阅读说明：本技术 一种抗紫外整理剂及其制备方法 (Anti-ultraviolet finishing agent and preparation method thereof ) 是由 于文慧 田家龙 陈雨洁 祁珍明 王春霞 马志鹏 贾高鹏 高大伟 陆振乾 王矿 吴 于 2021-10-29 设计创作，主要内容包括：本发明涉及一种抗紫外整理剂及其制备方法,将三聚氯氰作为活性反应基团,依次与2,4-二羟基二苯甲酮,对-β-羟基乙砜苯胺硫酸酯反应,合成了一种有暂水溶性的抗紫外线整理剂,合成过程简单,制得的抗紫外线整理剂上同时具备了两个反应性基团氯原子和-SO-(2)CH-(2)CH-(2)OSO-(3)Na,具有优异的抗紫外线效果,采用该抗紫外线整理剂整理的织物,对UVA和UVB的屏蔽率达95％以上,UPF值为50以上,具有优异的抗紫外线效果,并且性能稳定,不易被水洗去除,也不影响整理后织物的白度及正常服用性能。(The invention relates to an anti-ultraviolet finishing agent and a preparation method thereof, cyanuric chloride is taken as an active reaction group to react with 2, 4-dihydroxy benzophenone and p-beta-hydroxy ethyl sulfone aniline sulfate in sequence to synthesize the anti-ultraviolet finishing agent with temporary water solubility, the synthesis process is simple, and the prepared anti-ultraviolet finishing agent simultaneously has two reactive groups of chlorine atoms and-SO 2 CH 2 CH 2 OSO 3 Na has excellent anti-ultraviolet effect, and the fabric finished by the anti-ultraviolet finishing agent has the shielding rate of more than 95 percent to UVA and UVB, the UPF value of more than 50, excellent anti-ultraviolet effect, stable performance, difficult removal by washing, and no influence on the whiteness and normal wearability of the finished fabric.)

1. An uvioresistant finishing agent is characterized by having the following structural formula:

2. a process for preparing a uv-resistant finish according to claim 1, characterized in that it comprises the following steps:

(1) dissolving cyanuric chloride into an organic solvent to obtain a cyanuric chloride solution, and stirring at 0 ℃ for later use;

(2) adding 2, 4-dihydroxy benzophenone into an organic solvent, completely dissolving to obtain a 2, 4-dihydroxy benzophenone solution, mixing and uniformly stirring the 2, 4-dihydroxy benzophenone solution and a sodium hydroxide aqueous solution, slowly dropwise adding the obtained mixed solution into the cyanuric chloride solution obtained in the step (1), controlling the pH value of a reaction solution to be 7-8 and the temperature to be 0-5 ℃ after dropwise adding, reacting for 3-6 hours under the condition to obtain an intermediate product, heating to 40 ℃ while stirring, and preserving heat for later use;

(3) adding p-beta-hydroxy ethyl sulfone aniline sulfate into water, uniformly mixing to obtain a p-beta-hydroxy ethyl sulfone aniline sulfate suspension, dropwise adding a sodium carbonate solution into the p-beta-hydroxy ethyl sulfone aniline sulfate suspension within 30min while stirring at the temperature of 2.5 ℃ to obtain an off-white suspension, slowly dropwise adding the off-white suspension into the intermediate product obtained in the step (2), controlling the pH of the system to be 5-6, stirring at the temperature of 40 ℃ for reaction for 2-5h, and cooling to room temperature to obtain a reaction product;

(4) salting out the reaction product with saturated salt solution, then carrying out suction filtration to obtain a solid product, sequentially adopting water, ethanol and acetone for centrifugal washing, finally carrying out vacuum drying and grinding to obtain powder, namely the anti-ultraviolet finishing agent.

3. The process for preparing the anti-uv finish of claim 2, wherein in steps (1) and (2), the organic solvent is acetone.

4. The method for preparing the uvioresistant finish of claim 2, wherein in step (2), the molar ratio of the 2, 4-dihydroxybenzophenone to the cyanuric chloride is (1-1.2): 1.

5. The method for preparing the anti-ultraviolet finishing agent as claimed in claim 2, wherein in the step (3), the molar ratio of the p-beta-hydroxyethanesulfone aniline sulfate to the cyanuric chloride is (1-1.2): 1.

6. The process for preparing an anti-UV finishing agent according to any one of claims 2 to 5, wherein in step (4), the drying temperature is 40 to 50 ℃ and the drying time is 20 to 30 hours.

Technical Field

The invention relates to an anti-ultraviolet finishing agent and a preparation method thereof, belonging to the technical field of textile industry.

Background

Ultraviolet rays are invisible light having a frequency higher than that of blue-violet light emitted from the sun, and irradiation of ultraviolet rays is advantageous and disadvantageous to the human body. Proper ultraviolet radiation has many effects of sterilization, disinfection, rickets prevention and the like; however, excessive ultraviolet radiation can cause great health damage to human bodies, and particularly, the skin in the ultraviolet radiation area can be burnt, painful, tanned and reddened after being exposed to the ultraviolet radiation for a long time. At the same time, this condition can cause skin inactivation, and the skin resistance can be reduced, which can cause various skin diseases, and serious even induce skin cancer. With the development of economy, people pay more and more attention to health and have higher requirements on the ultraviolet resistance of clothes. The ultraviolet-resistant finishing principle is that fabrics or fibers are treated with an ultraviolet-resistant finishing agent to be adsorbed; when light irradiates on the fiber or fabric, most of the light is absorbed by the ultraviolet-resistant finishing agent and energy is converted into low energy through electron migration to be released or directly reflected, so that the aim of ultraviolet resistance is fulfilled. How to synthesize the high-efficiency and durable ultraviolet-resistant finishing agent becomes a hotspot of current research.

At present, benzophenone ultraviolet-resistant finishing agents are mostly applied to textiles, and are the earliest ultraviolet-resistant finishing agents, and are applied to sun cream in the last 70 years. The benzophenone ultraviolet resistant finishing agent has the characteristics of simple synthesis process, low price, almost no visible light absorption and the like, so the benzophenone ultraviolet resistant finishing agent is widely applied to textiles, but is easy to cause yellowing due to poor light stability, has affinity to skin, is easy to absorb by the skin, has certain toxicity, and is limited in application; benzotriazole type ultraviolet-resistant finishing agent is also a commonly used ultraviolet-resistant finishing agent, has a very wide ultraviolet absorption range, can almost absorb ultraviolet rays with the wavelength of 280-400nm and has a good ultraviolet-resistant effect, but has complex synthesis and extremely complex process, and has low reactivity and no reactive group, so that the ultraviolet-resistant performance can be realized only by adsorbing the benzotriazole type ultraviolet-resistant finishing agent on the surface of fiber.

With the increasing requirements of people on ultraviolet-resistant finishing agents, the research on the ultraviolet-resistant finishing agents gradually develops towards the trends of multifunctionality, reactivity, new structures and new processes. The ultraviolet-resistant finishing agent with remarkable ultraviolet-resistant effect is urgently needed to be provided, so that the ultraviolet-resistant finishing agent has higher reactivity and stable performance, and the whiteness of the fabric is not influenced.

Disclosure of Invention

An object of the present invention is to solve the above-mentioned deficiencies of the prior art and to provide an anti-uv finishing agent which has excellent anti-uv effect and high reactivity, and is stable in performance without affecting whiteness and other properties of the finished fabric.

The invention also aims to provide a preparation method of the ultraviolet-resistant finishing agent.

Technical scheme

An uvioresistant finishing agent has the following structural formula:

the preparation method of the anti-ultraviolet finishing agent comprises the following steps:

(1) dissolving cyanuric chloride into an organic solvent to obtain a cyanuric chloride solution, and stirring at 0 ℃ for later use;

(2) adding 2, 4-dihydroxy benzophenone into an organic solvent, completely dissolving to obtain a 2, 4-dihydroxy benzophenone solution, mixing and uniformly stirring the 2, 4-dihydroxy benzophenone solution and a sodium hydroxide aqueous solution, slowly dropwise adding the obtained mixed solution into the cyanuric chloride solution obtained in the step (1), controlling the pH value of a reaction solution to be 7-8 and the temperature to be 0-5 ℃ after dropwise adding, reacting for 3-6 hours under the condition to obtain an intermediate product, heating to 40 ℃ while stirring, and preserving heat for later use;

(3) adding p-beta-hydroxy ethyl sulfone aniline sulfate into water, uniformly mixing to obtain a p-beta-hydroxy ethyl sulfone aniline sulfate suspension, dropwise adding a sodium carbonate solution into the p-beta-hydroxy ethyl sulfone aniline sulfate suspension within 30min while stirring at the temperature of 2.5 ℃ to obtain an off-white suspension, slowly dropwise adding the off-white suspension into the intermediate product obtained in the step (2), controlling the pH of the system to be 5-6, stirring at the temperature of 40 ℃ for reaction for 2-5h, and cooling to room temperature to obtain a reaction product;

(4) salting out the reaction product with saturated salt solution, then carrying out suction filtration to obtain a solid product, sequentially adopting water, ethanol and acetone for centrifugal washing, finally carrying out vacuum drying and grinding to obtain powder, namely the anti-ultraviolet finishing agent.

Further, in the steps (1) and (2), the organic solvent is acetone.

Further, in the step (2), the molar ratio of the 2, 4-dihydroxy benzophenone to the cyanuric chloride is (1-1.2): 1.

Further, in the step (3), the molar ratio of the p-beta-hydroxy ethyl sulfone aniline sulfate to the cyanuric chloride is (1-1.2): 1.

Further, in the step (4), the drying temperature is 40-50 ℃ and the time is 20-30 h.

The invention has the beneficial effects that:

the invention takes cyanuric chloride as an active reaction group to react with 2, 4-dihydroxy benzophenone and p-beta-hydroxy ethyl sulfone aniline sulfate in sequence to synthesize the ultraviolet resistant finishing agent with temporary water solubility, the synthesis process is simple, and the prepared ultraviolet resistant finishing agent simultaneously has two groupsReactive groups (chlorine atoms (-Cl) and (-SO), respectively)₂CH₂CH₂OSO₃Na)), has excellent uvioresistant effect on the shielding rate of UVA and UVB of fabrics finished by the uvioresistant finishing agent, has a UPF value of more than 50, has stable performance, is not easy to be removed by washing, and does not influence the whiteness and the normal wearability of the finished fabrics.

Drawings

Figure 1 is an XRD pattern of the uv resistant finish prepared in example 1.

Detailed Description

The invention is further described with reference to the following figures and detailed description.

Example 1

An uvioresistant finishing agent has the following structural formula:

the preparation method of the anti-ultraviolet finishing agent comprises the following steps:

(1) cyanuric chloride (3.690 g; 0.020mol) is dissolved in 30mL of acetone to obtain cyanuric chloride solution, and the cyanuric chloride solution is stirred at 0 ℃ for standby;

(2) adding 2, 4-dihydroxy benzophenone (4.2844 g; 0.020mol) into 20mL of acetone, obtaining a 2, 4-dihydroxy benzophenone solution after completely dissolving, dissolving sodium hydroxide (0.80 g; 0.020mol) in 30mL of deionized water to obtain a sodium hydroxide aqueous solution, mixing and stirring the 2, 4-dihydroxy benzophenone solution and the sodium hydroxide aqueous solution uniformly, slowly dropwise adding the obtained mixed solution into the cyanuric chloride solution obtained in the step (1), after dropwise adding, controlling the pH of a reaction solution to be 7-8 and the temperature to be 0-5 ℃ by using the sodium hydroxide aqueous solution, reacting for 5 hours under the condition to obtain an intermediate product, heating to 40 ℃ while stirring, and preserving heat for later use;

(3) adding p-beta-hydroxyethyl sulfone aniline sulfate (5.6260 g; 0.020mol) into 30mL of water, uniformly mixing to obtain a p-beta-hydroxyethyl sulfone aniline sulfate suspension, dropwise adding a sodium carbonate solution (20mL) with the concentration of 1mol/L into the p-beta-hydroxyethyl sulfone aniline sulfate suspension within 30min while stirring at the temperature of 2.5 ℃ to obtain an off-white suspension, slowly dropwise adding the off-white suspension into the intermediate product obtained in the step (2), controlling the pH of the system to be 5-6 by adopting the sodium carbonate solution, stirring and reacting for 3h at the temperature of 40 ℃, and cooling to room temperature to obtain a reaction product;

(4) salting out the reaction product with saturated salt solution, carrying out suction filtration to obtain a solid product, sequentially adopting water, ethanol and acetone for centrifugal washing, finally carrying out vacuum drying at 45 ℃ for 24h, and grinding to obtain powder, namely the anti-ultraviolet finishing agent.

The XRD patterns of the UV resistant finish prepared in example 1 are shown in FIG. 1, and it can be seen that the final product is 1633, 1548, 1402cm^-1A strong absorption peak is present and is estimated as a benzene ring framework vibration peak; at 3203cm^-1A section of absorption band is arranged, and the stretching vibration is N-H; at 1018cm^-1A strong absorption peak should be a vibrational peak for the disubstituted aromatic hydrocarbon; at 1712cm^-1An absorption peak is formed, and the C ═ O vibration absorption peak is calculated; at 1342cm^-1The absorption peak is sulfoxide group; at 1243cm^-1The position is a C-N stretching vibration peak on a benzene ring; at 701cm^-1The peak is the stretching vibration peak of C-Cl.

And (3) performance testing:

the ultraviolet-resistant finishing agent prepared in example 1 was used to finish cotton fabric, and the ultraviolet protection coefficient, whiteness, wrinkle recovery angle and tensile property of the finished cotton fabric were tested by the following method: the anti-ultraviolet finishing agent prepared in the example 1 is prepared into finishing liquid with the concentration of (10g/L, 20g/L and 30g/L), sodium carbonate is added into the finishing liquid to obtain working liquid, the concentration of sodium carbonate in the working liquid is 20g/L, cotton fabrics with the size of 30cm multiplied by 6cm (warp multiplied by weft) are respectively and fully soaked in the corresponding working liquid, the bath ratio is 1:30, the two-time soaking and two-time rolling are carried out under the condition of room temperature, the mangle ratio is 70% -80%, then the cotton fabrics are placed in an air-blast drying box, the temperature is adjusted to 100 ℃, and the drying is carried out for 5 min. And (3) drying, taking out the cloth sample, adjusting the temperature of the air-blast drying oven to 150 ℃, putting the cloth sample into the air-blast drying oven when the temperature reaches 150 ℃, baking, and taking out after 5 min. After being taken out, the mixture is washed by warm water with the temperature of 55 ℃ and then washed twice by cold water. After washing, putting the mixture into a forced air drying oven, adjusting the temperature to 80 ℃, drying the mixture, and taking the mixture out after 5 min. And taking out the fabric sample, and performing fabric performance test together with the original fabric sample.

1. Measurement of ultraviolet protection factor

According to the test method, GB/T18830-2009 is selected as a standard to test according to the regulations of 'evaluation of ultraviolet resistance performance of textiles', each sample is tested for 4 times, and the average value of the test results is taken as a result.

The test results are shown in table 1:

TABLE 1

As can be seen from the test results in Table 1, the cotton fabric finished by the uvioresistant finishing agent of the embodiment 1 of the invention has excellent uvioresistant performance, and the ultraviolet protection performance of the finished fabric is gradually increased along with the continuous increase of the uvioresistant finishing concentration.

2. Whiteness, wrinkle recovery angle and breaking strength tests

The whiteness is measured according to the regulation of 'method for evaluating relative whiteness of textile color fastness test by instruments', and GB/T18401-2003 is used as a standard; the crease recovery angle test is carried out according to the regulation of a method for measuring the recovery angle of crease recovery of textile fabrics, and GB/T3819-1997 is adopted as a standard for measurement; the breaking strength test was carried out according to the specification of determination of tensile properties of textile fabrics (part 1) of breaking strength and breaking elongation (bar method) in GB/T3923.1-2013.

The test results are shown in table 2:

TABLE 2

As can be seen from the test results in table 2, the whiteness, wrinkle recovery angle and breaking strength of the finished fabric decreased with increasing concentration of the finishing agent, but the decrease was small and did not affect normal use.