CN1644589A - Chloro-N-trimethyl chitin hyamine - Google Patents
Chloro-N-trimethyl chitin hyamine Download PDFInfo
- Publication number
- CN1644589A CN1644589A CN 200410075510 CN200410075510A CN1644589A CN 1644589 A CN1644589 A CN 1644589A CN 200410075510 CN200410075510 CN 200410075510 CN 200410075510 A CN200410075510 A CN 200410075510A CN 1644589 A CN1644589 A CN 1644589A
- Authority
- CN
- China
- Prior art keywords
- acetone
- water
- washing
- methyl
- chloro
- 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
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
A chloride-n-trimethide chitose quaternary ammonium salt is characterized by the molecular formula is (C8H13NO5)n (C8H17NO4)m-x (C9H20NO4Cl)x, n=0.07-0.19, x=0.39-0.75, n+m+x=1. The production is carried out by expanding dissolving chitose into 1-methyl-2- pyrrolidone, adding sodium iodide, adding iodomethane, keeping temperature 50-65deg.C, agitating reacting, reacting liquid cooling, precipitating settling, washing deposit matter with acetone methyl - water solution, dissolving the deposit matter into water, dripping chlorhydric acid - alcohol solution and ion exchanging, adding acetone methyl into reacting liquid, washing the deposit matter, dissolving into water, adding into acetone methyl and settling, washing with acetone methyl - water solution, washing with acetone methyl, and drying. It achieves low cost, simple operation, and good water soluble performance.
Description
Technical field
The present invention relates to a kind of water-soluble chitosan quaternary ammonium salt derivative, particularly relate to a kind of chloro-N-trimethyl chitin hyamine.
Background technology
At present the report aspect the chitosan quaternary ammonium salt derivatives exploitation seldom, it is used and also only limits to flocculation agent and fungistat.See through the effect that the epithelial cell individual layer absorbs in the intestines and have good promotion water-soluble macromolecule medicine such as polypeptide and protein medicaments, can be used as not appearing in the newspapers as yet of macromolecular drug absorption enhancer.
Summary of the invention
The purpose of this invention is to provide a kind of chloro-N-trimethyl chitin hyamine, it can remedy the above-mentioned deficiency of prior art.
A kind of chloro-N-trimethyl chitin hyamine is characterized in that its molecular formula is (C
8H
13NO
5)
n(C
8H
17NO
4)
M-x(C
9H
20NO
4Cl)
x, its structural formula is:
N=0.07 in the formula～0.19, x=0.39～0.75, n+m+x=1.
The preparation method of above-mentioned chloro-N-trimethyl chitin hyamine, it is characterized in that chitosan is swollen in 1-methyl-2-than in the pyrrolidone, add sodium iodide, under alkaline condition, add methyl iodide in batches and keep 50-65 ℃ of stirring reaction, reaction solution is cooled to pour into after the room temperature separates out precipitation in the acetone, and with the acetone-water solution washing gained throw out of 70-80%; The gained throw out is dissolved in the water, stirring down, dropping 3-3.5% hydrochloric acid-ethanolic soln carries out ion-exchange, add acetone to reaction solution then and make precipitation, gained precipitates with water-soluble again behind the 70-80% acetone-water solution washing, join in the acetone again and precipitate, the gained precipitation continues with 70-80% acetone-water solution washing, washing with acetone, 70-80 ℃ of oven dry down.
The substitution value that the invention has the advantages that quaternary ammonium salt in the molecule can be controlled by the charging capacity of control methyl iodide, the good water solubility of product, and it can satisfy the requirement as antiseptic-germicide and macromolecular drug absorption enhancer.Simple to operate during preparation, cost is low, is applicable to industrialization preparation.
Embodiment
Below by example explanation the present invention.
1, the powdered granule 40.0g (0.24mol) behind chitosan pulverizing, mistake 120 eye mesh screens is swollen in the 1-Methyl-2-Pyrrolidone of 120mL, add 96.0g (0.64mol) sodium iodide solid, be heated to 60 ℃, stir and add 30% (concentration expressed in percentage by weight down, aqueous sodium hydroxide solution 220mL and methyl iodide liquid 120mL (1.93mol) down together), 60 ℃ of following constant temperature stirring reaction 2h; Add 30% aqueous sodium hydroxide solution 80mL and methyl iodide 80mL (1.29mol) again, continue to add 30% aqueous sodium hydroxide solution 40mL and methyl iodide 40mL (0.64mol) behind 60 ℃ of following constant temperature stirring reaction 1h, 60 ℃ are continued constant temperature stirring reaction 1h down, and total mol ratio of chitosan, sodium iodide, methyl iodide is 1: 2.7: 16.1.Reaction finishes and reaction solution is cooled to room temperature joins in the industrial acetone and precipitate, suction filtration collecting precipitation thing, and with 70-80% acetone-water solution washing, the gained throw out is dissolved in the 600mL distilled water, stirring down, dropping 1200mL3% hydrochloric acid-ethanolic soln carries out ion exchange reaction, add industrial acetone then and make abundant precipitation, suction filtration collecting precipitation thing, this throw out cleans with 70-80% acetone-water solution; The gained throw out is dissolved in the 200mL distilled water again, join in the industrial acetone under stirring and precipitate, suction filtration collecting precipitation thing, throw out is used 80% acetone-water solution again, acetone washs successively, 75 ℃ of following oven dry promptly obtain chloro-N-trimethyl chitin hyamine 33.5g of the present invention, x=39.8%.
2, structure is identified
Measure used instrument and condition:
Infrared spectra: NICOLET NEXUS-470 intelligence spectrograph, the KBr pressed disc method is measured.
NMR (Nuclear Magnetic Resonance) spectrum: JEOL JUM-ECP-600 nuclear magnetic resonance spectrometer.
With viscosity-average molecular weight is 5.0 * 10
4Chloro-N-trimethyl chitin hyamine is an example:
1) .FT-IR (KBr) cm
-1: 3500-3300 (stretching vibration peak of OH), 3000-2900 (CH
3Stretching vibration peak), 2900-2800 (N
+H (CH
3)
2Stretching vibration peak), 1639 (acid amides I band ,-the CO-carbonylic stretching vibration), 1475,1374,1310 (the stack peaks of C-H flexural vibration peak and acid amides III band), 1237 (stretching vibration peaks of C-N), 1152,1096,1059 (stretching vibration peaks of C-O-C).Compare 1599 places-NH with raw material
2The peak disappear 2955,1475,1374 places-CH
3Obviously strengthen and the enhancing of 1237 C-N of place stretching vibration peaks, the stretching vibration peak of C-O does not have considerable change, shows the generation of chitosan quaternary ammonium salt in the product.
2).
1H NMR (D
2O, DSS are interior mark, 80 ℃), δ: 2.07 (s ,-COCH
3), 3.00-3.15 (s ,-N (CH
3)
2), 3.30-3.40 (s ,-N
+(CH
3)
3), 3.40-3.50 (s, 6-O-CH
3), 3.50-3.60 (s, 3-O-CH
3).(3.80-4.10 chitosan ring C-2, C-3, C-4, C-5, the H of C-6), 4.80-5.50 (H of C-1).
3). determining of substitution value:
Get the 20mg sample dissolution in 1ml D
2Among the O, place 2h, lyophilize; Repeat this swap operation 2 times.The gained sample is with D after the freeze-drying
2O is a solvent, and DSS is interior mark, and 80 ℃ are carried out
1H NMR3). determining of substitution value:
Get the 20mg sample dissolution in 1ml D
2Among the O, place 2h, lyophilize; Repeat this swap operation 2 times.The gained sample is with D after the freeze-drying
2O is a solvent, and DSS is interior mark, and 80 ℃ are carried out
1H NMR POP is analyzed.The substitution value of chloro-N-trimethyl chitin hyamine is by calculating by following formula:
%DQ={[(CH
3)
3]/[H1] * 1/9} * 100%%DQ is the percentage composition of quaternized part in the chloro-N-trimethyl chitin hyamine molecule, [(CH
3)
3] be
1On the H NMR spectrogram-N
+(CH
3)
3Chemical shift is the peak area of 3.3ppm, [H1] be on the spectrogram chemical shift at the H1 of 4.7-5.7ppm fignal center area.
According to aforesaid method and corresponding
1H NMR spectral data: δ=3.34ppm place-N
+(CH
3)
3The peak area of H be 6.09, the peak area sum of δ=H-1 of 4.88-5.43 place is 1.70, records the quaternary ammonium salt substitution value DQ%={[6.09/1.70 of product of the present invention] * 1/9} * 100%=39.8%.
Claims (3)
1 one kinds of chloro-N-trimethyl chitin hyamines is characterized in that its molecular formula is (C
8H
13NO
5)
n(C
8H
17NO
4)
M-x(C
9H
20NO
4Cl)
x, structural formula is:
N=0.07 in the formula～0.19, x=0.39～0.75, n+m+x=1.
The preparation method of the described chloro-N-trimethyl chitin hyamine of 2 claims 1, it is characterized in that chitosan is swollen in the 1-Methyl-2-Pyrrolidone, add sodium iodide, under alkaline condition, add methyl iodide in batches and keep 50-65 ℃ of stirring reaction, reaction solution is cooled to pour into after the room temperature separates out precipitation in the acetone, and with the acetone-water solution washing gained throw out of 70-80%; The gained throw out is dissolved in the water, stirring down, dropping 3-3.5% hydrochloric acid-ethanolic soln carries out ion-exchange, then reaction solution is joined and make abundant precipitation in the acetone, gained precipitates with water-soluble again behind the 70-80% acetone-water solution washing, join in the acetone again and precipitate, gained precipitation 70-80% acetone-water solution washing, washing with acetone, 70-80 ℃ of oven dry.
3 preparation methods as claimed in claim 2 is characterized in that described chitosan: sodium iodide: total mol ratio of methyl iodide is: 1: 2.5-3: 13.6-16.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100755101A CN1300178C (en) | 2004-12-10 | 2004-12-10 | Chloro-N-trimethyl chitin hyamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100755101A CN1300178C (en) | 2004-12-10 | 2004-12-10 | Chloro-N-trimethyl chitin hyamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1644589A true CN1644589A (en) | 2005-07-27 |
| CN1300178C CN1300178C (en) | 2007-02-14 |
Family
ID=34869039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100755101A Expired - Fee Related CN1300178C (en) | 2004-12-10 | 2004-12-10 | Chloro-N-trimethyl chitin hyamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1300178C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391985C (en) * | 2006-05-30 | 2008-06-04 | 武汉大学 | Method for preparing Chitosan double quaternary ammonium salt |
| CN102153673A (en) * | 2011-03-15 | 2011-08-17 | 中国海洋大学 | N-parabenzyloxycarboxymethyl chitosan quaternary ammonium salt and preparation method thereof |
| CN102399304A (en) * | 2011-07-22 | 2012-04-04 | 中国科学院烟台海岸带研究所 | Chitosan quaternary amine salt gallate, synthetic method thereof and application thereof |
| CN104086670A (en) * | 2014-05-22 | 2014-10-08 | 中国科学院烟台海岸带研究所 | Chitosan quaternary ammonium salt containing triazole, and preparation method and application thereof |
| CN105019267A (en) * | 2014-04-18 | 2015-11-04 | 五邑大学 | Preparation method of chitosan direct quaternary ammonium salt dyeing and finishing low-salt assistant |
| CN105037583A (en) * | 2015-08-07 | 2015-11-11 | 成都易胜科生物科技有限公司 | N-trimethyl chitosan synthetic technology |
| CN106749760A (en) * | 2016-12-23 | 2017-05-31 | 中国科学院烟台海岸带研究所 | A kind of season phosphine chitosan quaternary ammonium salt and its preparation method and application |
| CN115474807A (en) * | 2022-07-25 | 2022-12-16 | 浙江蚕缘家纺股份有限公司 | High-fluffiness silk quilt manufacturing process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3245784A1 (en) * | 1982-12-10 | 1984-06-14 | Wella Ag, 6100 Darmstadt | COSMETIC AGENT BASED ON QUATERNAUS CHITOSAN DERIVATIVES, NEW QUATERNAERE CHITOSAN DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF |
| CN1266922A (en) * | 2000-01-25 | 2000-09-20 | 天津大学 | Antibacterial viscose fibre and its making method |
| CN1209378C (en) * | 2003-03-14 | 2005-07-06 | 天津大学 | Bactericidal chitin and its preparation and method for making cellulose solvent weaving liquid |
-
2004
- 2004-12-10 CN CNB2004100755101A patent/CN1300178C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391985C (en) * | 2006-05-30 | 2008-06-04 | 武汉大学 | Method for preparing Chitosan double quaternary ammonium salt |
| CN102153673A (en) * | 2011-03-15 | 2011-08-17 | 中国海洋大学 | N-parabenzyloxycarboxymethyl chitosan quaternary ammonium salt and preparation method thereof |
| CN102399304A (en) * | 2011-07-22 | 2012-04-04 | 中国科学院烟台海岸带研究所 | Chitosan quaternary amine salt gallate, synthetic method thereof and application thereof |
| CN105019267A (en) * | 2014-04-18 | 2015-11-04 | 五邑大学 | Preparation method of chitosan direct quaternary ammonium salt dyeing and finishing low-salt assistant |
| CN105019267B (en) * | 2014-04-18 | 2017-10-20 | 五邑大学 | The direct quaternary ammonium salt dyeing and finishing less salt auxiliary agent preparation method of chitosan |
| CN104086670A (en) * | 2014-05-22 | 2014-10-08 | 中国科学院烟台海岸带研究所 | Chitosan quaternary ammonium salt containing triazole, and preparation method and application thereof |
| CN104086670B (en) * | 2014-05-22 | 2016-09-07 | 中国科学院烟台海岸带研究所 | A kind of chitosan quaternary ammonium salt containing triazole and preparation thereof and application |
| CN105037583A (en) * | 2015-08-07 | 2015-11-11 | 成都易胜科生物科技有限公司 | N-trimethyl chitosan synthetic technology |
| CN106749760A (en) * | 2016-12-23 | 2017-05-31 | 中国科学院烟台海岸带研究所 | A kind of season phosphine chitosan quaternary ammonium salt and its preparation method and application |
| CN115474807A (en) * | 2022-07-25 | 2022-12-16 | 浙江蚕缘家纺股份有限公司 | High-fluffiness silk quilt manufacturing process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1300178C (en) | 2007-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ying et al. | Preparation, water solubility and antioxidant activity of branched-chain chitosan derivatives | |
| Sirviö et al. | Synthesis of highly cationic water-soluble cellulose derivative and its potential as novel biopolymeric flocculation agent | |
| CN100582123C (en) | Clexane and preparation method thereof | |
| Subhapradha et al. | Physicochemical characterisation of β-chitosan from Sepioteuthis lessoniana gladius | |
| CN1300178C (en) | Chloro-N-trimethyl chitin hyamine | |
| CN101284884A (en) | Preparation method of temperature sensitivity chitosan derivate-hydroxybutyl chitosan | |
| Khalil et al. | Novel water-soluble chitosan derivative prepared by graft polymerization of dicyandiamide: synthesis, characterisation, and its antibacterial property | |
| BR112020005508A2 (en) | ionic polymer, ionic polymer network, solid support, polymeric membrane, use of ionic polymers, method for producing one or more fine chemicals and method for producing sugars | |
| Bisht et al. | Enhanced dissolution of chitin using acidic deep eutectic solvents: A Sustainable and simple approach to extract chitin from crayfish shell wastes as alternative feedstocks | |
| Teng | From chitin to chitosan | |
| WO2017016022A1 (en) | Chito-oligosaccharide-o-kojic acid-mannich base derivative antibacterial agent and preparation method thereof | |
| Wang et al. | Synthesis and characterization of cinnamic acid conjugated N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride derivatives: A hybrid flocculant with antibacterial activity | |
| Pestov et al. | Role of Au (III) coordination by polymer in⿿ green⿿ synthesis of gold nanoparticles using chitosan derivatives | |
| CN100391985C (en) | Method for preparing Chitosan double quaternary ammonium salt | |
| Chagas et al. | Synthesis and characterization of dicarboxymethyl cellulose | |
| CN107459590A (en) | A kind of preparation method of hyaluronic acid quaternary ammonium salt | |
| CN102702389A (en) | Thermo-sensitive chitosan derivative-hydroxypentyl chitosan and preparation method thereof | |
| CN106905445B (en) | A kind of Polyaminated chitosan decolorising agent of carboxymethyl-and its preparation method and application | |
| CN103183743B (en) | A kind of preparation method of Cucurbituril [6] grafted chitosan | |
| CN109160959A (en) | A kind of chitosan pyridine quaternary ammonium salt and preparation method thereof based on ester-interchange method | |
| CN107602726B (en) | Low molecular weight C6-carboxyl chitin and preparation method thereof | |
| CN100526334C (en) | Method for preparing organic solvent soluble amphiphilic N,N-dilong chain alkyl chitosan | |
| CN101633701B (en) | Method for purifying hyaluronic acid | |
| WO2008141452A1 (en) | Chitosan salts, methods of manufacture and uses thereof | |
| CN101418049A (en) | A kind of hyaluronic preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070214 Termination date: 20100111 |