme provided according to the present invention, the synthetic route schematic diagram of chitosan quaternary ammonium salt is as shown in Figure 1.
The preparation method of a kind of chitosan quaternary ammonium salt, first chitosan obtain N by Eschweiler Clarke reaction,
N-dimethyl chitosan;Then, under ionic liquid environment, add quaternizing agent dimethyl carbonate and N, N-diformazan base enclosure is gathered
Sugar is quaternized;Finally will be dried after reaction product solution organic solvent washing, gained solid is N, N, N-front three base enclosure
Polysaccharide;
Specifically comprise the following steps that by weight
(1) preparation of N, N-dimethyl chitosan:
A, chitosan, formaldehyde, formic acid and distilled water are sequentially added in the there-necked flask being furnished with condensing tube, wherein chitosan 5 parts, first
Aldehyde 15-25 part, formic acid 15-25 part, distilled water 80-100 part, open magnetic stirring apparatus, rotating speed is 100-700r/min, at 50-
React 20-120 hour at 80 DEG C, obtain yellow solution;
After b, distillation 25-35min that gained yellow solution is reduced pressure at 0.05-0.1MPa, 45-65 DEG C, adjust with alkaline solution
Joint pH be 10-13 to form a large amount of gels, subsequently vacuum filtration under 0.05-0.1MPa, use absolute ethanol washing to neutrality,
Obtain light yellow gel shape material, dried at 60-120 DEG C, grind to form pale yellow powder;
C, use acid leach solution step b gained pale yellow powder, continuously adding acid solution regulation is 3-5 to pH, now can
Access white precipitate, with distilled water wash 5-10 time, lyophilization at-30 ~-60 DEG C, i.e. obtain N, N-diformazan base enclosure and gather
Sugar;
(2) N, the preparation of N, N-N-trimethyl chitosan TMC:
D, taking ionic liquid 100 parts and be heated to 80-120 DEG C, point being slowly added to step (1) for 3-5 time while stirring prepares gained
N, N-dimethyl chitosan 1-10 part, mixing speed is 100-700r/min;Continue gained mixed liquor agitating heating, stirring
Speed is 100-700 r/min, and heating-up temperature is 90-130 DEG C, until N, N-dimethyl chitosan is completely dissolved;
E, by step d gained N, N-dimethyl chitosan solution regulate to 130-170 DEG C, add quaternizing agent, addition is
5-20 times of N, N-dimethyl chitosan weight, is sufficiently stirred under condensing reflux reacting 2-5h;Mixing speed is 100-700 r/
min;
F, by organic solvent washing 5-10 time of the solution obtained by step e, put into baking oven and be dried at 60-120 DEG C, gained is solid
Body is chitosan quaternary ammonium salt N, N, N-N-trimethyl chitosan TMC.
The cation of ionic liquid described in step d is 1,3-alkyl substituted imidazol ion [R1R3im]+, quaternary ammonium alkyl from
Son [NRxH4-x]+, alkyl quaternary phosphonium ion [PRxH4-x] +Pyridinium ion substituted with N-base [Rpy] +In one or more;Cloudy
Ion is Cl-、HSO4 -、COO-、BF4 -、PF6 -、NO3 -And CF3SO3 -In one or more.
Alkaline solution described in step b is NaOH solution or the KOH solution of 1mol/L.
Acid solution described in step c is HCl solution or the HAC solution of 1mol/L.
Quaternizing agent described in step e is dimethyl carbonate.
Organic solvent described in step f is dehydrated alcohol or acetone.
Beneficial effects of the present invention: the quaternizing agent dimethyl carbonate that the present invention uses is nontoxic, and the product of reaction is two
Carbonoxide and methanol, methanol reusable edible prepares dimethyl carbonate, environmental protection again.Meanwhile, compared with dimethyl sulfate,
Dimethyl carbonate and amine carry out having during methylation reaction preferable selectivity.
Additionally, present invention ionic liquid reacts at ambient pressure as solvent and catalyst, overcome carbonic acid diformazan
Ester needs the situation of pressurization when carrying out quaterisation, greatly reduces energy consumption.
Accompanying drawing explanation
Fig. 1 is the synthetic route schematic diagram of chitosan quaternary ammonium salt.
Fig. 2 is the nuclear magnetic spectrogram (quaternary ammonium degree is 9.67%) that embodiment 1 prepares gained chitosan quaternary ammonium salt.
Detailed description of the invention
Below by way of being embodied as example and further describe the feasibility of this method, but it is not intended that the invention be limited to
These examples.
Embodiment 1
Take 5 grams of chitosans, 20 grams of formaldehyde, 90 grams of distilled water of 20 grams of formic acid join in there-necked flask, and magnetic agitation speed is 500r/
Min, reacts 120 hours under 70 DEG C of condensing refluxes, obtains yellow solution.By gained yellow solution at 0.05MPa, at 65 DEG C
After decompression distillation 25min, regulating to pH=13, sucking filtration under 0.05-0.1MPa with sodium hydroxide solution, absolute ethanol washing is extremely
After neutrality, then regulate to pH=4 with the hydrochloric acid of 1mol/L ,-30 DEG C of lyophilizations after obtained white precipitate is washed,
To N, N-dimethyl chitosan;
Take 10 grams of chlorinations (1-butyl-3-Methylimidazole .), be added in the there-necked flask of 50mL, open magnetic stirring apparatus and condensation
Water, arranging rotating speed is 500r/min.After temperature reaches 100 DEG C, 0.5 gram of N, N-dimethyl chitosan is added in three times, stirs
After mixing reaction 2 hours, i.e. obtain the N of homogeneous thickness, N-dimethyl chitosan mixed liquor;By 10 grams of dimethyl carbonate (20 times of mistakes
Amount) add in mixed liquor, react 3 hours under 150 DEG C of condensing refluxes, gained solution absolute ethanol washing 10 times, put into baking
Case is dried at 70 DEG C, and gained solid is N, N, N-N-trimethyl chitosan TMC.
Pass through1H NMR and13It is 9.67% that C NMR analysis obtains the quaternary ammonium degree of product, and concrete nuclear magnetic spectrogram is as shown in Figure 2.
Embodiment 2
The preparation method of N, N-dimethyl chitosan is with example 1;
Take 5 grams of 1-ethyl-3-methylimidazole acetate, be added in the there-necked flask of 50mL, open magnetic stirring apparatus and condensation
Water, arranging rotating speed is 600r/min.After temperature reaches 90 DEG C, 0.5 gram of N, N-dimethyl chitosan is added, instead in three times
After answering 2 hours, i.e. obtain the N of homogeneous thickness, N-dimethyl chitosan mixed liquor;5 grams of dimethyl carbonate (10 times of excess) are added
Enter in mixed liquor, react 2.5 hours under 130 DEG C of condensing refluxes, gained solution absolute ethanol washing 5 times, put into baking oven and exist
Being dried at 110 DEG C, gained solid passes through1H NMR and13C NMR analyzes and obtains the chitosan quaternary ammonium that product is quaternary ammonium degree 8.78%
Salt.
Embodiment 3
The preparation method of N, N-dimethyl chitosan is with example 1;
Take 15 grams of chlorination 1-pi-allyl-3-Methylimidazole .s to be added in the there-necked flask of 50mL, open magnetic stirring apparatus and condensation
Water, arranging rotating speed is 400r/min.After temperature reaches 110 DEG C, 0.5 gram of N, N-dimethyl chitosan is added, instead in three times
After answering 2 hours, i.e. obtain the N of homogeneous thickness, N-dimethyl chitosan mixed liquor;By 2.5 grams of dimethyl carbonate (5 times of excess)
Add in mixed liquor, react 3 hours under 170 DEG C of condensing refluxes, gained solution absolute ethanol washing 6 times, put into baking oven and exist
Being dried at 120 DEG C, gained solid is N, N, N-N-trimethyl chitosan TMC.
Pass through1H NMR and13It is 12.39% that C NMR analysis obtains the quaternary ammonium degree of product chitosan quaternary ammonium salt.
Embodiment 4
The preparation method of N, N-dimethyl chitosan is with example 1;
Take 30 grams of N-(4-sulfonic group) butyI-pyridinium disulfate, be added in the there-necked flask of 50ml, open magnetic stirring apparatus
And condensed water, arranging rotating speed is 500 r/min.After temperature reaches 130 DEG C, by 0.5 gram of N, N-dimethyl chitosan in three times
Add, after reacting 1.5 hours, i.e. obtain the N of homogeneous thickness, N-dimethyl chitosan mixed liquor;By 5 grams of dimethyl carbonate (10
Times excess) add in mixed liquor, react 5 hours under 150 DEG C of condensing refluxes, gained solution washing with acetone 5 times, put into baking oven
Being dried at 105 DEG C, gained solid is N, N, N-N-trimethyl chitosan TMC.
Embodiment 5
The preparation method of N, N-dimethyl chitosan is with example 1;
Take 50 grams of N-(4-sulfonic group) butyl-imidazolium hydrophosphate, be added in the there-necked flask of 50ml, open magnetic stirring apparatus
And condensed water, arranging rotating speed is 700 r/min.After temperature reaches 100 DEG C, by 0.5 gram of N, N-dimethyl chitosan in three times
Add, after reacting 4.5 hours, i.e. obtain the N of homogeneous thickness, N-dimethyl chitosan mixed liquor;By 10 grams of dimethyl carbonate
(20 times of excess) adds in mixed liquor, reacts 3.5 hours under 145 DEG C of condensing refluxes, and gained solution first uses washing with acetone 8 times,
Putting into baking oven to be dried at 115 DEG C, gained solid is N, N, N-N-trimethyl chitosan TMC.
Embodiment 6
The preparation method of N, N-dimethyl chitosan is with example 1;
Take 20 grams of 1-butyl-3-methyl imidazolium tetrafluoroborate, be added in the there-necked flask of 50ml, open magnetic stirring apparatus and
Condensed water, arranging rotating speed is 300 r/min.After temperature reaches 90 DEG C, 0.5 gram of N, N-dimethyl chitosan is added in three times
Enter, after reacting 5 hours, i.e. obtain the N of homogeneous thickness, N-dimethyl chitosan mixed liquor;By 7.5 grams of dimethyl carbonate (15 times
Excess) add in mixed liquor, react 5 hours under 140 DEG C of condensing refluxes, gained solution first uses washing with acetone 5 times, puts into baking oven
Being dried at 80 DEG C, gained solid is N, N, N-N-trimethyl chitosan TMC.
Claims (6)
1. a preparation method for chitosan quaternary ammonium salt, is characterized in that: first chitosan is anti-by Eschweiler Clarke
N, N-dimethyl chitosan should be obtained;Then, under ionic liquid environment, quaternizing agent dimethyl carbonate is added by N, N-
Dimethyl chitosan quaternary ammonium;Finally will be dried after reaction product solution organic solvent washing, gained solid is N, N,
N-N-trimethyl chitosan TMC;
Specifically comprise the following steps that by weight
(1) preparation of N, N-dimethyl chitosan:
A, chitosan, formaldehyde, formic acid and distilled water are sequentially added in the there-necked flask being furnished with condensing tube, wherein chitosan 5 parts, first
Aldehyde 15-25 part, formic acid 10-25 part, distilled water 80-100 part, open magnetic stirring apparatus, rotating speed is 100-700r/min, at 50-
React 20-120 hour at 80 DEG C, obtain yellow solution;
After b, distillation 25-35min that gained yellow solution is reduced pressure at 0.05-0.1MPa, 45-65 DEG C, adjust with alkaline solution
Joint pH be 10-13 to form a large amount of gels, subsequently vacuum filtration under 0.05-0.1MPa, use absolute ethanol washing to neutrality,
Obtain light yellow gel shape material, dried at 60-120 DEG C, grind to form pale yellow powder;
C, use acid leach solution step b gained pale yellow powder, continuously adding acid solution regulation is 3-5 to pH, now can
Access white precipitate, with distilled water wash 5-10 time, lyophilization at-30 ~-60 DEG C, i.e. obtain N, N-diformazan base enclosure and gather
Sugar;
(2) N, the preparation of N, N-N-trimethyl chitosan TMC:
D, taking ionic liquid 100 parts and be heated to 80-120 DEG C, point being slowly added to step (1) for 3-5 time while stirring prepares gained
N, N-dimethyl chitosan 1-10 part, mixing speed is 100-700r/min;Continue gained mixed liquor agitating heating, stirring
Speed is 100-700 r/min, and heating-up temperature is 90-130 DEG C, until N, N-dimethyl chitosan is completely dissolved;
E, by step d gained N, N-dimethyl chitosan solution regulate to 130-170 DEG C, add quaternizing agent, addition is
5-20 times of N, N-dimethyl chitosan weight, is sufficiently stirred under condensing reflux reacting 2-5h;Mixing speed is 100-700 r/
min;
F, by organic solvent washing 5-10 time of the solution obtained by step e, put into baking oven and be dried at 60-120 DEG C, gained is solid
Body is chitosan quaternary ammonium salt N, N, N-N-trimethyl chitosan TMC.
2. the preparation method of as claimed in claim 1 chitosan quaternary ammonium salt, is characterized in that: the sun of ionic liquid described in step d from
Son is 1,3-alkyl substituted imidazol ion [R1R3im]+, alkyl quaternary ammonium ion [NRxH4-x]+, alkyl quaternary phosphonium ion [PRxH4-x
] +Pyridinium ion substituted with N-base [Rpy] +In one or more;Anion is Cl-、HSO4 -、COO-、BF4 -、PF6 -、
NO3 -And CF3SO3 -In one or more.
3. the preparation method of chitosan quaternary ammonium salt as claimed in claim 1, is characterized in that: alkaline solution described in step b is 1mol/
The NaOH solution of L or KOH solution.
4. the preparation method of chitosan quaternary ammonium salt as claimed in claim 1, is characterized in that: acid solution described in step c is 1mol/
The HCl solution of L or HAC solution.
5. the preparation method of chitosan quaternary ammonium salt as claimed in claim 1, is characterized in that: quaternizing agent described in step e is carbon
Dimethyl phthalate.
6. the preparation method of chitosan quaternary ammonium salt as claimed in claim 1, is characterized in that: organic solvent described in step f is anhydrous
Ethanol or acetone.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610855194.2A CN106167532B (en) | 2016-09-27 | 2016-09-27 | A kind of preparation method of chitosan quaternary ammonium salt |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610855194.2A CN106167532B (en) | 2016-09-27 | 2016-09-27 | A kind of preparation method of chitosan quaternary ammonium salt |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106167532A true CN106167532A (en) | 2016-11-30 |
CN106167532B CN106167532B (en) | 2018-10-26 |
Family
ID=57377050
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610855194.2A Active CN106167532B (en) | 2016-09-27 | 2016-09-27 | A kind of preparation method of chitosan quaternary ammonium salt |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106167532B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106589166A (en) * | 2016-12-30 | 2017-04-26 | 齐鲁工业大学 | Preparation method of nitrogen-replaced chitosan quaternary ammonium salt |
CN108653197A (en) * | 2018-05-15 | 2018-10-16 | 九江高科制药技术有限公司 | A kind of carboxymethyl chitosan quaternary ammonium salt thermo-sensitive gel and preparation method thereof |
CN111593566A (en) * | 2020-05-28 | 2020-08-28 | 安徽省天助纺织科技集团股份有限公司 | Degradable functional wet tissue and preparation method thereof |
CN112480288A (en) * | 2020-11-23 | 2021-03-12 | 浙江工商大学 | Ionized chitosan and preparation method and application thereof |
US11535684B2 (en) | 2018-08-23 | 2022-12-27 | Primex Ehf. | Chitosan derivatives and methods for preparing the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
CN101157735A (en) * | 2007-11-27 | 2008-04-09 | 江南大学 | Method for synthesizing N,N,N-trimethyl chitosan sulfate methyl ammonium |
CN102532346A (en) * | 2011-12-30 | 2012-07-04 | 沈阳药科大学 | Environmentally-friendly method for preparing chitosan quaternary ammonium salt in ion liquid |
US20140107329A1 (en) * | 2011-06-13 | 2014-04-17 | Rival, Societe En Commandite | N,n,n-trilakylaminopolymers, methods of their preparation and uses thereof |
-
2016
- 2016-09-27 CN CN201610855194.2A patent/CN106167532B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
CN101157735A (en) * | 2007-11-27 | 2008-04-09 | 江南大学 | Method for synthesizing N,N,N-trimethyl chitosan sulfate methyl ammonium |
US20140107329A1 (en) * | 2011-06-13 | 2014-04-17 | Rival, Societe En Commandite | N,n,n-trilakylaminopolymers, methods of their preparation and uses thereof |
CN102532346A (en) * | 2011-12-30 | 2012-07-04 | 沈阳药科大学 | Environmentally-friendly method for preparing chitosan quaternary ammonium salt in ion liquid |
Non-Patent Citations (1)
Title |
---|
郑学晶等主编: "《天然高分子材料》", 31 December 2010 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106589166A (en) * | 2016-12-30 | 2017-04-26 | 齐鲁工业大学 | Preparation method of nitrogen-replaced chitosan quaternary ammonium salt |
CN108653197A (en) * | 2018-05-15 | 2018-10-16 | 九江高科制药技术有限公司 | A kind of carboxymethyl chitosan quaternary ammonium salt thermo-sensitive gel and preparation method thereof |
CN108653197B (en) * | 2018-05-15 | 2021-06-04 | 九江高科制药技术有限公司 | Carboxymethyl chitosan quaternary ammonium salt temperature-sensitive gel and preparation method thereof |
US11535684B2 (en) | 2018-08-23 | 2022-12-27 | Primex Ehf. | Chitosan derivatives and methods for preparing the same |
CN111593566A (en) * | 2020-05-28 | 2020-08-28 | 安徽省天助纺织科技集团股份有限公司 | Degradable functional wet tissue and preparation method thereof |
CN112480288A (en) * | 2020-11-23 | 2021-03-12 | 浙江工商大学 | Ionized chitosan and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN106167532B (en) | 2018-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106167532A (en) | A kind of preparation method of chitosan quaternary ammonium salt | |
CN110467591A (en) | Rare earth metal complex promote one pot process cosmetic active object Bose because | |
CN105949129B (en) | A kind of imidazoles bromide ionic liquid and its preparation method and application with amino | |
CN103965372B (en) | The preparation method of a kind of chitosan-gallic acid graft copolymer | |
CN103045700B (en) | Method for pretreating lignocellulose by using renewable ionic liquid aqueous solution | |
CN103951582B (en) | A kind of preparation method of alpha.-acetylacetanilide compounds | |
CN109280179A (en) | A kind of covalent organic framework material and preparation method thereof and the application in hindered amines synthesis | |
CN105384788A (en) | Tildipirosin preparation method | |
CN103539868A (en) | Method for preparing carboxymethyl chitosan | |
CN106519060A (en) | Preparation of carboxymethyl curdlan | |
CN103951622B (en) | A kind of chitin kind biomass-making that utilizes is for the method for nitrogen-containing heterocycle compound | |
CN108689870A (en) | A kind of preparation method of tranexamic acid | |
CN105330560A (en) | Enzalutamide intermediate preparation method | |
CN106928152A (en) | A kind of preparation method of uracil | |
CN101422415A (en) | Moisture-absorption humectant and preparation method thereof | |
CN108929348A (en) | The preparation method of isopropyl-β-D thiogalactoside | |
CN111574416B (en) | Method for preparing tiamulin from isothiourea salt and pleuromutilin p-toluenesulfonate | |
CN103804342A (en) | Preparation method for piperonyl acetate | |
CN108530546B (en) | Synthesis and application of pseudochitosan and derivatives thereof | |
CA2771279A1 (en) | Modification of solid polysaccharide with transesterification agent | |
CN105481782A (en) | Preparation method of sulfaquinoxaline | |
CN103073481A (en) | Preparation method for 4-azaspiro [2.4] heptane hydrochloride | |
CN101792506B (en) | Acrylamide hydrophobically associating water soluble polymer and preparation method thereof | |
CN105399862A (en) | Preparation method for chitosan acetic ester | |
CN104557684A (en) | Method for preparing 3-chloro-2-aminomethyl-5-trifluoromethylpyridine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |