CN108623708A - A kind of chitosan quaternary ammonium salt and its preparation method and application containing halogenated acetic acids - Google Patents
A kind of chitosan quaternary ammonium salt and its preparation method and application containing halogenated acetic acids Download PDFInfo
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- CN108623708A CN108623708A CN201810554090.7A CN201810554090A CN108623708A CN 108623708 A CN108623708 A CN 108623708A CN 201810554090 A CN201810554090 A CN 201810554090A CN 108623708 A CN108623708 A CN 108623708A
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- 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
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Abstract
The present invention relates to marine chemical industry field of engineering technology, more particularly to a kind of chitosan quaternary ammonium salt and its preparation method and application containing halogenated acetic acids, using chitosan, 3 chlorine, 2 hydroxypropyl-trimethyl ammonium chloride, sodium hydroxide, isopropanol and halogenated acetic acids class compound as raw material, chitosan is scattered in isopropanol and is swollen first, it is stirred at room temperature 4 hours, 3 chlorine, 2 hydroxypropyl-trimethyl ammonium chloride and sodium hydroxide solution is added, the reaction was continued 12 hours, then it is precipitated with ethanol in proper amount, obtains chitosan quaternary ammonium salt.Finally chitosan quaternary ammonium salt is dissolved in water, ion exchange is carried out with halogenated acetic acids salt, obtains final product.It is an advantage of the invention that preparation process is simple, material therefor is at low cost, and is had shown that through research, and derivative is water-soluble good, has good bacteriostatic activity, can be widely applied to the fields such as medicine and pesticide.
Description
Technical field
The present invention relates to marine chemical industry field of engineering technology, and in particular to a kind of chitosan quaternary ammonium salt containing halogenated acetic acids and
Preparation method and application.
Background technology
Chitosan (CTS) is the natural polymer that chitin deacetylation reaches 50% or more, is not only maintained
The biocompatibility of chitin, and application performance is obviously improved than chitin.But since chitosan can only be dissolved in such as acetic acid
A small number of organic solvents and pH<In 4 water, be widely applied for it and bring limitation, thus to chitosan carry out chemical modification with
Improve its dissolubility and to widen its application range very necessary.Chitosan quaternary ammonium salt has bioactivity more better than chitosan,
And it is greatly improved the water solubility of chitosan.The anion that chitosan quaternary ammonium salt general involved at present has be iodine from
The bioactivity influence of son or chlorion, both ion pair chitosan quaternary ammonium salts is smaller.
Hydroxypropyl-trimethyl ammonium chloride group is introduced in chitosan molecule, prepares the Hydroxyproyl Trimethyl chlorine replaced on N
Change ammonium chitosan (chitosan quaternary ammonium salt), chlorion can change in hydroxypropyltrimethylammonium chloride chitosan (chitosan quaternary ammonium salt)
At with other anionic groups similar in chitosan quaternary ammonium salt bioactivity so that zwitterion is all in the same compound
Have certain bioactivity, according to active principle of stacking, the chitosan quaternary ammonium salt sun with same or similar bioactivity from
The salt that son is formed with halogenated acetic acids anion has higher bioactivity.
Invention content
In order to solve the above technical problems, the present invention propose it is a kind of containing the chitosan quaternary ammonium salt of halogenated acetic acids and its preparation side
Method and application.
Specific technical solution is as follows：
A kind of chitosan quaternary ammonium salt containing halogenated acetic acids, the structural formula of the chitosan quaternary ammonium salt containing halogenated acetic acids is such as
Under：
The average value range of wherein n is 300-900.
The chitosan quaternary ammonium salt containing halogenated acetic acids can be applied to the fields such as medicine and pesticide.
With chitosan, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide, isopropanol and halogenated acetic acids class chemical combination
Object is raw material, and specific preparation process is as follows：
(1) it weighs a certain amount of chitosan to be scattered in the isopropanol of certain volume, at room temperature swelling reaction 4 hours, according to
Secondary addition 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides solution, sodium hydroxide solution, react 10-12 hours under the conditions of 75 DEG C；So
After appropriate absolute ethyl alcohol precipitation is added, be used in combination the washing of 85% ethyl alcohol to filter and obtains filter cake, 65 DEG C drying to constant weight gathers to get to shell
Sugared quaternary ammonium salt；
(2) gained chitosan quaternary ammonium salt is dissolved in deionized water, stirs 1 hour and is dissolved to abundant at room temperature, it will be described
Fully dissolving chitosan quaternary ammonium salt is transferred in the bag filter that molecular cut off is 500, molten in certain density halogenated acetic acids sodium
It dialyses 12 hours in liquid, then removes halogenated acetic acids sodium solution, dialyse for 24 hours, be freeze-dried to get to containing halogenated in distilled water
The chitosan quaternary ammonium salt of acetic acid.
Above-mentioned steps (2) could alternatively be the chitosan quaternary ammonium salt and be dissolved in deionized water, be slowly dropped to certain dense
In the halogenated acetic acids sodium solution of degree, then solution is dialysed for 24 hours in distilled water, be freeze-dried to get to containing halogenated acetic acids
Chitosan quaternary ammonium salt.
The dosage of above-mentioned steps (1) chitosan, isopropanol, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide
Ratio is：Per 1-1.5g chitosans, isopropanol 20-40mL, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride 6-12ml, hydrogen-oxygen are used
Change sodium 1-1.5g.
Above-mentioned steps (2) chitosan quaternary ammonium salt, halogenated acetic acids sodium dosage be：Chitosan quaternary ammonium salt 1-1.5g, halogen
For sodium acetate 1.5g-3g.
Compared with prior art, advantageous effects of the invention are as follows：
(1) chitosan has many advantages, such as biocompatibility, raw without degradability and green non-poisonous, but its own antibiotic property
It is weak, by chemical modification, retain chitosan own biological degradability and it is avirulent simultaneously, improve its bioactivity.Knot
Fruit shows that the bacteriostatic activity of the chitosan quaternary ammonium salt containing halogenated acetic acids significantly improves, and good inhibition can be played to phytopathogen
Effect.The derivative can be developed into novel agrochemical and substitute traditional pesticide, and ecological disruption caused by solve chemical pesticide etc. is asked
Topic.It can also be widely used in medicinal antibiosis field simultaneously.
(2) chitosan is not soluble in water, and by chemical modification, the derivative is water-soluble good, and application prospect is more extensive.
(3) the derivative preparation process is simple, and material therefor is at low cost and target product yield is high.With under normal circumstances
Iodomethane synthesis chitosan quaternary ammonium salt is compared, and 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides prepare chitosan quaternary ammonium used in the present invention
The preparation process of salt is simple, and material therefor is at low cost, and yield is high, is suitble to extensive mass production, use value high.
Description of the drawings
Fig. 1 is the infrared spectrogram of chitosan；
Fig. 2 is the infrared spectrogram that the embodiment of the present invention 1 provides chitosan quaternary ammonium salt；
Fig. 3 is that the embodiment of the present invention 1 provides the infrared spectrogram containing chloroacetic chitosan quaternary ammonium salt；
Fig. 4 is the infrared spectrogram that the embodiment of the present invention 2 provides the chitosan quaternary ammonium salt containing dichloroacetic acid；
Fig. 5 is the infrared spectrogram that the embodiment of the present invention 3 provides the chitosan quaternary ammonium salt containing trichloroacetic acid；
Fig. 6 is the infrared spectrogram that the embodiment of the present invention 4 provides the chitosan quaternary ammonium salt containing difluoroacetic acid；
Fig. 7 is the infrared spectrogram that the embodiment of the present invention 5 provides the chitosan quaternary ammonium salt containing trifluoroacetic acid；
Fig. 8 is the infrared spectrogram that the embodiment of the present invention 6 provides the chitosan quaternary ammonium salt containing bromoacetic acid.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is not by attached
Figure and specific embodiment are limited.
Fig. 1 is the infrared spectrogram of chitosan.
Embodiment 1
The average value range of structural formula containing chloroacetic chitosan quaternary ammonium salt such as formula (1), wherein n is 300-900.
The preparation of chitosan quaternary ammonium salt：With chitosan, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide, isopropanol
And halogenated acetic acids class compound is raw material, takes 1g chitosans to be scattered in 20mL isopropanols and is swollen, room temperature condition stirring 4 is small
When, sequentially add 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides 6mL, sodium hydroxide solution 1g, it is 12 small that the reaction was continued under the conditions of 75 DEG C
When, then with ethanol in proper amount precipitation, washing, drying, obtain chitosan quaternary ammonium salt.
The chitosan quaternary ammonium salt 1g is soluble in water, dialyses 12 hours in the sodium chloroacetate sodium solution of 100mL3%, so
After remove halogenated acetic acids sodium solution, dialyse in distilled water for 24 hours, be freeze-dried after concentration, obtain contain chloroacetic chitosan season
Ammonium salt.
Fig. 2 is the infrared spectrogram that the embodiment of the present invention 1 provides chitosan quaternary ammonium salt, as can be seen from Figure 2, with chitosan raw material
(referring to Fig. 1) is compared, and chitosan quaternary ammonium salt is in 1478cm-1Place and 1420cm-1Occurs the absorption of vibrations of quaternary ammonium salt at two
Peak, the above analysis data, it was demonstrated that chitosan quaternary ammonium salt synthesizes.
Fig. 3 is that the embodiment of the present invention 1 provides the infrared spectrogram containing chloroacetic chitosan quaternary ammonium salt, as can be seen from Figure 3,
1478cm-1Place's vibration absorption peak still also exists, and in 918cm-1There is the absorption of vibrations of C-Cl keys in chloroacetate root ion in place
Thus peak proves chlorion success in chloroacetate root anion exchange chitosan quaternary ammonium salt.
Embodiment 2
The average value range of the structural formula of chitosan quaternary ammonium salt containing dichloroacetic acid such as formula (2), wherein n is 300-900.
Difference from Example 1 is：
With chitosan, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide, isopropanol and halogenated acetic acids class chemical combination
Object is raw material, takes 1.2g chitosans to be scattered in 20mL isopropanols and is swollen, and room temperature condition stirs 4 hours, sequentially adds the chloro- 2- of 3-
Hydroxypropyl-trimethyl ammonium chloride 8mL, sodium hydroxide solution 1.2g, the reaction was continued 12 hours, is then precipitated, is washed with ethanol in proper amount
It washs, obtains chitosan quaternary ammonium salt.
The chitosan quaternary ammonium salt 1g is dissolved in 20mL distilled water, is slowly dropped in 15% dichloroacetic acid sodium solution, so
Solution is dialysed for 24 hours in distilled water afterwards, is freeze-dried after concentration, the chitosan quaternary ammonium salt containing dichloroacetic acid is obtained.
Fig. 4 is the infrared spectrogram that the embodiment of the present invention 2 provides the chitosan quaternary ammonium salt containing dichloroacetic acid, as can be seen from Figure 4,
1478cm-1Place's vibration absorption peak still also exists, and in 917cm-1There is the absorption of vibrations of C-Cl keys in dichloroacetic acid radical ion in place
Thus peak proves chlorion success in dichloroacetic acid root anion exchange chitosan quaternary ammonium salt.
Embodiment 3
The average value range of the structural formula of chitosan quaternary ammonium salt containing trichloroacetic acid such as formula (3), wherein n is 300-900.
Difference from Example 1 is：
With chitosan, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide, isopropanol and halogenated acetic acids class chemical combination
Object is raw material, takes 1.5g chitosans to be scattered in 20mL isopropanols and is swollen, and room temperature condition stirs 4 hours, sequentially adds the chloro- 2- of 3-
Hydroxypropyl-trimethyl ammonium chloride 10mL, 40% sodium hydroxide solution 6mL, the reaction was continued 12 hours, then heavy with ethanol in proper amount
It forms sediment, washing, obtains chitosan quaternary ammonium salt.
The chitosan quaternary ammonium salt 1.3g is dissolved in 20mL distilled water, is slowly dropped in 15% trichloroacetic acid sodium solution,
Then solution is dialysed for 24 hours in distilled water, is freeze-dried after concentration, obtain the chitosan quaternary ammonium salt containing trichloroacetic acid.
Fig. 5 is the infrared spectrogram that the embodiment of the present invention 3 provides the chitosan quaternary ammonium salt containing trichloroacetic acid, as can be seen from Figure 5,
1478cm-1Place's vibration absorption peak still also exists, and in 814cm-1There is the absorption of vibrations of C-Cl keys in trichloroacetic acid ion in place
Thus peak proves chlorion success in trichloroacetic acid root anion exchange chitosan quaternary ammonium salt.
Embodiment 4
The average value range of the structural formula of chitosan quaternary ammonium salt containing difluoroacetic acid such as formula (4), wherein n is 300-900.
Difference from Example 1 is：
With chitosan, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide, isopropanol and halogenated acetic acids class chemical combination
Object is raw material, takes 1.5g chitosans to be scattered in 20mL isopropanols and is swollen, and room temperature condition stirs 4 hours, sequentially adds the chloro- 2- of 3-
Hydroxypropyl-trimethyl ammonium chloride 12mL, 40% sodium hydroxide solution 6mL, the reaction was continued 12 hours, then heavy with ethanol in proper amount
It forms sediment, washing, obtains chitosan quaternary ammonium salt.
The chitosan quaternary ammonium salt 1.5g is dissolved in 20mL distilled water, is stirred 2 hours under room temperature, is sequentially added 40%
Sodium hydrate aqueous solution 3mL, 15% difluoroacetic acid sodium sodium solution 30mL, react 12h under normal temperature condition, then solution existed
It dialyses in distilled water for 24 hours, is freeze-dried after concentration, obtain the chitosan quaternary ammonium salt containing difluoroacetic acid.
Fig. 6 is the infrared spectrogram that the embodiment of the present invention 4 provides the chitosan quaternary ammonium salt containing difluoroacetic acid, as can be seen from Figure 6,
1478cm-1Place's vibration absorption peak still also exists, and in 1195cm-1And 817cm-1There are C-F keys in difluoroacetic acid radical ion in place
Thus vibration absorption peak proves chlorion success in difluoroacetic acid root anion exchange chitosan quaternary ammonium salt.
Embodiment 5
The average value range of the structural formula of chitosan quaternary ammonium salt containing trifluoroacetic acid such as formula (5), wherein n is 300-900.
Difference from Example 1 is：
With chitosan, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide, isopropanol and halogenated acetic acids class chemical combination
Object is raw material, takes 1.5g chitosans to be scattered in 20mL isopropanols and is swollen, and room temperature condition stirs 4 hours, sequentially adds the chloro- 2- of 3-
Hydroxypropyl-trimethyl ammonium chloride 10mL, 40% sodium hydroxide solution 6mL, the reaction was continued 12 hours, then heavy with ethanol in proper amount
It forms sediment, washing, obtains chitosan quaternary ammonium salt.
The chitosan quaternary ammonium salt 1.3g is dissolved in 20mL distilled water, is slowly dropped in 15% trifluoroacetic acid sodium solution,
Then solution is dialysed for 24 hours in distilled water, is freeze-dried after concentration, obtain the chitosan quaternary ammonium salt containing trifluoroacetic acid.
Fig. 7 is the infrared spectrogram that the embodiment of the present invention 5 provides the chitosan quaternary ammonium salt containing trifluoroacetic acid, as can be seen from Figure 7,
1478cm-1Place's vibration absorption peak still also exists, and in 1045cm-1And 801cm-1There are C-F keys in trifluoroacetic acid radical ion in place
Thus vibration absorption peak proves chlorion success in trifluoroacetic acid root anion exchange chitosan quaternary ammonium salt.
Embodiment 6
The average value range of the structural formula of chitosan quaternary ammonium salt containing bromoacetic acid such as formula (6), wherein n is 300-900.
Difference from Example 1 is：
With chitosan, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide, isopropanol and halogenated acetic acids class chemical combination
Object is raw material, takes 1.5g chitosans to be scattered in 20mL isopropanols and is swollen, and room temperature condition stirs 4 hours, sequentially adds the chloro- 2- of 3-
Hydroxypropyl-trimethyl ammonium chloride 10mL, 40% sodium hydroxide solution 6mL, the reaction was continued 12 hours, then heavy with ethanol in proper amount
It forms sediment, washing, obtains chitosan quaternary ammonium salt.
The chitosan quaternary ammonium salt 1.3g is dissolved in 20mL distilled water, is slowly dropped in 15% bromoacetic acid sodium solution, so
Solution is dialysed for 24 hours in distilled water afterwards, is freeze-dried after concentration, the chitosan quaternary ammonium salt containing bromoacetic acid is obtained.
Fig. 8 is the infrared spectrogram that the embodiment of the present invention 6 provides the chitosan quaternary ammonium salt containing bromoacetic acid, as it can be observed in the picture that
1478cm-1Place's vibration absorption peak still also exists, and in 913cm-1There is the absorption of vibrations of C-Br keys in bromoacetic acid radical ion in place
Thus peak proves chlorion success in bromoacetic acid root anion exchange chitosan quaternary ammonium salt.
Application examples
Antibacterial Activity
(1) inhibit the survey of Botrytis cinerea germ, cucumber fusarium axysporum, asparagus stem wilt bacteria and withered germ of water-melon ability
It is fixed：
Chitosan, chitosan quaternary ammonium salt and synthesized chitosan quaternary ammonium containing monoxone are measured using mycelial growth rate method
Salt, chitosan quaternary ammonium salt containing trichloroacetic acid, chitosan quaternary ammonium salt containing difluoroacetic acid, contains chitosan quaternary ammonium salt containing dichloroacetic acid
The inhibiting effect of trifluoroacetic acid chitosan quaternary ammonium salt and brominated chitosan acetate quaternary ammonium salt to phytopathogenic fungi.For measuring plants
Pathomycete includes Botrytis cinerea germ, cucumber fusarium axysporum, asparagus stem wilt bacteria and withered germ of water-melon.Concrete operations are：
By the chitosan raw material of experiment in embodiment, chitosan quaternary ammonium salt with synthesized chitosan quaternary ammonium salt containing monoxone, containing dichloro
Chitosan acetate quaternary ammonium salt, chitosan quaternary ammonium salt containing trichloroacetic acid, chitosan quaternary ammonium salt containing difluoroacetic acid, shell containing trifluoroacetic acid
After glycan quaternary ammonium salt and brominated chitosan acetate quaternary ammonium salt vacuum freeze drying to constant weight, with water as solvent, it is configured to 5mg/
After the sample aqueous solution of mL, it is 11.8mL, 11mL and 10mL to take 0.2mL, 1mL and 2mL sample solution to be added to volume respectively
In commercially available fungi culture medium, shakes up and pour into cooled and solidified in the batch cultur ware of a diameter of 6cm while hot, sample is finally dense
Degree is 0.1mg/mL, 0.5mg/mL and 1.0mg/mL.After its completely solidification, bacteria cake is carefully inoculated in aseptic nipper solidifying
Solid solid medium center, cultivate 48h under 28 DEG C, 60% damp condition.Using the carbendazim of isoconcentration as positive control, with
Isometric sterile water replaces sample as blank control.Then crossing method is used to measure the diameter of mycelia formation zone,
It is averaged.The calculation formula of the bacteriostasis rate of sample is as follows：
Bacteriostasis rate (%)=[1- (DSample-5)/(DBlank-5)]×100
Wherein DSampleFor sample sets mycelia growth diameter, DBlankFor blank group mycelia growth diameter
(2) bacteria inhibition assay result：
Chitosan quaternary ammonium salt containing monoxone synthesized by the present invention, contains trichloroacetic acid at chitosan quaternary ammonium salt containing dichloroacetic acid
It is poly- to change chitosan quaternary ammonium salt, chitosan quaternary ammonium salt containing difluoroacetic acid, chitosan quaternary ammonium salt containing trifluoroacetic acid and shell containing bromoacetic acid
Sugared quaternary ammonium salt inhibits Botrytis cinerea germ ability as shown in table 1, and inhibition cucumber fusarium axysporum ability is as shown in table 2, inhibits asparagus
Phoma asparagi Sacc ability is as shown in table 3, inhibits withered germ of water-melon ability as shown in table 4：
The ability (%) of the inhibition Botrytis cinerea germ of 1 chitosan quaternary ammonium salt containing halogen of table
The ability (%) of the inhibition cucumber fusarium axysporum germ of 2 chitosan quaternary ammonium salt containing halogen of table
The ability (%) of the inhibition asparagus stem wilt bacteria of 3 chitosan quaternary ammonium salt containing halogen of table
The ability (%) of the inhibition withered germ of water-melon of 4 chitosan quaternary ammonium salt containing halogen of table
As a result as it can be seen that due to halogenated acetic acids have stronger sterilizing ability, therefore with chitosan raw material and chitosan quaternary ammonium
Salt is compared, and the bacteriostasis containing halogenated chitosan acetate quaternary ammonium salt synthesized by the present invention is obviously improved.By being tied to experiment
Fruit is analyzed, we obtain：(1) in chloracetic acid chitosan quaternary ammonium salt, the quantity of contained chlorine atom has one to bacteriostasis
Fixed influence, chlorine atom quantity is more, and antibacterial activity is also stronger.(2) suppression of the halogen in halogenated acetic acids to chitosan derivatives
Bacterium ability has a significant effect, and concrete outcome is the bacteriostatic activity of fluorine-containing chitosan acetate quaternary ammonium salt>Chitosan quaternary ammonium containing monoxone
The bacteriostatic activity of salt>The bacteriostatic activity of brominated chitosan acetate quaternary ammonium salt.
Claims (6)
1. a kind of chitosan quaternary ammonium salt containing halogenated acetic acids, it is characterised in that：The chitosan quaternary ammonium salt containing halogenated acetic acids
Structural formula is as follows：
R=CH2Cl, CHCl2, CCl3, CHF2, CF3,CH2Br
The average value range of wherein n is 300-900.
2. the application of the chitosan quaternary ammonium salt containing halogenated acetic acids as described in claim 1, it is characterised in that：It is described to contain halogenated second
The chitosan quaternary ammonium salt of acid can be applied to the fields such as medicine and pesticide.
3. the preparation method of the chitosan quaternary ammonium salt containing halogenated acetic acids as described in claim 1, it is characterised in that：It is poly- with shell
Sugar, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide, isopropanol and halogenated acetic acids class compound are raw material, specific to make
It is standby that steps are as follows：
(1) it weighs a certain amount of chitosan to be scattered in the isopropanol of certain volume, swelling reaction 4 hours, adds successively at room temperature
Enter 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides solution, sodium hydroxide solution, is reacted 10-12 hours under the conditions of 75 DEG C；Then plus
Enter appropriate absolute ethyl alcohol precipitation, 85% ethyl alcohol washing suction filtration be used in combination to obtain filter cake, 65 DEG C drying to constant weight to get to chitosan season
Ammonium salt；
(2) gained chitosan quaternary ammonium salt is dissolved in deionized water, stirs 1 hour and is dissolved to abundant at room temperature, it will be described abundant
Dissolving chitosan quaternary ammonium salt is transferred in the bag filter that molecular cut off is 500, in certain density halogenated acetic acids sodium solution
Dialysis 12 hours, then removes halogenated acetic acids sodium solution, dialyses for 24 hours, is freeze-dried to get to containing halogenated acetic acids in distilled water
Chitosan quaternary ammonium salt.
4. the preparation method of the chitosan quaternary ammonium salt containing halogenated acetic acids as claimed in claim 3, it is characterised in that：Above-mentioned steps
(2) it could alternatively be the chitosan quaternary ammonium salt to be dissolved in deionized water, it is molten to be slowly dropped to certain density halogenated acetic acids sodium
In liquid, then solution is dialysed in distilled water for 24 hours, freeze-drying is to get to the chitosan quaternary ammonium salt containing halogenated acetic acids.
5. the preparation method of the chitosan quaternary ammonium salt containing halogenated acetic acids as claimed in claim 3, it is characterised in that：Above-mentioned steps
(1) chitosan, isopropanol, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, sodium hydroxide usage ratio be：Per 1-1.5g
Chitosan uses isopropanol 20-40mL, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride 6-12ml, sodium hydroxide 1-1.5g.
6. the preparation method of the chitosan quaternary ammonium salt containing halogenated acetic acids as claimed in claim 3, it is characterised in that：Above-mentioned steps
(2) chitosan quaternary ammonium salt, halogenated acetic acids sodium dosage be：Chitosan quaternary ammonium salt 1-1.5g, halogenated acetic acids sodium 1.5g-3g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613420A (en) * | 2009-08-06 | 2009-12-30 | 浙江澳兴生物科技有限公司 | A kind of preparation method of 2-HACC |
| CN107163160A (en) * | 2017-07-03 | 2017-09-15 | 中国科学院烟台海岸带研究所 | A kind of Ascorbic acid chitosan quaternary ammonium salt and its preparation method and application |
| CN107163159A (en) * | 2017-07-03 | 2017-09-15 | 中国科学院烟台海岸带研究所 | A kind of halogen-containing chitosan quaternary ammonium salt and its preparation method and application |
-
2018
- 2018-06-01 CN CN201810554090.7A patent/CN108623708A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613420A (en) * | 2009-08-06 | 2009-12-30 | 浙江澳兴生物科技有限公司 | A kind of preparation method of 2-HACC |
| CN107163160A (en) * | 2017-07-03 | 2017-09-15 | 中国科学院烟台海岸带研究所 | A kind of Ascorbic acid chitosan quaternary ammonium salt and its preparation method and application |
| CN107163159A (en) * | 2017-07-03 | 2017-09-15 | 中国科学院烟台海岸带研究所 | A kind of halogen-containing chitosan quaternary ammonium salt and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| JINGJING ZHANG等: "Synthesis of Quaternary Ammonium Salts of Chitosan Bearing Halogenated Acetate for Antifungal and Antibacterial Activities", 《POLYMERS》 * |
| WENQIANG TAN等: "Synthesis,characterization, and antifugal property of chitosan ammonium salts with halogens", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
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| CN109943977A (en) * | 2019-03-26 | 2019-06-28 | 泰州億达彩印包装有限公司 | A kind of nanofiber antimicrobial preservative film |
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| CN110256607B (en) * | 2019-08-14 | 2022-03-08 | 中国科学院烟台海岸带研究所 | Anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and preparation method and application thereof |
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| CN116987211B (en) * | 2023-09-25 | 2023-12-01 | 中国科学院烟台海岸带研究所 | Benzimidazole acid-containing hydroxypropyl trimethyl chitosan quaternary ammonium salt derivative and preparation and application thereof |
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