CN113429493A - Preparation method of non-release type high-molecular antibacterial anti-mite agent - Google Patents

Preparation method of non-release type high-molecular antibacterial anti-mite agent Download PDF

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CN113429493A
CN113429493A CN202110730983.4A CN202110730983A CN113429493A CN 113429493 A CN113429493 A CN 113429493A CN 202110730983 A CN202110730983 A CN 202110730983A CN 113429493 A CN113429493 A CN 113429493A
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antibacterial
release type
reaction
carboxymethyl chitosan
diethylhydrazine
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CN113429493B (en
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马晓飞
张丽
张志成
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Jixiang Sanbao High Tech New Materials Co ltd
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Jixiang Sanbao High Tech Textile Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/00272-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003Chitin, 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
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/103Agents inhibiting growth of microorganisms
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses a preparation method of a non-release type high molecular antibacterial and acaricidal agent, which relates to the technical field of antibacterial and acaricidal agents, wherein the non-release type high molecular antibacterial and acaricidal agent is prepared by carrying out acyl chlorination reaction and amidation reaction on carboxymethyl chitosan, thionyl chloride and N, N-diethylhydrazine thioamide; the modified chitosan is prepared from carboxymethyl chitosan and N, N-diethylhydrazine thioamide by utilizing a splicing principle, belongs to a non-release type high-molecular antibacterial anti-mite agent, has antibacterial anti-mite performance far superior to that of carboxymethyl chitosan, can solve the problem of poor antibacterial durability of carboxymethyl chitosan, and can remarkably optimize the antibacterial anti-mite effect of textiles when the modified chitosan is applied to textile processing as the antibacterial anti-mite agent.

Description

Preparation method of non-release type high-molecular antibacterial anti-mite agent
The technical field is as follows:
the invention relates to the technical field of antibacterial and anti-mite agents, and particularly relates to a preparation method of a non-release type high-molecular antibacterial and anti-mite agent.
Background art:
bacteria and mites are all micro-organisms invisible to the naked eye, and under appropriate circumstances they can rapidly multiply with sweat, secretions and shed dander secreted by humans as nutrients. In addition, secretion, metabolite and corpse of the mites are allergens which can cause diseases, and allergic dermatitis or respiratory diseases are very easy to cause. Therefore, the preparation of the antibacterial and anti-mite fabric is very necessary.
At present, the antibacterial and mite-proof agents are mainly divided into three categories, namely inorganic antibacterial and mite-proof agents, organic antibacterial and mite-proof agents and natural antibacterial and mite-proof agents. Wherein, the natural antibacterial and acaricidal agent has relatively high safety, but weak antibacterial and acaricidal effect; the organic antibacterial and mite-proof agent has a remarkable effect, but part of the organic antibacterial and mite-proof agent has high toxicity, so that potential safety hazards to human bodies exist after long-time use; most of inorganic antibacterial and mite-proof agents are release type antibacterial and mite-proof mechanisms, the durability is poor, the blending compatibility with high polymer materials is poor, and the mechanical properties of the high polymer materials can be influenced.
The invention content is as follows:
chitosan has a broad-spectrum antibacterial effect, but the difficulty in dissolving chitosan in water and common organic solvents limits the wide application of chitosan in the field of antibacterial agents. Therefore, the carboxymethyl chitosan synthesized by people has good water solubility and strong antibacterial property, but the antibacterial durability is poor. In addition, carboxymethyl chitosan has a weak anti-mite effect, and the carboxymethyl chitosan alone serving as an anti-mite agent cannot achieve a good control effect.
The invention aims to solve the technical problem of providing a preparation method of a non-release type high-molecular antibacterial anti-mite agent, which takes carboxymethyl chitosan as a starting raw material, and sequentially carries out acyl chlorination reaction and amidation reaction with thionyl chloride and N, N-diethylhydrazine thioamide to prepare modified chitosan, wherein the antibacterial anti-mite performance of the modified chitosan is far superior to that of the carboxymethyl chitosan although the modified chitosan contains a chitosan structure.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention aims to provide a non-release type high-molecular antibacterial and acaricidal agent which is prepared from carboxymethyl chitosan, thionyl chloride and N, N-diethylhydrazine thioamide through an acyl chlorination reaction and an amidation reaction.
The molar amount of the thionyl chloride is 2-5 times of the molar amount of carboxyl contained in the carboxymethyl chitosan.
The thionyl chloride is used as an acyl chlorination reagent, the excessive thionyl chloride can ensure that all carboxyl groups contained in the carboxymethyl chitosan are converted into acyl chloride, and the unreacted thionyl chloride can be removed by distillation.
The molar amount of the N, N-diethylhydrazine thioamide is 0.8-1 time of that of carboxyl contained in the carboxymethyl chitosan.
The excessive carboxymethyl chitosan is used because excessive carboxymethyl chitosan can generate excessive acyl chloride intermediate through acyl chlorination reaction, the excessive acyl chloride intermediate can ensure complete reaction of N, N-diethylhydrazine thioamide, the excessive acyl chloride intermediate is reduced into carboxymethyl chitosan when meeting water during post-treatment, the carboxymethyl chitosan is easy to dissolve in water, and the unreacted carboxymethyl chitosan can be separated and removed through the post-treatment.
The synthetic route of the non-release type high molecular antibacterial anti-mite agent is as follows:
Figure BDA0003139293060000021
the invention also aims to provide a preparation method of the non-release type high molecular antibacterial and acaricidal agent, which comprises the following steps:
(1) ultrasonic dispersing carboxymethyl chitosan in SOCl2Heating to 70-80 ℃, carrying out heat preservation reaction, stopping the reaction when the conversion rate of carboxyl contained in the carboxymethyl chitosan reaches 100% is detected in the infrared, and distilling to remove redundant SOCl2Obtaining an intermediate;
(2) heating the intermediate to 55-65 ℃, keeping the temperature, stirring, dropwise adding a DMF solution dissolved with N, N-diethylhydrazine thioamide and triethylamine, continuing to keep the temperature at 55-65 ℃ for reaction after dropwise adding, stopping the reaction when TLC detects that the N, N-diethylhydrazine thioamide is completely reacted, dropwise adding deionized water into the reaction solution until no precipitate is separated out, standing, filtering, washing with water, and drying in vacuum to obtain the non-release type high-molecular antibacterial and acarid-preventing agent.
The frequency of the ultrasonic wave is 20-40kHz, and the power is 100-1000W.
The molar amount of the triethylamine is 1-1.05 times of that of the N, N-diethylhydrazine thioamide.
The standing time is 0.5-2 h.
The number of washing times is 2-3.
The temperature of the vacuum drying is 60-80 ℃, and the vacuum degree is-0.1 to-0.01 MPa.
The invention has the beneficial effects that: the modified chitosan is prepared from carboxymethyl chitosan and N, N-diethylhydrazine thioamide according to a splicing principle, belongs to a non-release high-molecular antibacterial anti-mite agent, has antibacterial anti-mite performance far superior to that of carboxymethyl chitosan, can solve the problem of poor antibacterial durability of carboxymethyl chitosan, can obviously optimize the antibacterial anti-mite effect of textiles, improves the use quality of the textiles, prolongs the service life of the textiles and improves the market competitiveness of the textiles when the modified chitosan is applied to textile processing as the antibacterial anti-mite agent.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
(1) Dispersing carboxymethyl chitosan (0.2mol, based on carboxyl molar weight) in SOCl by ultrasonic2(1mol), wherein the frequency of ultrasonic wave is 40kHz, the power is 1000W, the time is 30min, the temperature is increased to 75 ℃, the reaction is kept for 5h, when the conversion rate of carboxyl contained in carboxymethyl chitosan is detected to reach 100 percent in the infrared, the reaction is stopped, and redundant SOCl is removed by distillation2And obtaining an intermediate.
(2) Heating the intermediate to 60 ℃, keeping the temperature and stirring, dropwise adding a DMF solution dissolved with N, N-diethylhydrazine thioamide (0.16mol) and triethylamine (0.168mol), continuing to keep the temperature at 60 ℃ for reacting for 4 hours after dropwise adding is finished, stopping the reaction when TLC detects that the N, N-diethylhydrazine thioamide is completely reacted, dropwise adding deionized water into the reaction solution until no precipitate is separated out, standing for 1 hour, filtering, washing for 3 times, and drying in vacuum at 70 ℃ and the vacuum degree of-0.05 MPa for 5 hours to obtain the non-release type high molecular antibacterial and acaricidal agent.
Example 2
(1) Dispersing carboxymethyl chitosan (0.2mol, based on carboxyl molar weight) in SOCl by ultrasonic2(0.8mol), ultrasonic frequency is 40kHz, power is 500W, time is 30min, heating to 75 ℃, keeping the temperature and reacting for 4h, stopping the reaction when the conversion rate of carboxyl contained in carboxymethyl chitosan reaches 100% in infrared detection, distilling to remove excessive SOCl2And obtaining an intermediate.
(2) Heating the intermediate to 60 ℃, keeping the temperature and stirring, dropwise adding a DMF solution dissolved with N, N-diethylhydrazine thioamide (0.18mol) and triethylamine (0.189mol), continuing to keep the temperature at 60 ℃ for reaction for 3 hours after dropwise adding is finished, stopping the reaction when TLC detects that the N, N-diethylhydrazine thioamide reaction is finished, dropwise adding deionized water into the reaction solution until no precipitate is separated out, standing for 2 hours, filtering, washing for 3 times, and drying in vacuum at 65 ℃ and the vacuum degree of-0.08 MPa for 5 hours to obtain the non-release type high molecular antibacterial and acaricidal agent.
Example 3
(1) Dispersing carboxymethyl chitosan (0.2mol, based on carboxyl molar weight) in SOCl by ultrasonic2(1mol), wherein the frequency of ultrasonic wave is 40kHz, the power is 800W, the time is 30min, the temperature is increased to 75 ℃, the reaction is kept for 5h, when the conversion rate of carboxyl contained in carboxymethyl chitosan is detected to reach 100 percent in the infrared, the reaction is stopped, and redundant SOCl is removed by distillation2And obtaining an intermediate.
(2) Heating the intermediate to 65 ℃, keeping the temperature and stirring, dropwise adding DMF solution dissolved with N, N-diethylhydrazine thioamide (0.16mol) and triethylamine (0.168mol), continuing to keep the temperature at 65 ℃ for reaction for 3h after dropwise adding, stopping the reaction when TLC detects that the N, N-diethylhydrazine thioamide reaction is complete, dropwise adding deionized water into the reaction solution until no precipitate is separated out, standing for 1h, filtering, washing for 3 times, and vacuum-drying at 70 ℃ and the vacuum degree of-0.1 MPa for 4h to obtain the non-release type high molecular antibacterial and acaricidal agent.
Example 4
(1) Dispersing carboxymethyl chitosan (0.2mol, based on carboxyl molar weight) in SOCl by ultrasonic2(1mol), the frequency of the ultrasonic wave is 40kHz, the power is 1000W, the time is 30min, the temperature is raised to 75 ℃, the reaction is carried out for 5h under the condition of heat preservation,stopping the reaction when the infrared detection shows that the conversion rate of the carboxyl contained in the carboxymethyl chitosan reaches 100 percent, and distilling to remove the excessive SOCl2And obtaining an intermediate.
(2) Heating the intermediate to 60 ℃, keeping the temperature and stirring, dropwise adding a DMF solution dissolved with N, N-diethylhydrazine thioamide (0.18mol) and triethylamine (0.189mol), continuing to keep the temperature at 60 ℃ for reaction for 3 hours after dropwise adding is finished, stopping the reaction when TLC detects that the N, N-diethylhydrazine thioamide reaction is finished, dropwise adding deionized water into the reaction solution until no precipitate is separated out, standing for 1 hour, filtering, washing for 3 times, and drying in vacuum at 65 ℃ and the vacuum degree of-0.05 MPa for 5 hours to obtain the non-release type high molecular antibacterial and acaricidal agent.
The antibacterial and anti-mite agent prepared in the embodiment 1 is mixed with polyacrylonitrile and then dissolved in DMF to obtain spinning solution, the dosage of the antibacterial and anti-mite agent is 0.5 percent of the weight of the polyacrylonitrile, the spinning solution is subjected to electrostatic spinning to obtain polyacrylonitrile fibers, and the polyacrylonitrile fibers are woven to prepare the polyacrylonitrile fabric. Meanwhile, a comparative example using the same amount of carboxymethyl chitosan as the antibacterial and anti-mite agent is set.
According to the standard GB/T20944.2-2007 evaluation part 2 of antibacterial properties of textiles: the antibacterial and anti-mite performance is measured by an absorption method and GB/T24253 plus 2009 evaluation of anti-mite performance of textiles, and the textile is washed for 30 times according to a standard FZ/T73023 plus 2006 washing test method of antibacterial textile appendix C antibacterial fabric sample, and the measurement result is shown in Table 1.
TABLE 1 antibacterial and mite-repelling ratio of the antibacterial and mite-repellent agent of the present invention
Figure BDA0003139293060000051
As can be seen from the data in Table 1, the antibacterial and acaricidal agent prepared by the invention has excellent antibacterial and acaricidal properties and good antibacterial and acaricidal durability.
Therefore, the antibacterial and anti-mite agent prepared by the invention has an antibacterial and anti-mite effect and antibacterial and anti-mite durability which are obviously superior to those of carboxymethyl chitosan.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. A non-release type high molecular antibacterial anti-mite agent is characterized in that: prepared by the acyl chlorination reaction and the amidation reaction of carboxymethyl chitosan, thionyl chloride and N, N-diethylhydrazine thioamide.
2. The non-releasing polymeric antibacterial acaricidal agent according to claim 1, wherein: the molar amount of the thionyl chloride is 2-5 times of the molar amount of carboxyl contained in the carboxymethyl chitosan.
3. The non-releasing polymeric antibacterial acaricidal agent according to claim 1, wherein: the molar amount of the N, N-diethylhydrazine thioamide is 0.8-1 time of that of carboxyl contained in the carboxymethyl chitosan.
4. The method for preparing the non-release type polymeric antibacterial and acaricidal agent according to any one of claims 1 to 3, comprising the steps of:
(1) ultrasonic dispersing carboxymethyl chitosan in SOCl2Heating to 70-80 ℃, carrying out heat preservation reaction, stopping the reaction when the conversion rate of carboxyl contained in the carboxymethyl chitosan reaches 100% is detected in the infrared, and distilling to remove redundant SOCl2Obtaining an intermediate;
(2) heating the intermediate to 55-65 ℃, keeping the temperature, stirring, dropwise adding a DMF solution dissolved with N, N-diethylhydrazine thioamide and triethylamine, continuing to keep the temperature at 55-65 ℃ for reaction after dropwise adding, stopping the reaction when TLC detects that the N, N-diethylhydrazine thioamide is completely reacted, dropwise adding deionized water into the reaction solution until no precipitate is separated out, standing, filtering, washing with water, and drying in vacuum to obtain the non-release type high-molecular antibacterial and acarid-preventing agent.
5. The method for preparing the non-release type polymer antibacterial and acaricidal agent according to claim 4, wherein the method comprises the following steps: the frequency of the ultrasonic wave is 20-40kHz, and the power is 100-1000W.
6. The method for preparing the non-release type polymer antibacterial and acaricidal agent according to claim 4, wherein the method comprises the following steps: the molar amount of the triethylamine is 1-1.05 times of that of the N, N-diethylhydrazine thioamide.
7. The method for preparing the non-release type polymer antibacterial and acaricidal agent according to claim 4, wherein the method comprises the following steps: the standing time is 0.5-2 h.
8. The method for preparing the non-release type polymer antibacterial and acaricidal agent according to claim 4, wherein the method comprises the following steps: the number of washing times is 2-3.
9. The method for preparing the non-release type polymer antibacterial and acaricidal agent according to claim 4, wherein the method comprises the following steps: the temperature of the vacuum drying is 60-80 ℃, and the vacuum degree is-0.1 to-0.01 MPa.
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