CN101225601B - Multifunctional reactive cotton ultraviolet absorber, its synthesis method and application - Google Patents

Abstract

The present invention relates to a multifunctional reactive cotton ultraviolet absorber, its synthesis method and application. The general structural formula I of the absorber is as follows: Its synthesis method includes: (1) adding functional finishing agents such as triclosan antibacterial compounds, hindered amine light-stabilizing compounds or amino silicone oil softening compounds to cyanuric chloride, using water as a solvent, and reacting at 0-5°C 1~2h, introduce functional finishing agent groups; (2) add linking group substances, use water as solvent, react at 40~50°C for 3~4h, connect two triazine rings; (3) or combine with other reactive The substance uses water as a solvent, reacts at 80-90°C for 3-4 hours, and introduces other active groups on the triazine ring. The ultraviolet absorbent of the present invention has good reactivity, water solubility, ultraviolet absorption ability and other finishing functions (such as antibacterial property, light stability, etc.) on cotton fabrics.

Description

Multifunctional reactive cotton ultraviolet absorber, its synthesis method and application

technical field

The invention belongs to the field of ultraviolet absorbers, in particular to a multifunctional reactive cotton ultraviolet absorber, its synthesis method and application.

Background technique

Ultraviolet rays are electromagnetic waves with a wavelength of 180-400nm. An appropriate amount of ultraviolet radiation has a bactericidal effect and can promote the synthesis of vitamin D, which is beneficial to human health, but excessive ultraviolet radiation is very harmful to the human body. Modern scientific research shows that the harmful effects of ultraviolet rays on the human body far outweigh its beneficial effects. Excessive ultraviolet radiation can induce skin diseases, even skin cancer, and also cause cataracts and reduce the immune function of the human body. Therefore, the protection of ultraviolet rays has attracted more and more attention.

Ultraviolet absorbers are substances that can strongly and selectively absorb high-energy ultraviolet light and convert energy, releasing or consuming energy in the form of heat or harmless low-radiation. They are widely used in polymer materials, textile processing and other fields . Common UV absorbers mainly include salicylates, benzophenones, benzotriazoles, hindered amines, substituted acrylonitriles, triazines, etc., of which benzophenones and benzotriazoles Azole UV absorbers are widely used.

Most of the traditional UV absorbers are fixed into the textile fibers by means of physical adsorption, adhesion, crosslinking, doping, etc. The products have the following disadvantages during use: (1) The UV absorbers are firmly combined with the textile fibers It is easy to lose, and with the prolongation of use time or the increase of washing times, the anti-ultraviolet function gradually decreases and finally disappears; (2) the use of cross-linking or bonding methods will not only affect the performance of textiles, but also Sometimes it also reduces the UV resistance; (3) The method of doping is mainly suitable for the finishing of synthetic fibers. Since the doping needs to be carried out before spinning, the compatibility between the UV absorber and the textile fiber is very important . In order to solve the above-mentioned problems, in recent years, UV absorbers for cotton are being developed in the direction of reactivity, durability, and multifunctionality.

At present, there have been a lot of researches on reactive and durable cotton UV rays both at home and abroad. For example, Clariant has synthesized a series of new 1,3,5-s-triazine compounds, and found that these compounds can react with hydroxyl or amino groups on the fiber to make the fiber obtain durable UV protection and antifouling properties, and the treatment The method of fiber dyeing is similar to the method of dyeing fiber with reactive dyes, and it can be dyed simultaneously with reactive dyes; the plateau of Donghua University uses aminobenzenesulfonic acid, cyanuric chloride and 2,4-dihydroxybenzophenone as raw materials to synthesize A cotton UV absorber with its own reactive groups was developed; Wang Fang from Shenyang Institute of Chemical Technology took the benzotriazole UV absorber as the matrix with strong absorption capacity, safe and effective, and introduced into the molecule a UV absorber capable of interacting with cotton fibers. Active groups such as cyanuric chloride or vinyl sulfone that have reacted have synthesized a reactive UV absorber for cotton; Jin Fang and others have synthesized a UV absorber with a halogenated heterocyclic active group, and its The water-soluble group is a sulfonic acid group, the linking group is -NH-, and the ultraviolet absorbing group is an aromatic ring structure; Cui Guoshi and others use cinnamic acid derivatives and γ-chloropropyltrimethoxysilane as raw materials, through A series of siloxycinnamate compounds such as γ-p-methoxycinnamoyloxypropyltrimethoxysilane and the like were synthesized through esterification. Although some progress has been made in the research of reactive ultraviolet absorbers in China, a series of compounds with both the ability to react with cotton fibers and a certain ultraviolet absorption effect have been developed, but the reported compounds do not have other finishing functions. Can not satisfy people's growing multifunctional demand.

In summary, research and development of reactive cotton UV absorbers with good reactivity, water solubility and UV absorption effect, as well as other finishing functions, has become a very important topic.

Contents of the invention

The purpose of the present invention is to provide a multifunctional reactive cotton UV absorber, its synthesis method and application, by introducing other groups with functional finishing effects in the molecules of triazine UV absorbers, so that the compound not only It has good reactivity and excellent ultraviolet absorption effect, and also has other finishing functions.

Multifunctional reactive cotton UV absorber of the present invention, its general structural formula I is as follows:

Wherein, in the general formula I, X represents a reactive group: halogen groups such as F-, Cl-,

等含有氨基的脂肪族或芳香族乙基砜化合物基团。

Such as aliphatic or aromatic ethyl sulfone compound groups containing amino groups.

等芳香族二元胺化合物基团。In general formula I, R is -NHCH ₂ CH ₂ NH-, -NHCH ₂ CH ₂ CH ₂ NH-, -NHCH ₂ CH ₂ CH ₂ CH ₂ NH-, -NHCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH-, etc. Aliphatic diamine compound group or

and other aromatic diamine compound groups.

等含有氨基或羟基的受阻胺类光稳定基团，

等三氯生类抗菌基团，

等氨基硅油类柔软整理基团。In the general formula I, R' represents other functional finishing groups:

Such as hindered amine photostable groups containing amino or hydroxyl groups,

and other triclosan antibacterial groups,

Amino silicone oil softening finishing group.

The synthesis method of the multifunctional reactive cotton ultraviolet absorber of the present invention is to take functional finishing agent, cyanuric chloride and linking group substance etc. as raw materials, and the substitution reaction takes place to synthesize, and its specific synthesis steps are as follows:

(1) Add a functional finishing agent to cyanuric chloride, use water as a solvent, react at 0-5°C for 1-2 hours, and introduce functional finishing agent groups;

(2) Add linking group substances, use water as solvent, react at 40-50°C for 3-4 hours, and connect two triazine rings;

(3) or react with other reactive substances, using water as a solvent, react at 80-90° C. for 3-4 hours, and introduce other active groups on the triazine ring.

The molar ratio of reactant cyanuric chloride, functional finishing agent, linking group substance and other reactive substances is 1:1:0.5:1.

等三氯生类抗菌化合物或

含有氨基或羟基的受阻胺类光稳定剂；

等氨基硅油类化合物。The functional finishing agent is

Antibacterial compounds such as triclosan or

Hindered amine light stabilizers containing amino or hydroxyl groups;

Amino silicone oil compounds.

等芳香族二元胺化合物基团；The _linking group substance is H ₂ NCH ₂ CH ₂ NH ₂ , H ₂ NCH 2 CH ₂ CH ₂ NH ₂ , H ₂ NCH ₂ CH 2 CH ₂ CH ₂ NH ₂ , H ₂ NCH ₂ CH ₂ CH _{2 CH 2} Aliphatic dibasic amine compound groups such as CH ₂ NH ₂ or

and other aromatic diamine compound groups;

等含有氨基的脂肪族或芳香族乙基砜化合物基团。The other reactive substances are

Such as aliphatic or aromatic ethyl sulfone compound groups containing amino groups.

The application of multifunctional reactive cotton ultraviolet absorber of the present invention, its step:

(1) Obtain the optimized finishing process by orthogonal experiment;

(2) On the basis of optimizing the finishing process, test the anti-ultraviolet performance and washability;

(3) On the basis of optimizing the finishing process, test other finishing functions (such as antibacterial effect, light fastness, etc.).

Beneficial effects of the present invention:

The ultraviolet absorber synthesized by the invention has good reactivity, water solubility, ultraviolet absorption ability and other finishing functions (such as antibacterial property, light stability, etc.) on cotton fabrics.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

The water used in the following examples is tap water, and the chemicals are chemically pure. The specifications of pure cotton poplin are yarn count JC40×40, warp density 100×weft density 90, and width 67″.

Example 1

Weigh 30.6g of 23.5% aqueous solution of 2,4-dichloro-5-(2,4-dichlorophenyl)oxybenzenesulfonic acid and add it to a four-neck flask, adjust the pH to 6 with 30% aqueous NaOH ~8, then 47 g of water was added to the solution. Cool down to 0-5°C in an ice bath. Slowly add 5g of cyanuric chloride, and keep the reaction at 0-5°C for 90min. Then use 30% NaOH aqueous solution to adjust the pH value to 6.0-6.2, raise the temperature to 50°C, add 2.2g of 2,4-diaminobenzenesulfonic acid, and keep the temperature for 3 hours. During the reaction, use 10% Na ₂ CO ₃ solution to adjust the pH value to keep it in the range of 5-6. Finally, a yellow-brown transparent solution is obtained, and compound a is obtained after separation and purification. Compound a is a multifunctional finishing agent for cotton with anti-ultraviolet properties and antibacterial properties. The resulting solution can be directly used for cotton fabric finishing without finishing.

Example 2

This example is a research on the anti-ultraviolet and antibacterial performance of compound a, including determining the optimized finishing process, the test results of anti-ultraviolet performance and the test results of antibacterial performance.

For the optimized finishing process of compound a on pure cotton poplin, five factors and six levels of orthogonal experiments were used to finally obtain the optimized finishing process as follows: bath ratio 1:15, put finishing agent and cotton cloth at room temperature, and the amount of finishing agent was fabric weight 1 to 10% of the solution, heat up to 65°C, add 40g/L sodium sulfate, keep warm for 40min, then add 30g/L soda ash, heat up to 90°C, keep warm for 25min, wash once with hot water, rinse with cold water, and dry.

Under the optimized finishing process conditions, the light brown viscous liquid obtained in Example 1 is used to directly carry out anti-ultraviolet finishing to the pure cotton poplin, and the pure cotton poplin after finishing is soaped 50 times, and the fabric is treated respectively before and after finishing. Tested with the UPF value after soaping 50 times, the test results are shown in Table 1. The UPF value of pure cotton poplin after finishing increases significantly with the increase of the amount of ultraviolet absorber. When the amount of finishing agent reaches 3% of the fabric weight, the UPF of the fabric can reach more than 50. After finishing, the retention rate of UPF value of pure cotton high-density poplin is still above 90% after 50 times of washing.

Table 1 UV resistance and washability test results

Under the optimized finishing process conditions, the yellowish-brown transparent liquid obtained in Example 1 is used to directly carry out antibacterial finishing on pure cotton poplin, and Escherichia coli and Staphylococcus aureus are used as test bacteria to carry out antibacterial tests respectively to investigate the antibacterial effects of different bacterial species. Performance, the results are shown in Table 2. As the amount of finishing agent increases, the antibacterial rate of fabrics against Escherichia coli and Staphylococcus aureus increases continuously. The reason is that as the amount of finishing agent increases, the covalent bonds formed between finishing agent and fiber increase, and the antibacterial active ingredients on the fiber surface increase. In conclusion, the finishing agent has good antibacterial effect on both Escherichia coli and Staphylococcus aureus.

Table 2 antibacterial performance test results

Example 3

Add 4.3g of sodium bicarbonate into 80g of ice water, after completely dissolved, slowly add 7.8g of 2,2,6,6-tetramethylpiperidinol, and stir until the solution becomes clear. Then add 9.2 g of cyanuric chloride several times in small batches, and keep warm at 0-5°C for 90 minutes. After the reaction is completed, use a certain concentration of sodium hydroxide solution to adjust the pH to 6-6.2, then raise the temperature to 40°C, add 4.7g of 2,4-diaminobenzenesulfonic acid dropwise, and keep the reaction for 3h. During the reaction process, adjust the pH to 5-6 with a certain concentration of sodium hydroxide solution every half hour. Finally, 16 g of p-(β-sulfate ethylsulfone) aniline was slowly added, and stirred at 85-90° C. for 3 hours. After the reaction, a light brown solution is obtained, which is separated by filtration and dried to obtain compound b, which is a multifunctional finishing agent with both anti-ultraviolet and light-stabilizing properties. The resulting solution can be directly used for cotton fabric finishing without finishing.

Example 4

This example is a research on the anti-ultraviolet and light stability properties of compound b, including determining the optimized finishing process, anti-ultraviolet performance test and light fastness test.

For the optimized finishing process of compound b on pure cotton poplin, five factors and six levels of orthogonal experiments were used to finally obtain the optimized finishing process as follows: liquor ratio 1:15, UV absorber and cotton cloth were placed at room temperature, and the amount of finishing agent was 1 to 10% of the weight, heat up to 50°C, add 20g/L Yuanming powder, keep warm for 35min, then add 30g/L soda ash, heat up to 80°C, keep warm for 25min, wash once with hot water, wash with cold water, and dry.

Under optimized finishing process conditions, the white milky liquid obtained in Example 3 is used to directly carry out anti-ultraviolet finishing to pure cotton poplin, and 50 times of soaping is carried out to pure cotton poplin after finishing, before fabric finishing, after finishing and The UPF value after soaping 50 times is tested, and the test results are shown in Table 3. The UPF value of pure cotton poplin after finishing increases significantly with the increase of the amount of ultraviolet absorber. When the amount of finishing agent reaches 1% of the fabric weight, the fabric UPF can reach more than 50. When the amount reaches 9%, the fabric UPF reaches 80 or more. It can be seen that the finished cotton poplin has excellent UV protection performance. The retention rate of the UPF value of pure cotton high-density poplin after 50 times of washing is still above 90%, which indicates that the prepared ultraviolet absorber has excellent washing resistance.

Table 3 UV resistance and washability test results

Under the condition of optimized finishing process, the finishing agents of 5%, 10%, 15% and 20% of the fabric weight were respectively used for anti-ultraviolet finishing of pure cotton poplin, and the finished fabric samples and the original fabric were dyed, and the fabric samples were tested. Light fastness to investigate the effect of the use of ultraviolet absorbers on the light fastness of fabrics. The test results are shown in Table 4. It can be seen from Table 4 that the light fastness of the original fabric is low, which is because the light has an impact on the dye during the sun exposure process. Since the hindered amine light-stabilizing group reacted on the fabric weakens the influence of ultraviolet rays on the dye, the light fastness of the finished fabric sample has been improved to a certain extent. As the amount of finishing agent increases, the light fastness improvement effect increases significantly; and when the amount of finishing agent reaches 10% of the weight of the fabric, its light fastness can be improved by about 1 level.

Table 4 Light fastness test results

Claims (2)

1. a multifunctional reactive cotton ultraviolet absorber is characterized in that the structural formula of the absorber is

2. the synthetic method of multifunctional reactive cotton ultraviolet absorber as claimed in claim 1, its concrete synthetic steps are as follows: (1) Add functional finishing agent to cyanuric chloride

Use water as a solvent, react at 0-5°C for 1-2 hours, and introduce functional finishing groups; (2) Add linking group substances Use water as a solvent, react at 40-50°C for 3-4 hours, and connect two triazine rings; (3) or with other reactive substances

Use water as a solvent, react at 80-90°C for 3-4 hours, and introduce other active groups on the triazine ring.