CN103936886A - O-thiazolidine methyl ester-N-trimethyl chitosan quaternary ammonium salt as well as preparation method and application thereof - Google Patents
O-thiazolidine methyl ester-N-trimethyl chitosan quaternary ammonium salt as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of the high polymer compound materials and discloses an O-thiazolidine methyl ester-N-trimethyl chitosan quaternary ammonium salt as well as a preparation method and application thereof. The preparation method of the O-thiazolidine methyl ester-N-trimethyl chitosan quaternary ammonium salt comprises the following steps: carrying out a microwave reaction on starting raw materials (including chitosan, formaldehyde and formic acid) to obtain a chitosan Schiff base and then reacting the chitosan Schiff base with methyl iodide to obtain N-trimethyl chitosan; preparing thiazolidine formyl chloride by using L-thiazolidine-4-formic acid and thionyl chloride, adding the thiazolidine formyl chloride to N-trimethyl chitosan to obtain the O-thiazolidine methyl ester-N-trimethyl chitosan quaternary ammonium salt. The O-thiazolidine methyl ester-N-trimethyl chitosan quaternary ammonium salt is greatly improved in term of antibacterial property in contrast with the chitosan, and thus can be applied to various fields such as antibacterial materials, chemical products of daily use and industrial wastewater treatment.
Description
Technical field
The invention belongs to high molecular condensation material field, be specifically related to functional deriv O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt of a kind of Chemical Modifying of Chitosan and preparation method thereof and application.
Background technology
Along with social development and scientific and technological progress, people more and more pay attention to anti-biotic material, and in daily life, conventional antiseptic-germicide mainly contains three classes: inorganic metal mineral material, the antibacterial material of organic heterocyclic and natural antibacterial material.Due to natural antibiotic antiseptic derive from nature, high and meet environment protection requirement to human safety, welcomed by the people in recent years.The research and development of natural antibacterial agent has utilized a focus into applied chemistry.
Chitosan is widespread in nature among the cell walls of the shell of shrimp, crab and insect and algae, mushroom, is that multiple bioactive natural polymer is enriched, has in a kind of source.In recent years; biological degradability, biocompatibility, film forming characteristics, adsorption sustained-release and stronger antibacterial anti-corrosive fresh-keeping ability that chitosan is good have caused to be paid close attention to widely and payes attention to, very active in the Application and Development research of the aspects such as environment protection, biological medicine, foodstuffs industry and chemical industry.By chitosan being carried out to acylations, alkylation, hydroxylation, aldimine groups, sulphating, carboxymethylation, the chemical modification such as quaternized, can obtain having the chitosan derivatives of certain functional group, effectively improve its performance.There are some researches show, chitosan is carried out to methylating of N position and can effectively improve its water-soluble and raising anti-microbial property (Domard A, Rinaudo M, Terrassin C.New method for the quaternization of chitosan.[J] Int J Biol Macromol, 1986,8:105-107.).
Azole is the internal-suction type sterilization that a kind of activity is very strong, heterogeneous ring compound (the Kwasi A.O. of anti-inflammatory ability, Van N.N.2-Substituted Phenyl-benzimidazole Antibacterial Agents[P] .US, 5942532.1999-11-3.).It is by with β 2 tubulin bindings of fungal pathogen, destroy β 2 tubulin functions, the mitotic division of Antifungi and Morphogenesis.Research shows that (1) Top Form Wormer compound different position on thiazolidine ring introduces different groups, has the sterilization effect (especially [1,2-a] Top Form Wormer compounds) of wide spectrum; (2) the heteroatomic introducing such as aromatic ring and N, S can improve compound fungicidal activity preferably; (3) connect the structure with electron-withdrawing group, its bacteriostatic activity can improve a lot.
Chitosan has water-fast characteristic, limited its application in antibacterial.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of novel water-solubility chitosan derivative with antibacterial effect: O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt;
Another object of the present invention is to provide the preparation method of above-mentioned O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt;
A further object of the present invention is to provide the application of above-mentioned O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt.
Object of the present invention is achieved through the following technical solutions:
O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, its structure is suc as formula shown in (1):
Formula (1):
Wherein, the molecular weight of described O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt is 5.0 × 10
4～7.5 × 10
4, the natural number that n is 100～150.
A preparation method for above-mentioned O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, comprises the steps:
(1) taking chitosan, formaldehyde and formic acid as starting raw material, prepared by microwave reaction chitosan schiff-base; Make N-trimethyl chitin with iodomethane reaction again;
(2) first L-thiazolidine-4-formic acid is joined in sulfur oxychloride at 0 DEG C of ice bath agitation condition, oil bath is warmed up to gradually 160 DEG C of back flow reaction distillations and obtains thiazolidine formyl chloride solution; The N-trimethyl chitin that step (1) is prepared joins in N-Methyl pyrrolidone and dissolves completely, dropwise drip again thiazolidine formyl chloride solution, dropping finishes continuation reaction 2.5h under rear room temperature condition, oil bath return stirring reaction 12～48h at 60～100 DEG C of temperature again, after finishing, reaction utilize acetone to precipitate, filter the precipitation absolute ethanol washing obtaining with G4 funnel, under vacuum environment, be dried to constant weight, dialysis postlyophilization obtains O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt.
Preferably, chitosan described in step (1) is the chitosan that deacetylation is 95%, viscosity-average molecular weight is 50000Da; Described chitosan and the mass ratio of methyl iodide are 1:(5～20).
Preferably, described in step (1), the condition of microwave reaction is: microwave power is that 400～800W, temperature of reaction are stirring reaction 60～240min under the condition of 30～60 DEG C.
Preferably, in step (2), preparing L-thiazolidine-4-formic acid that thiazolidine acyl chlorides uses and the mass ratio of sulfur oxychloride is 1:(2～10).
Preferably, the N-chitosan quaternary ammonium salt described in step (2) and the mass ratio of N-Methyl pyrrolidone are 1:(5～20).
Preferably, the thiazolidine formyl chloride described in step (2) and the mass ratio of N-trimethyl chitin are (1～6): 1.
The application of above-mentioned O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt in antibacterial biological material, daily chemical product and Industrial Wastewater Treatment field.
The present invention is synthetic corresponding L-thiazolidine-4-formic acid taking Cys hydrochloride as raw material, then continue esterification occurs by chloride step and N-trimethyl chitin, by the carboxyl of L-thiazolidine-4-formic acid and the C of N-trimethyl chitin
6on hydroxyl carry out esterification, there is bioactive group bonding together by 2, prepare O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, to obtaining better bacteriostatic activity.
The preparation process schematic diagram of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt of the present invention as shown in Figure 1.
The present invention has following advantage and effect with respect to prior art:
Chitosan derivatives O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt of the present invention, in chitosan N position, having accessed trimethylammonium group has improved the water-soluble of chitosan and has strengthened biocidal property, introduced again thiazolidine methyl esters group in O position, anti-microbial activity and the wetting ability of chitosan are further strengthened, two kinds of active groups effectively combine, mutually produce synergetic, the chitosan quaternary ammonium salt that germ resistance is more single or chitosan are good, have expanded the range of application of chitosan.
Brief description of the drawings
Fig. 1 is the preparation process schematic diagram of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
In preparation method of the present invention, each starting raw material can be buied from market or prepare according to art methods.In an embodiment, the synthetic method that can report according to prior art of N-trimethyl chitin obtains (Synthesis, characterization, and antibacterial activity of N, O-quaternary ammonium chitosan[J] Carbohydrate Research, Volume346, Issue15,8November2011, Pages2445-2450); The method that thiazolidine formyl chloride can have been reported according to prior art obtains (Preparation and antimicrobial activity of some carboxymethyl chitosan acylthiourea derivatives[J] International Journal of Biological Macromolecules50 (2012) 1280 – 1285), but the acquisition of N-trimethyl chitin and thiazolidine formyl chloride is not limited to this kind of mode.
Embodiment 1
A kind of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, its preparation method is as follows:
(1) chitosan of 4g is dissolved in the formic acid of 200mL deionized water and 15mL, stirs and be warming up to 70 DEG C, add the formaldehyde solution of 10mL, after mixing, be transferred in microwave normal pressure reactor, regulate microwave power to 30 DEG C of reaction 240min of 400W temperature; With the NaOH solution adjusting pH of 15% massfraction, to alkalescence, suction filtration, is washed to neutrality, joins in 50mL METHYLPYRROLIDONE (NMP) after oven dry, adds 20mL methyl iodide, 40 DEG C of reaction 120h; Add V (ether)/V (the ethanol)=1:1 mixed solvent of two volumes to precipitate, utilize deionized water dialysis postlyophilization to make N-trimethyl chitin.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N ultimate analysis calculate N-trimethyl chitin quaternary ammonium salt is 63%.
(2) pipette the Cys hydrochloride (0.06mol) of 10g, 100mL deionized water, the formaldehyde solution (0.084mol) of 9g sodium acetate (0.06mol) and 7mL is to single necked round bottom flask, to be mixedly be transferred in microwave normal pressure reactor after evenly, regulate microwave power to leave standstill 10min to 30 DEG C of reaction 60min of 100W temperature, in solution, add pyridine 5.2mL (0.06mol), white crystal is separated out in stirring, slightly ethanol, water recrystallization for product, can obtain white needles L-thiazolidine-4-formic acid; Get 1.0g L-thiazolidine-4-formic acid and be scattered in 10mL methylene dichloride (DCM), add the sulfur oxychloride of 2.32g under ice-water bath condition, be warming up to gradually 160 DEG C and distill after 0 DEG C of stirring 0.5h, collection component obtains the thiazolidine formyl chloride of 1g; The N – trimethyl chitin that takes 1g dropwise drips thiazolidine solution of acid chloride after joining and fully dissolving in the N-Methyl pyrrolidone of 5mL, under room temperature condition, continue reaction 2.5h, be warming up to gradually 100 DEG C, under oil bath stirring and refluxing condition, react 6h, after finishing, reaction utilize acetone to precipitate, utilize G4 funnel filtering-depositing absolute ethanol washing, under vacuum environment, be dried to the lyophilize of dialysing after constant weight and obtain product O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N, O ultimate analysis calculate the thiazolidine methyl esters that records N-trimethyl chitin O-position is 13%; The molecular weight that is recorded O-fumaryl-N-chitosan quaternary ammonium salt by gel permeation chromatography (GPC) is 5.0 × 10
4.
Embodiment 2
A kind of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, its preparation method is as follows:
(1) chitosan of 4g is dissolved in the formic acid of 200mL deionized water and 15mL, stirs and be warming up to 70 DEG C, add the formaldehyde solution of 10mL, after mixing, be transferred in microwave normal pressure reactor, regulate microwave power to 40 DEG C of reaction 180min of 500W temperature; With the NaOH solution adjusting pH of 15% massfraction, to alkalescence, suction filtration, is washed to neutrality, joins in 50mL METHYLPYRROLIDONE after oven dry, adds 40mL methyl iodide, 40 DEG C of reaction 120h; Add V (ether)/V (the ethanol)=1:1 mixed solvent of two volumes to precipitate, utilize deionized water dialysis postlyophilization to make N-trimethyl chitin.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N ultimate analysis calculate N-trimethyl chitin quaternary ammonium salt is 69%.
(2) pipette the Cys hydrochloride (0.06mol) of 10g, 100mL deionized water, the formaldehyde solution (0.084mol) of 9g sodium acetate (0.06mol) and 7mL is to single necked round bottom flask, to be mixedly be transferred in microwave normal pressure reactor after evenly, regulate microwave power to leave standstill 10min to 30 DEG C of reaction 60min of 100W temperature, in solution, add pyridine 5.2mL (0.06mol), white crystal is separated out in stirring, slightly ethanol, water recrystallization for product, can obtain white needles L-thiazolidine-4-formic acid; Get 2.5gL-thiazolidine-4-formic acid and be scattered in 10mL methylene dichloride, under ice-water bath condition, add the sulfur oxychloride of 9.0g, after 0 DEG C of stirring reaction 0.5h, be warming up to gradually 160 DEG C and distill, collect component and obtain 2g thiazolidine formyl chloride liquid; The N-trimethyl chitin that takes 1g dropwise drips thiazolidine formyl chloride after joining and dissolving completely in the N-Methyl pyrrolidone of 10mL, dropping finishes continuation reaction 2.5h under rear room temperature condition, be warming up to gradually 90 DEG C, under oil bath stirring and refluxing condition, react 12h, after finishing, reaction utilize acetone to precipitate, utilize G4 funnel to filter, the precipitation absolute ethanol washing obtaining, is dried to the lyophilize of dialysing after constant weight and obtains product O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt under vacuum environment.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N, O ultimate analysis calculate the rich horse ester of N-trimethyl chitin O-position is 17%; The molecular weight that is recorded O-thiazolidine methyl esters-N-chitosan quaternary ammonium salt by gel permeation chromatography (GPC) is 6.62 × 10
4.
Embodiment 3
A kind of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, its preparation method is as follows:
(1) chitosan of 4g is dissolved in the formic acid of 200mL deionized water and 15mL, stirs and be warming up to 70 DEG C, add the formaldehyde solution of 10mL, after mixing, be transferred in microwave normal pressure reactor, regulate microwave power to 600W temperature 50 C reaction 120min; With the NaOH solution adjusting pH of 15% massfraction, to alkalescence, suction filtration, is washed to neutrality, joins in 50mL METHYLPYRROLIDONE after oven dry, adds 60mL methyl iodide, 40 DEG C of reaction 120h; Add V (ether)/V (the ethanol)=1:1 mixed solvent of two volumes to precipitate, utilize deionized water dialysis postlyophilization to make N-trimethyl chitin.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N ultimate analysis calculate N-trimethyl chitin quaternary ammonium salt is 73%.
(2) pipette the Cys hydrochloride (0.06mol) of 10g, 100mL deionized water, the formaldehyde solution (0.084mol) of 9g sodium acetate (0.06mol) and 7mL is to single necked round bottom flask, to be mixedly be transferred in microwave normal pressure reactor after evenly, regulate microwave power to leave standstill 10min to 30 DEG C of reaction 60min of 100W temperature, in solution, add pyridine 5.2mL (0.06mol), white crystal is separated out in stirring, slightly ethanol, water recrystallization for product, can obtain white needles L-thiazolidine-4-formic acid; Get 3.6g L-thiazolidine-4-formic acid and be scattered in 10mL methylene dichloride, under ice-water bath condition, add the sulfur oxychloride of 21.6g, after 0 DEG C of stirring reaction 0.5h, be warming up to gradually 160 DEG C and distill, collect component and obtain 3g thiazolidine formyl chloride liquid; The N-trimethyl chitin that takes 1g dropwise drips thiazolidine formyl chloride liquid after joining and fully dissolving in the N-Methyl pyrrolidone of 15mL, dropping finishes continuation reaction 2.5h under rear room temperature condition, be warming up to gradually 70 DEG C, under oil bath stirring and refluxing condition, react 24h, after finishing, reaction utilize acetone to precipitate, utilize G4 funnel to filter, precipitation absolute ethanol washing, is dried to the lyophilize of dialysing after constant weight and obtains product O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt under vacuum environment.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N, O ultimate analysis calculate the thiazolidine methyl esters of N-trimethyl chitin O-position is 23%; The molecular weight that is recorded the rich horse ester-N-of O-chitosan quaternary ammonium salt by gel permeation chromatography (GPC) is 6.99 × 10
4.
Embodiment 4
A kind of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, its preparation method is as follows:
(1) chitosan of 4g is dissolved in the formic acid of 200mL deionized water and 15mL, stirs and be warming up to 70 DEG C, add the formaldehyde solution of 10mL, after mixing, be transferred in microwave normal pressure reactor, regulate microwave power to 800W temperature 60 C reaction 60min; With the NaOH solution adjusting pH of 15% massfraction, to alkalescence, suction filtration, is washed to neutrality, joins in 50mL METHYLPYRROLIDONE after oven dry, adds 80mL methyl iodide, 40 DEG C of reaction 120h; Add V (ether)/V (the ethanol)=1:1 mixed solvent of two volumes to precipitate, utilize deionized water dialysis postlyophilization to make N-trimethyl chitin.Utilize deionized water dialysis postlyophilization to make N-trimethyl chitin.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N ultimate analysis calculate N-trimethyl chitin quaternary ammonium salt is 79%.
(2) pipette the Cys hydrochloride (0.06mol) of 10g, 100mL deionized water, the formaldehyde solution (0.084mol) of 9g sodium acetate (0.06mol) and 7mL is to single necked round bottom flask, to be mixedly be transferred in microwave normal pressure reactor after evenly, regulate microwave power to leave standstill 10min to 30 DEG C of reaction 60min of 100W temperature, in solution, add pyridine 5.2mL (0.06mol), white crystal is separated out in stirring, slightly ethanol, water recrystallization for product, can obtain white needles L-thiazolidine-4-formic acid; Get 7.0g L-thiazolidine-4-formic acid and be scattered in 10mL methylene dichloride, under ice-water bath condition, add the sulfur oxychloride of 70g, after 0 DEG C of stirring 0.5h, be warming up to gradually 160 DEG C and distill, collect component and obtain 6g thiazolidine formyl chloride liquid; The N-trimethyl chitin that takes 1g joins in N-Methyl pyrrolidone and fully after dissolving, dropwise drips thiazolidine solution of acid chloride, continues reaction 2.5h under room temperature condition, is warming up to gradually 60 DEG C, under oil bath stirring and refluxing condition, reacts 48h.The precipitation absolute ethanol washing that utilizes G4 funnel filtering reacting solution to obtain, is dried to the lyophilize of dialysing after constant weight and obtains product O-thiazolidine acyl-N-trimethyl chitin quaternary ammonium salt under vacuum environment.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N, O ultimate analysis calculate the thiazolidine methyl esters of N-trimethyl chitin O-position is 26%; The molecular weight that is recorded O-thiazolidine methyl esters-N-chitosan quaternary ammonium salt by gel permeation chromatography (GPC) is 7.5 × 10
4.
Embodiment 5, O-thiazolidine methyl esters--the test of N-trimethyl chitin quaternary ammonium salt anti-microbial property
The mensuration of the bacteriostatic activity of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt of the present invention:
Adopt substratum diffusion process to determine that O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt sample is to gram-positive microorganism streptococcus aureus and the colibacillary anti-microbial activity of Gram-negative bacteria.According to the judgement to bacteriostatic action in " disinfection technology standard 2006 ": antibacterial circle diameter is greater than 20mm and represents to have strong fungistatic effect, inhibition zone is medium antibacterial at 10mm～20mm, it is weak antibacterial that inhibition zone is less than 10mm, and inhibition zone has biocidal property and judge the fungistatic effect of compound at 7mm.Nutrient broth dilution method is measured the minimal inhibitory concentration (MIC) of chitosan raw material and product O-thiazolidine acyl-N-trimethyl chitin quaternary ammonium salt of the present invention.
Bacteria inhibition assay result is as shown in table 1:
Table 1 chitosan and O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt anti-microbial property test result
Product O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt of the present invention is compared chitosan and in bacteriostatic action, is had advantage progress.From antibacterial circle diameter experimental data in table, product O-thiazolidine acyl-N-trimethyl chitin quaternary ammonium salt of the present invention is obviously better than unmodified chitosan to gram-positive microorganism streptococcus aureus and the colibacillary bacteriostatic action of Gram-negative bacteria; And the fungistatic effect to Gram-negative bacteria is better than gram positive bacterium, be the antibacterial materials of the good biomass of a kind of fungistatic effect, can be widely used in numerous Application Areass such as anti-biotic material, domestic chemical products, Industrial Wastewater Treatment.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1.O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, is characterized in that structure is suc as formula shown in (1):
Formula (1):
Wherein, the molecular weight of described O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt is 5.0 × 10
4～7.5 × 10
4, the natural number that n is 100～150.
2. a preparation method for O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt according to claim 1, is characterized in that comprising the steps:
(1) taking chitosan, formaldehyde and formic acid as starting raw material, prepared by microwave reaction chitosan schiff-base; Make N-trimethyl chitin with iodomethane reaction again;
(2) first L-thiazolidine-4-formic acid is joined in sulfur oxychloride at 0 DEG C of ice bath agitation condition, oil bath is warmed up to gradually 160 DEG C of back flow reaction distillations and obtains thiazolidine formyl chloride solution; The N-trimethyl chitin that step (1) is prepared joins in N-Methyl pyrrolidone and dissolves completely, dropwise drip again thiazolidine formyl chloride solution, dropping finishes continuation reaction 2.5h under rear room temperature condition, oil bath return stirring reaction 12～48h at 60～100 DEG C of temperature again, after finishing, reaction utilize acetone to precipitate, filter the precipitation absolute ethanol washing obtaining with G4 funnel, under vacuum environment, be dried to constant weight, dialysis postlyophilization obtains O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt.
3. preparation method according to claim 2, is characterized in that: chitosan described in step (1) is the chitosan that deacetylation is 95%, viscosity-average molecular weight is 50000Da; Described chitosan and the mass ratio of methyl iodide are 1:(5～20).
4. preparation method according to claim 2, is characterized in that: described in step (1), the condition of microwave reaction is: microwave power is that 400～800W, temperature of reaction are stirring reaction 60～240min under the condition of 30～60 DEG C.
5. preparation method according to claim 2, is characterized in that: in step (2), preparing L-thiazolidine-4-formic acid that thiazolidine acyl chlorides uses and the mass ratio of sulfur oxychloride is 1:(2～10).
6. preparation method according to claim 2, is characterized in that: the N-chitosan quaternary ammonium salt that step (2) is described and the mass ratio of N-Methyl pyrrolidone are 1:(5～20).
7. preparation method according to claim 2, is characterized in that: the thiazolidine formyl chloride that step (2) is described and the mass ratio of N-trimethyl chitin are (1～6): 1.
8. the application of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt according to claim 1 in antibacterial biological material, daily chemical product and Industrial Wastewater Treatment field.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106380526A (en) * | 2016-09-22 | 2017-02-08 | 湖南工业大学 | O-alpha-methyl mandelate-N-trimethyl chitosan quaternary ammonium salt as well as preparation method and application thereof |
| CN114014955A (en) * | 2022-01-10 | 2022-02-08 | 中国科学院烟台海岸带研究所 | N, O-carboxymethyl chitosan containing thiazole salt and preparation and application thereof |
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