CN103936886B - O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt and method for making and application - Google Patents
O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt and method for making and application Download PDFInfo
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Abstract
The invention belongs to high molecular condensation material field, functional deriv O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt disclosing a kind of Chemical Modifying of Chitosan and preparation method thereof and application.The preparation method of described O-thiazolidine ester-N-trimethyl chitin quaternary ammonium salt comprises the steps:, with chitosan, formaldehyde and formic acid for starting raw material, to obtain N-trimethyl chitin again after prepared by microwave reaction chitosan schiff-base with iodomethane reaction; Utilize L-thiazolidine-4-formic acid and sulfur oxychloride to obtain thiazolidine formyl chloride to join in N-trimethyl chitin and obtain O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt.Described O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt is compared chitosan in germ resistance and is greatly improved, and can be applied to numerous Application Areass such as anti-biotic material, domestic chemical products, Industrial Wastewater Treatment.
Description
Technical field
The invention belongs to high molecular condensation material field, functional deriv O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt being specifically related to a kind of Chemical Modifying of Chitosan and preparation method thereof and application.
Background technology
Along with the development of society and the progress of science and technology, people more and more pay attention to anti-biotic material, and antiseptic-germicide conventional in daily life mainly contains three classes: inorganic metal mineral material, organic heterocyclic antibacterial material 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 a kind of abundance, has multiple bioactive natural polymer.In recent years; the biological degradability that chitosan is good, biocompatibility, film forming characteristics, adsorption sustained-release and stronger Antimicrobial preservative preservativity have caused to be paid close attention to widely and payes attention to, and the Application and Development research in environment protection, biological medicine, foodstuffs industry and chemical industry etc. is very active.By carrying out acylations, alkylation, hydroxylation, aldimine groups, sulphating, carboxymethylation, the chemical modification such as quaternized to chitosan, the chitosan derivatives with certain functional group can be obtained, effectively improve its performance.There are some researches show, methylating of N position is carried out to chitosan and effectively can improve its water-soluble and raising anti-microbial property (DomardA, RinaudoM, TerrassinC.Newmethodforthequaternizationofchitosan. [J] IntJBiolMacromol, 1986,8:105-107.).
Azole is the heterogeneous ring compound (KwasiA.O. of internal-suction type sterilization that a kind of activity is very strong, anti-inflammatory power, VanN.N.2-SubstitutedPhenyl-benzimidazoleAntibacterialAge nts [P] .US, 5942532.1999-11-3.).It is by β 2 tubulin binding with fungal pathogen, destroys β 2 tubulin function, the mitotic division of Antifungi and Morphogenesis.Research shows that different group is introduced in the position different on thiazolidine ring of (1) Top Form Wormer compound, 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, limit its antibacterial in application.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, 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 the preparation method that above-mentioned O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt is provided;
Another object of the present invention is the application providing 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 such as formula shown in (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, n is the natural number of 100 ~ 150.
A preparation method for above-mentioned O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt, comprises the steps:
(1) with chitosan, formaldehyde and formic acid for starting raw material, prepared by microwave reaction chitosan schiff-base; N-trimethyl chitin is obtained again with iodomethane reaction;
(2) first join in sulfur oxychloride by L-thiazolidine-4-formic acid at 0 DEG C of ice bath agitation condition, oil bath is warmed up to 160 DEG C of back flow reaction distillations gradually and obtains thiazolidine formyl chloride solution; The N-trimethyl chitin that step (1) prepares is joined in N-Methyl pyrrolidone and dissolves completely, dropwise drip thiazolidine formyl chloride solution again, dropping continues reaction 2.5h under terminating rear room temperature condition, oil bath return stirring reaction 12 ~ 48h at 60 ~ 100 DEG C of temperature again, acetone is utilized to precipitate after reaction terminates, the precipitation absolute ethanol washing obtained is filtered with G4 funnel, be dried to constant weight under vacuum environment, dialysis postlyophilization obtains O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt.
Preferably, chitosan described in step (1) is deacetylation is 95%, viscosity-average molecular weight is the chitosan of 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 400 ~ 800W, temperature of reaction is stirring reaction 60 ~ 240min under the condition of 30 ~ 60 DEG C.
Preferably, the mass ratio preparing L-thiazolidine-4-formic acid that thiazolidine acyl chlorides uses and sulfur oxychloride in step (2) 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 above-mentioned application of O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt in antibacterial biological material, daily chemical product and field of industrial waste water treatment.
The present invention take L-cysteine hydrochloride as the corresponding L-thiazolidine of Material synthesis-4-formic acid, then continues esterification occurs, by the carboxyl of L-thiazolidine-4-formic acid and the C of N-trimethyl chitin by chloride step and N-trimethyl chitin
6on hydroxyl carry out esterification, there is bioactive group bonding together by 2, preparing 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 relative to prior art:
Chitosan derivatives O-thiazolidine methyl esters-N-trimethyl chitin quaternary ammonium salt of the present invention, in chitosan N position, access trimethylammonium group improve the water-soluble of chitosan and enhance biocidal property, thiazolidine methyl esters group is introduced again in O position, further enhancing anti-microbial activity and the wetting ability of chitosan, two kinds of active groups effectively combine, mutual generation synergetic, the chitosan quaternary ammonium salt that germ resistance is more single or chitosan good, expand the range of application of chitosan.
Accompanying drawing explanation
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 thereto.
In preparation method of the present invention, each starting raw material can be buied from market or conventionally method prepares.In an embodiment, the method that the synthesis of N-trimethyl chitin can conventionally have been reported obtains (Synthesis, characterization, andantibacterialactivityofN, O-quaternaryammoniumchitosan [J] CarbohydrateResearch, Volume346, Issue15,8November2011, Pages2445-2450); The method that thiazolidine formyl chloride can conventionally have been reported obtains (Preparationandantimicrobialactivityofsomecarboxymethylch itosanacylthioureaderivatives [J] InternationalJournalofBiologicalMacromolecules50 (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, be transferred in microwave normal pressure reactor after mixing, regulate microwave power to 400W temperature 30 DEG C reaction 240min; Regulate pH to alkalescence by the NaOH solution of 15% massfraction, suction filtration, is washed to neutrality, joins in 50mLN-N-methyl-2-2-pyrrolidone N-(NMP) after oven dry, adds 20mL methyl iodide, 40 DEG C of reaction 120h; V (ether)/V (the ethanol)=1:1 mixed solvent adding two volumes precipitates, and utilizes deionized water dialysis postlyophilization to obtain N-trimethyl chitin.
Carry out C by photoelectron spectrum quantitative analysis (XPS), substitution value that N element analytical calculation obtains N-trimethyl chitin quaternary ammonium salt is 63%.
(2) L-cysteine hydrochloride (0.06mol) of 10g is pipetted, 100mL deionized water, the formaldehyde solution (0.084mol) of 9g sodium acetate (0.06mol) and 7mL is in single necked round bottom flask, to be mixed evenly after be transferred in microwave normal pressure reactor, microwave power is regulated to leave standstill 10min to 100W temperature 30 DEG C reaction 60min, pyridine 5.2mL (0.06mol) is added in solution, stir and separate out white crystal, thick product ethanol, water recrystallization, can obtain white needles L-thiazolidine-4-formic acid; Get 1.0gL-thiazolidine-4-formic acid to be scattered in 10mL methylene dichloride (DCM), under ice-water bath condition, add the sulfur oxychloride of 2.32g, be warming up to 160 DEG C gradually after stirring 0.5h in 0 DEG C and distill, collect the thiazolidine formyl chloride that component obtains 1g; The N – trimethyl chitin taking 1g dropwise drips thiazolidine solution of acid chloride after joining and fully dissolving in the N-Methyl pyrrolidone of 5mL, reaction 2.5h is continued under room temperature condition, be warming up to 100 DEG C gradually, 6h is reacted under oil bath stirring and refluxing condition, acetone is utilized to precipitate after reaction terminates, utilize G4 funnel filtering-depositing absolute ethanol washing, lyophilize of dialysing after being dried to constant weight under vacuum environment obtains 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 calculates the thiazolidine methyl esters recording N-trimethyl chitin O-position is 13%; The molecular weight being 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, be transferred in microwave normal pressure reactor after mixing, regulate microwave power to 500W temperature 40 DEG C reaction 180min; Regulate pH to alkalescence by the NaOH solution of 15% massfraction, suction filtration, is washed to neutrality, joins in 50mLN-N-methyl-2-2-pyrrolidone N-after oven dry, adds 40mL methyl iodide, 40 DEG C of reaction 120h; V (ether)/V (the ethanol)=1:1 mixed solvent adding two volumes precipitates, and utilizes deionized water dialysis postlyophilization to obtain N-trimethyl chitin.
Carry out C by photoelectron spectrum quantitative analysis (XPS), substitution value that N element analytical calculation obtains N-trimethyl chitin quaternary ammonium salt is 69%.
(2) L-cysteine hydrochloride (0.06mol) of 10g is pipetted, 100mL deionized water, the formaldehyde solution (0.084mol) of 9g sodium acetate (0.06mol) and 7mL is in single necked round bottom flask, to be mixed evenly after be transferred in microwave normal pressure reactor, microwave power is regulated to leave standstill 10min to 100W temperature 30 DEG C reaction 60min, pyridine 5.2mL (0.06mol) is added in solution, stir and separate out white crystal, thick product ethanol, water recrystallization, can obtain white needles L-thiazolidine-4-formic acid; Getting 2.5gL-thiazolidine-4-formic acid is scattered in 10mL methylene dichloride, adds the sulfur oxychloride of 9.0g, be warming up to 160 DEG C gradually and distill after 0 DEG C of stirring reaction 0.5h under ice-water bath condition, collects component and obtains 2g thiazolidine formyl chloride liquid; The N-trimethyl chitin taking 1g dropwise drips thiazolidine formyl chloride after joining and dissolving completely in the N-Methyl pyrrolidone of 10mL, dropping continues reaction 2.5h under terminating rear room temperature condition, be warming up to 90 DEG C gradually, 12h is reacted under oil bath stirring and refluxing condition, acetone is utilized to precipitate after reaction terminates, utilize G4 funnel to filter, the precipitation absolute ethanol washing obtained, lyophilize of dialysing after being dried to constant weight under vacuum environment obtains 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 calculates the rich horse ester of N-trimethyl chitin O-position is 17%; The molecular weight being 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, be transferred in microwave normal pressure reactor after mixing, regulate microwave power to 600W temperature 50 C reaction 120min; Regulate pH to alkalescence by the NaOH solution of 15% massfraction, suction filtration, is washed to neutrality, joins in 50mLN-N-methyl-2-2-pyrrolidone N-after oven dry, adds 60mL methyl iodide, 40 DEG C of reaction 120h; V (ether)/V (the ethanol)=1:1 mixed solvent adding two volumes precipitates, and utilizes deionized water dialysis postlyophilization to obtain N-trimethyl chitin.
Carry out C by photoelectron spectrum quantitative analysis (XPS), substitution value that N element analytical calculation obtains N-trimethyl chitin quaternary ammonium salt is 73%.
(2) L-cysteine hydrochloride (0.06mol) of 10g is pipetted, 100mL deionized water, the formaldehyde solution (0.084mol) of 9g sodium acetate (0.06mol) and 7mL is in single necked round bottom flask, to be mixed evenly after be transferred in microwave normal pressure reactor, microwave power is regulated to leave standstill 10min to 100W temperature 30 DEG C reaction 60min, pyridine 5.2mL (0.06mol) is added in solution, stir and separate out white crystal, thick product ethanol, water recrystallization, can obtain white needles L-thiazolidine-4-formic acid; Getting 3.6gL-thiazolidine-4-formic acid is scattered in 10mL methylene dichloride, adds the sulfur oxychloride of 21.6g, be warming up to 160 DEG C gradually and distill after 0 DEG C of stirring reaction 0.5h under ice-water bath condition, collects component and obtains 3g thiazolidine formyl chloride liquid; The N-trimethyl chitin taking 1g dropwise drips thiazolidine formyl chloride liquid after joining and fully dissolving in the N-Methyl pyrrolidone of 15mL, dropping continues reaction 2.5h under terminating rear room temperature condition, be warming up to 70 DEG C gradually, 24h is reacted under oil bath stirring and refluxing condition, acetone is utilized to precipitate after reaction terminates, utilize G4 funnel to filter, precipitation absolute ethanol washing, lyophilize of dialysing after being dried to constant weight under vacuum environment obtains 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 calculates the thiazolidine methyl esters of N-trimethyl chitin O-position is 23%; The molecular weight being recorded the rich horse ester of O--N-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, be transferred in microwave normal pressure reactor after mixing, regulate microwave power to 800W temperature 60 C reaction 60min; Regulate pH to alkalescence by the NaOH solution of 15% massfraction, suction filtration, is washed to neutrality, joins in 50mLN-N-methyl-2-2-pyrrolidone N-after oven dry, adds 80mL methyl iodide, 40 DEG C of reaction 120h; V (ether)/V (the ethanol)=1:1 mixed solvent adding two volumes precipitates, and utilizes deionized water dialysis postlyophilization to obtain N-trimethyl chitin.Deionized water dialysis postlyophilization is utilized to obtain N-trimethyl chitin.
Carry out C by photoelectron spectrum quantitative analysis (XPS), substitution value that N element analytical calculation obtains N-trimethyl chitin quaternary ammonium salt is 79%.
(2) L-cysteine hydrochloride (0.06mol) of 10g is pipetted, 100mL deionized water, the formaldehyde solution (0.084mol) of 9g sodium acetate (0.06mol) and 7mL is in single necked round bottom flask, to be mixed evenly after be transferred in microwave normal pressure reactor, microwave power is regulated to leave standstill 10min to 100W temperature 30 DEG C reaction 60min, pyridine 5.2mL (0.06mol) is added in solution, stir and separate out white crystal, thick product ethanol, water recrystallization, can obtain white needles L-thiazolidine-4-formic acid; Getting 7.0gL-thiazolidine-4-formic acid is scattered in 10mL methylene dichloride, adds the sulfur oxychloride of 70g under ice-water bath condition, is warming up to 160 DEG C gradually and distills, collect component and obtain 6g thiazolidine formyl chloride liquid after 0 DEG C of stirring 0.5h; The N-trimethyl chitin taking 1g dropwise drips thiazolidine solution of acid chloride after joining and fully dissolving in N-Methyl pyrrolidone, continues reaction 2.5h, be warming up to 60 DEG C gradually, react 48h under oil bath stirring and refluxing condition under room temperature condition.The precipitation absolute ethanol washing utilizing G4 funnel filtering reacting solution to obtain, lyophilize of dialysing after being dried to constant weight under vacuum environment obtains product O-thiazolidine acyl-N-trimethyl chitin quaternary ammonium salt.
Carrying out by photoelectron spectrum quantitative analysis (XPS) substitution value that C, N, O ultimate analysis calculates the thiazolidine methyl esters of N-trimethyl chitin O-position is 26%; The molecular weight being 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:
Substratum diffusion process is adopted 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.Judgement according 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 moderate antibacterial at 10mm ~ 20mm, it is weak antibacterial that inhibition zone is less than 10mm, and namely inhibition zone has biocidal property to judge the fungistatic effect of compound at 7mm.Nutrient broth dilution method measures 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 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 gram positive bacterium is better than to the fungistatic effect of Gram-negative bacteria, be the excellent biomass antibacterial material of a kind of fungistatic effect, numerous Application Areass such as anti-biotic material, domestic chemical products, Industrial Wastewater Treatment can be widely used in.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within 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 such as formula shown in (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, n is the natural number of 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) with chitosan, formaldehyde and formic acid for starting raw material, prepared by microwave reaction chitosan schiff-base; N-trimethyl chitin quaternary ammonium salt is obtained again with iodomethane reaction;
(2) first join in sulfur oxychloride by L-thiazolidine-4-formic acid at 0 DEG C of ice bath agitation condition, oil bath is warmed up to 160 DEG C of back flow reaction distillations gradually and obtains thiazolidine formyl chloride solution; N-trimethyl chitin quaternary ammonium salt step (1) prepared joins in N-Methyl pyrrolidone and dissolves completely, dropwise drip thiazolidine formyl chloride solution again, dropping continues reaction 2.5h under terminating rear room temperature condition, oil bath return stirring reaction 12 ~ 48h at 60 ~ 100 DEG C of temperature again, acetone is utilized to precipitate after reaction terminates, the precipitation absolute ethanol washing obtained is filtered with G4 funnel, be dried to constant weight under vacuum environment, 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 deacetylation is 95%, viscosity-average molecular weight is the chitosan of 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 400 ~ 800W, temperature of reaction is stirring reaction 60 ~ 240min under the condition of 30 ~ 60 DEG C.
5. preparation method according to claim 2, is characterized in that: the mass ratio preparing L-thiazolidine-4-formic acid that thiazolidine formyl chloride uses and sulfur oxychloride in step (2) is 1:(2 ~ 10).
6. preparation method according to claim 2, is characterized in that: the N-trimethyl chitin quaternary ammonium salt described in step (2) and the mass ratio of N-Methyl pyrrolidone are 1:(5 ~ 20).
7. preparation method according to claim 2, is characterized in that: the mass ratio of the thiazolidine formyl chloride described in step (2) and N-trimethyl chitin quaternary ammonium salt is (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 field of industrial waste water treatment.
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