阅读说明：本技术 一种抗菌抗霉整理剂及其制备方法 (Antibacterial and anti-mildew finishing agent and preparation method thereof ) 是由 王楠 于 2020-06-02 设计创作，主要内容包括：本发明涉及一种真皮抗菌抗霉整理剂及其制备方法。所述真皮抗菌抗霉整理剂由二苯并-18-C-6冠醚交联壳聚糖溶于适量蒸馏水中,加入50份水合肼溶液,振摇混合均匀,10min后加入10份硝酸银溶液,定容,将反应混合液置于一定温度水浴中,待其变色稳定,钝化12h制备而得。所述二苯并-18-C-6冠醚交联壳聚糖由Schiff碱壳聚糖的合成、二苯并-18-C-6冠醚的合成制备而成。真皮抗菌抗霉整理剂具有高效抗菌活性、安全无毒、稳定性高、分散性好,为新型皮革防霉材料提供一种新思路。(The invention relates to a leather antibacterial and anti-mildew finishing agent and a preparation method thereof. The antibacterial and anti-mildew finishing agent for the dermis is prepared by dissolving dibenzo-18-C-6 crown ether crosslinked chitosan in a proper amount of distilled water, adding 50 parts of hydrazine hydrate solution, shaking and mixing uniformly, adding 10 parts of silver nitrate solution after 10min, fixing the volume, placing reaction mixed solution in water bath at a certain temperature, and passivating for 12h after the color of the reaction mixed solution is stable. The dibenzo-18-C-6 crown ether crosslinked chitosan is prepared by synthesizing Schiff base chitosan and dibenzo-18-C-6 crown ether. The leather antibacterial and antifungal finishing agent has high-efficiency antibacterial activity, safety, no toxicity, high stability and good dispersibility, and provides a new idea for novel leather mildewproof materials.)

1. The antibacterial and antifungal finishing agent is characterized by being prepared from the following components in percentage by weight: 2-4 parts of chitosan, 10 parts of acetic acid solution, 5 parts of methanol, 8-10 parts of benzaldehyde, 5 parts of diethyl ether, 15-17 parts of catechol, 48 parts of n-butanol, 5-8 parts of sodium hydroxide, 10 parts of dichloroethyl ether, 1-2 parts of concentrated hydrochloric acid, 5-10 parts of acetone, 60 parts of chloroform, 30 parts of pyridine, 2-5 parts of bromo-crown ether, 10-15 parts of absolute ethyl alcohol, 10 parts of hydrochloric acid, 50 parts of hydrazine hydrate and 10 parts of silver nitrate.

2. The preparation method of the antibacterial and antifungal finishing agent is characterized by comprising the following steps:

step one, synthesis of Schiff alkali chitosan:

dissolving chitosan in acetic acid solution under stirring at room temperature, adding 50ml of methanol after 1.5h, continuously stirring for 0.5h, dissolving benzaldehyde in methanol, dropwise adding into the chitosan solution under stirring, reacting at room temperature for 24h, sequentially washing with methanol and diethyl ether after the reaction is finished, vacuum drying at 60 ℃, crushing, and sieving with a 60-mesh sieve to obtain Schiff base chitosan;

step two, synthesis of dibenzo-18-C-6 crown ether:

adding catechol and n-butanol into a three-neck flask, adding sodium hydroxide under stirring and introducing nitrogen, stirring and refluxing for 0.5h at 115 ℃, dropwise adding dichloroethyl ether and n-butanol by using a constant-pressure dropping funnel, finishing dropping for 0.5h, reducing the temperature to 90 ℃ after refluxing for 1h, adding sodium hydroxide, continuously refluxing for 0.5h, dropwise adding dichloroethyl ether and n-butanol again, finishing dropping within 0.5h, continuously reacting for 16h, and dropwise adding concentrated hydrochloric acid to acidify;

pouring the solvent in the three-neck flask into a distillation flask, dropwise adding water into the distillation flask at a speed that the volume of the mixture in the flask is kept unchanged, continuously distilling until the temperature of steam reaches 96 ℃, continuously distilling for 10min, cooling to 30-40 ℃, diluting the remaining slurry with acetone, stirring the coagulated precipitate, stirring the precipitate and water, performing suction filtration, stirring with acetone, performing suction filtration, alternately washing with distilled water and acetone for 2-3 times, performing suction filtration, performing vacuum drying at 60 ℃ to obtain an off-white product, and then recrystallizing in benzene to obtain a white fibrous crystal, namely dibenzo-18-C-6 crown ether;

step three, synthesizing dibenzo-18-C-6 crown ether cross-linked chitosan:

dispersing Schiff chitosan in chloroform and pyridine, magnetically stirring and soaking at 60 ℃, slowly dropwise adding a solution obtained by dissolving bromo-crown ether in chloroform into a chloroform and pyridine solution in which the Schiff chitosan is dispersed, reacting at 60 ℃ for 24 hours, performing vacuum filtration, and washing and filtering with distilled water and absolute ethyl alcohol in sequence to obtain a filter cake; hydrolyzing the filter cake with hydrochloric acid at room temperature for 24h, adding anhydrous absolute ethyl alcohol, performing suction filtration, performing vacuum drying at 60 ℃ to obtain a light yellow product, grinding, and sieving with a 60-mesh sieve for later use to obtain dibenzo-18-C-6 crown ether crosslinked chitosan;

step four, preparing the antibacterial and anti-mildew finishing agent for the dermis:

dissolving a certain amount of dibenzo-18-C-6 crown ether crosslinked chitosan in distilled water, adding a hydrazine hydrate solution, shaking and mixing uniformly, adding a silver nitrate solution after 10min, fixing the volume to obtain a reaction mixed solution, placing the reaction mixed solution in a water bath at 60 ℃, and obtaining the antibacterial and antifungal finishing agent for the dermis after the color of the reaction mixed solution is stable.

3. The method for preparing the antibacterial and antifungal finishing agent as claimed in claim 2, characterized in that: the concentration of the acetic acid solution is 1 mol/L.

4. The method for preparing the antibacterial and antifungal finishing agent according to claim 2, characterized in that: the concentration of the hydrochloric acid is 0.25 mol/L.

5. The method for preparing the antibacterial and antifungal finishing agent according to claim 2, characterized in that: the molar ratio of hydrazine hydrate to silver nitrate is 5:1.

6. The method for preparing the antibacterial and antifungal finishing agent according to claim 2, characterized in that: the grain diameter of the particles of the dermal antibacterial and antifungal finishing agent is 30-40 nm.

7. The method for preparing the antibacterial and antifungal finishing agent according to claim 2, characterized in that: the concentration of the silver nitrate is 0.1mol/L, and the passivation time is 12 h.

Technical Field

The invention relates to a leather antibacterial and anti-mildew finishing agent and a preparation method thereof.

Technical Field

Leather products are necessary for human life, and the usage amount of the leather products is increased along with the improvement of living standard of people. However, the raw materials used in tanning are rich in nutrients such as protein and fat, and are very susceptible to the invasion of microorganisms during the preservation process. The processing change is that although the resistance to microorganism is increased, the mildew still occurs, especially ester adding agent produced by natural oil is introduced in the leather production process, and the agent is also a hotbed for microorganism proliferation. In addition, the porosity and polar structure of the leather structure make it easy to absorb moisture, and the leather is acidic.

The above causes constitute a basic condition for mold. The mildewed leather products can generate white, blue, yellow and black bacterial colonies or color spots, and the bacterial colonies on the surface simultaneously face to the inside of the leather, so that the wear resistance, the strength and the elasticity of the leather are also influenced.

Therefore, mold is a serious detriment to the appearance and the intrinsic quality of leather and its articles, and is very important in the leather industry.

Besides mildew resistance, leather products should also be endowed with an antibacterial function like fiber products so as to meet the living needs of people.

Disclosure of Invention

Embodiments of the present invention will be described below with reference to examples. An antibacterial and antimildew treatment agent for dermis, which is composed of the following raw materials: 2-4 parts of chitosan, 10 parts of acetic acid solution, 5 parts of methanol, 8-10 parts of benzaldehyde, 5 parts of diethyl ether, 15-17 parts of catechol, 48 parts of n-butanol, 5-8 parts of sodium hydroxide, 10 parts of dichloroethyl ether, 1-2 parts of concentrated hydrochloric acid, 5-10 parts of acetone, 60 parts of chloroform, 30 parts of pyridine, 2-5 parts of bromo-crown ether, 10-15 parts of absolute ethyl alcohol, 10 parts of hydrochloric acid, 50 parts of hydrazine hydrate and 10 parts of silver nitrate.

The antibacterial and anti-mildew treatment agent is prepared from the following components in parts by mass:

step one, synthesis of Schiff alkali chitosan

Dissolving chitosan in acetic acid solution under stirring at room temperature, adding 50ml methanol after 1.5 hr, and stirring for 0.5 hr to obtain transparent colloid. Dissolving 15.5g benzaldehyde in 100ml methanol, dropwise adding into the chitosan solution under stirring, reacting at room temperature for 24h, sequentially washing with methanol and diethyl ether after reaction, filtering, and vacuum drying at 60 deg.C. Grinding, and sieving with 60 mesh sieve.

Step two, synthesis of dibenzo-18-C-6 crown ether

In a 500ml three-necked flask equipped with a thermometer, a reflux condenser, a gas-guide tube and an electromagnetic stirrer, catechol and n-butanol were added, sodium hydroxide was added under stirring and nitrogen gas introduction, and stirred and refluxed at about 115 ℃ for 0.5h to completely dissolve the sodium hydroxide. And dropwise adding a solution prepared from dichloroethyl ether and n-butanol by using a constant-pressure dropping funnel, and finishing dropping within about 0.5 h. After 1h of reflux the temperature was reduced to 90 ℃. And adding sodium hydroxide, continuously refluxing for 0.5h, dropwise adding a solution prepared from g of dichloroethyl ether and n-butanol again, dropwise adding the solution within 0.5h, continuously reacting for 16h, and dropwise adding concentrated hydrochloric acid to acidify. After about 100ml of solvent was removed by flash distillation, water was added dropwise to the flask at such a rate that the volume of the mixture in the flask remained constant. The distillation was continued until the temperature of the steam reached 96 ℃ and continued for 10 min. Cooling to 30-40 ℃, diluting the remaining slurry with acetone, stirring the coagulated precipitate, and performing suction filtration. And stirring the crude product with 100ml of water, performing suction filtration, stirring with acetone, performing suction filtration, and performing suction filtration by alternately washing with distilled water and acetone for 2-3 times. Vacuum drying at 60 deg.C to obtain off-white product. Recrystallizing in benzene to obtain white fibrous crystal.

Step three, synthesis of dibenzo-18-C-6 crown ether cross-linked chitosan

Dispersing Schiff chitosan protecting amino in chloroform and pyridine, magnetically stirring and soaking at 60 ℃, slowly dripping solution obtained by dissolving bromo-crown ether in chloroform into the solution, reacting at 60 ℃ for 24 hours, carrying out vacuum filtration, sequentially washing and carrying out vacuum filtration by using distilled water and absolute ethyl alcohol, hydrolyzing a filter cake by using 0.25mol/l hydrochloric acid at room temperature for 24 hours, then adding a proper amount of absolute ethyl alcohol, precipitating a product, carrying out vacuum filtration, drying at 60 ℃ in vacuum to obtain a light yellow product, grinding, and sieving by using a 60-mesh sieve for later use.

Step four, preparation of antibacterial and anti-mildew finishing agent for leather

Dissolving a certain amount of dibenzo-18-C-6 crown ether crosslinked Chitosan (CTSG) in a proper amount of distilled water, adding a certain volume of hydrazine hydrate solution, shaking and mixing uniformly, adding a certain amount of silver nitrate solution after 10min, and fixing the volume. And placing the reaction mixed solution in a water bath at a certain temperature, and passivating for 12 hours after the color of the reaction mixed solution is stable.

In some of these embodiments, the chitosan has a degree of deacetylation greater than 80%.

In some of the embodiments, the concentration of the acetic acid solution is 1 mol/L.

In some of these embodiments, the hydrochloric acid concentration is 0.25 mol/L.

In some of these embodiments, the hydrazine hydrate and silver nitrate are present in a 5:1 molar ratio.

In some embodiments, the particle size of the particles of the dermal antibacterial and antifungal finishing agent is 30-40 nm.

In some of these embodiments, the silver nitrate concentration is 0.1 mol/L.

The specific technical scheme is as follows:

the application of the antibacterial finishing agent for the genuine leather in the genuine leather material.

The principle of the invention is as follows:

the chitosan is a deacetylation product of chitin, has rich resources, is a natural high molecular compound with wide application value, and has two active groups of amino and hydroxyl distributed on a macromolecular chain. By utilizing the groups, chitosan is chemically modified through reactions such as acylation, esterification, etherification, grafting, crosslinking and the like, and different groups are introduced into the molecular structure of the chitosan, so that chitosan derivatives with different physicochemical characteristics and different purposes can be prepared, and the application range of the chitosan is expanded. Crown ethers have a unique molecular structure and can form host-guest complexes with many ionic and neutral molecules. The low molecular crown ether is made into high molecular crown ether through graft cross-linking reaction, which not only overcomes the defects of high price and certain toxicity of the low molecular crown ether, but also has the matching selectivity of the crown ether.

The experiment synthesizes dibenzo-18-C-6 crown ether, and the dibenzo-18-C-6 crown ether cross-linked chitosan with the double structure and the specificity of chitosan and crown ether is prepared. In order to ensure that the grafting reaction of the chitosan is only carried out on hydroxyl, in the experiment, the Schiff base chitosan is firstly prepared by the reaction of benzaldehyde and the amino group of the chitosan, the protection of the amino group at the C2 position is realized, and finally, the protecting group is removed under the acidic condition to obtain the dibenzo-18-C-6 crown ether cross-linked chitosan which is used as the protecting agent for preparing the leather antibacterial and anti-mildew finishing agent.

Therefore, the invention has the following beneficial effects:

1) the synthesized dibenzo-18-C-6 crown ether cross-linked chitosan structure contains a large amount of amino and hydroxyl, so that the chitosan has good water solubility, accords with experimental assumptions, and is used as a protective agent for preparing a dermal antibacterial and antifungal finishing agent.

2) The dibenzo-18-C-6 crown ether crosslinked chitosan serving as a new adsorbent and protective agent can effectively prevent the growth and agglomeration of silver particle grains and enable a reaction system to exist stably.

3) The usage amount of the leather antibacterial and anti-mildew finishing agent reaches 5 percent or 8 percent of the weight of the leather, and the leather antibacterial and anti-mildew finishing agent can achieve the level 1 mildew-proof effect and is within the qualified range.

Detailed Description

In order that the nature of the invention may be better understood, the invention will now be further illustrated by reference to the following specific examples.

The raw materials used in the embodiment of the invention are as follows: