CN110629550A - A kind of method of photocatalytic maleic anhydride grafted linen - Google Patents

Abstract

A method for photocatalyzing maleic anhydride grafted linen, which relates to the field of composite material preparation, the specific scheme is as follows: a method for photocatalyzing maleic anhydride grafted linen, comprising the following steps: Take it out in 16% sodium hydroxide aqueous solution for 30 seconds, wash it with distilled water until neutral, put it in a vacuum drying oven and dry it; step 2, soak the dried linen in a maleic anhydride solution containing a photocatalyst for 15 minutes Take it out, and then irradiate each side of the linen cloth with ultraviolet light for 2-4 minutes; step 3, after the irradiation is completed, take out the linen cloth, wash it with distilled water to neutrality, put it into a vacuum drying oven and dry it to obtain the linen cloth grafted with maleic anhydride. The ultraviolet photocatalytic photografting method grafts maleic anhydride on the surface of linen cloth, which overcomes the shortcomings of traditional melting method and solution method such as high energy consumption, complicated process, and large pollution. The process is simple and the grafting rate is high.

Description

A kind of method of photocatalytic maleic anhydride grafted linen

technical field

The invention relates to the field of composite material preparation, in particular to a method for photocatalyzing maleic anhydride grafted linen.

Background technique

At present, the methods of grafting maleic anhydride include methods such as thermal grafting, photografting, and radiation grafting according to the different ways of free radical initiation ^[1] ; according to the state of the natural fiber, there are solution method, melting method and solid phase method. Law.

The solution grafting method ^[1] is troublesome to recycle, and the production cost is high, and the organic solvent used will cause harm to the human body and damage to the environment. The same grafted fibers need to be re-drawn and woven into linen.

The melt-grafting method ^[2] has the characteristics of simple operation, low cost, and is suitable for industrial production. However, the high reaction temperature of this method will seriously degrade the natural fibers and reduce the mechanical properties of the matrix. The grafted fibers need to be re-drawn and woven into linen.

The thermal grafting method generally adopts grafting at a certain temperature. This grafting method has higher requirements for temperature. For some materials with low melting point or poor stability, they are easy to denature during the reaction. For the material linen.

The radiation grafting method ^[3]-[4] requires high-priced equipment to generate high-energy rays, and this method is easy to damage the substrate, so it is not suitable for industrial continuous production.

Jun Qian ^[5] et al. grafted maleic anhydride (MAH) onto PP by means of ultrasound, high-energy ray radiation and co-radiation, and compared the effects of different co-monomers on the grafting rate. This method consumes more energy. The biggest disadvantage of radiation grafting is that when the polymer monomer mixed system is irradiated at the same time, the homopolymerization reaction of monomers will inevitably occur, which reduces the grafting efficiency and increases the steps of removing homopolymers.

The references are as follows:

[1] Jiang Dawei, Xu Qingling, Ren Biaobiao, Wang Yuanheng, Sun Caiying. Na～+ Flame Retardant Modified Flax Fiber and Its Effect on Fiber Properties[J]. Fine Chemical Industry, 2019,36(09):1809-1815 .

[2] Chang Yanjie, Zhang Dewen, Yang Shuai, et al. Comparison of Polypropylene Melt Grafting and Pre-radiation Grafting Maleic Anhydride [J]. Plastic Industry, 2016,44(6):41-45.

[3] Xing Zhe, Wang Mouhua, Wu Guozhong. Study on γ-ray radiation grafting of methyl acrylate on ultra-high molecular weight polyethylene fibers [J]. 2011.

[4] Wang Feng, Tong Bin. Preparation and Characterization of Polypropylene Radiation Grafted Silane[J]. Journal of Radiation Research and Radiation Technology, 2009,27(5):261-264.

[5] Qian Jun, Huang Zhijuan, Dang Shuaiying, et al. Improvements of polypropylene grafted maleic anhydride with untrasonication, pre-irradiation and co-irradiation methods [J]. Journal of Polymer Research, 2011, 18(1): 1557-1565.

Contents of the invention

The purpose of the present invention is to graft maleic anhydride on the linen cloth by ultraviolet photocatalysis, introduce double bonds and carboxyl functional groups, and then modify the linen cloth according to requirements such as flame retardancy and conductivity, and provide a photocatalytic maleic anhydride Method of grafting linen.

Natural linen has the advantages of breathability, antibacterial, and wear resistance, and is often used as decorative materials for clothing, home furnishing, vehicles, ships, and airplanes. Linen itself does not conduct electricity.

To achieve the above object, the present invention takes the following technical solutions:

A method for photocatalyzed maleic anhydride grafted linen, comprising the steps:

Step 1. Put the linen cloth in 16% sodium hydroxide aqueous solution for 30 seconds, wash it with distilled water until neutral, and dry it in a vacuum drying oven;

Step 2. Soak the dried linen cloth in the maleic anhydride solution containing photocatalyst for 15 minutes and take it out, and then irradiate each side of the linen cloth with ultraviolet light for 2-4 minutes;

Step 3: After the irradiation is completed, take out the linen cloth, wash it with distilled water until neutral, put it into a vacuum drying oven and dry it to obtain the linen cloth grafted with maleic anhydride.

Further, in step 1, the drying temperature is 60° C., and the drying time is 90 minutes.

Further, in step 2, the solvent of the maleic anhydride solution is N,N-dimethylformamide solution (DMF).

Further, in step 2, the mass concentration of maleic anhydride in the maleic anhydride solution is 10-50%wt.

Further, in step 2, the photocatalyst is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

Further, in step 2, the mass of the photocatalyst is 2% of the mass of maleic anhydride weighed.

Further, the power of the ultraviolet lamp for irradiating ultraviolet light in step 2 is 112-280w, and the wavelength is 395nm.

Further, in step 3, the drying temperature is 60° C., and the drying time is 90 minutes.

The beneficial effects of the present invention are:

(1) The ultraviolet photocatalytic photografting method grafts maleic anhydride on the surface of linen cloth, which overcomes the shortcomings of traditional melting method and solution method such as high energy consumption, complicated process, and large pollution. The process is simple and the grafting rate is high. Under the condition that the mass concentration of maleic anhydride is 40% and the irradiation time is 4 minutes on both sides, the grafting rate can reach 62.11%.

(2) Ultraviolet light is less penetrating to materials than high-energy radiation, so graft polymerization can be strictly limited to the surface or subsurface of the material without damaging the bulk properties of the material.

(3) The light source of ultraviolet radiation and its equipment cost are low, the degree of reaction is easy to control, and it is easy to realize continuous industrial production; at the same time, photografting is an environmentally friendly green grafting technology, which has low polymerization energy consumption and high polymerization speed. Fast, high production efficiency, low polymerization reaction temperature, simple reaction equipment, less environmental pollution and other advantages, in line with the concept of green environmental chemistry.

Description of drawings

Fig. 1 is the infrared spectrograms of the linen before and after grafting, where the ordinate is the absorbance, the unit is %, and the abscissa is the absorption wavelength, the unit is cm ^-1 .

Detailed ways

The technical solution of the present invention will be further described below in conjunction with the accompanying drawings 1 and specific embodiments, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention is acceptable. Should be included in the protection scope of the present invention.

Specific implementation mode one

A method for photocatalyzed maleic anhydride grafted linen, is characterized in that: comprises the steps:

Step 1. Put the linen cloth in 16% sodium hydroxide aqueous solution for 30 seconds, swell it, take it out immediately, wash it with distilled water until neutral, put it in a vacuum drying oven, and dry it at 60°C for 90 minutes. Take out spare;

Step 2, prepare maleic anhydride (MAH) N,N-dimethylformamide solution (DMF), wherein, the mass concentration of maleic anhydride (MAH) is 40%, add photocatalyst 2,4,6-trimethylformamide Benzoyl-diphenylphosphine oxide (TPO), the quality of TPO is 2% of the MAH quality that takes by weighing; Linen cloth is placed in the DMF solution of prepared MAH and soaks 15min, puts into the ultraviolet light instrument immediately , the power is 280w, the wavelength is 395nm, and the front and back sides of the linen are irradiated for 4 minutes;

Step 3: After the irradiation is completed, take out the linen cloth, wash it with distilled water until neutral, put it in a vacuum drying oven, dry it at 60°C for 90 minutes, and take it out, finally obtaining the linen cloth grafted with maleic anhydride.

Specific implementation mode two

A method for photocatalyzed maleic anhydride grafted linen, is characterized in that: comprises the steps:

Step 1. Put the linen cloth in 16% sodium hydroxide aqueous solution for 30 seconds, swell it, take it out immediately, wash it with distilled water until neutral, put it in a vacuum drying oven, and dry it at 60°C for 90 minutes. Take out spare;

Step 2, prepare maleic anhydride (MAH) N,N-dimethylformamide solution (DMF), wherein, the mass concentration of maleic anhydride (MAH) is 50%, add photocatalyst 2,4,6-trimethylformamide Benzoyl-diphenylphosphine oxide (TPO), the quality of TPO is 2% of the MAH quality that takes by weighing; Linen cloth is placed in the DMF solution of prepared MAH and soaks 15min, puts into the ultraviolet light instrument immediately , the power is 80% of the maximum power (the maximum power is 280w, the wavelength is 395nm), and the front and back sides of the linen are illuminated for 2 minutes;

Step 3: After the irradiation is completed, take out the linen cloth, wash it with distilled water until neutral, put it in a vacuum drying oven, dry it at 60°C for 90 minutes, and take it out, finally obtaining the linen cloth grafted with maleic anhydride.

Specific implementation mode three

A method for photocatalyzed maleic anhydride grafted linen, is characterized in that: comprises the steps:

Step 1. Put the linen cloth in 16% sodium hydroxide aqueous solution for 30 seconds, swell it, take it out immediately, wash it with distilled water until neutral, put it in a vacuum drying oven, and dry it at 60°C for 90 minutes. Take out spare;

Step 2, prepare maleic anhydride (MAH) N,N-dimethylformamide solution (DMF), wherein, the mass concentration of maleic anhydride (MAH) is 10%, add photocatalyst 2,4,6-trimethylformamide Benzoyl-diphenylphosphine oxide (TPO), the quality of TPO is 2% of the MAH quality that takes by weighing; Linen cloth is placed in the DMF solution of prepared MAH and soaks 15min, puts into the ultraviolet light instrument immediately , the power is selected as 40% of the maximum power (the maximum power is 280w, the wavelength is 395nm), and the front and back sides of the linen are irradiated for 3 minutes;

Step 3: After the irradiation is completed, take out the linen cloth, wash it with distilled water until neutral, put it in a vacuum drying oven, dry it at 60°C for 90 minutes, and take it out, finally obtaining the linen cloth grafted with maleic anhydride.

The invention relates to a preparation process of a flax fiber composite for deepening the development of the flax cloth application field. A key step in the method for preparing the flax fiber composite is to graft the flax fiber with maleic anhydride.

The flax fiber composite finally prepared has excellent functions such as flame retardancy, electrical conductivity, heat conduction, shielding and absorption of electromagnetic waves, etc., and can be applied to conductive mesh and conductive work clothes in the electronics and power industries; electric heating clothes, electric heating surfaces, and electric heating bandages in the medical industry; aviation , aerospace, and electromagnetic shielding covers in the precision electronics industry, etc. It can be used in fields such as antistatic textiles, anti-electromagnetic radiation textiles, intelligent textiles and military textiles.

Can be applied to:

1. Antistatic textiles

Conductive fiber is a functional fiber based on the mechanism of electronic conduction, which eliminates static electricity through electronic conduction and corona discharge. Since the fiber contains free electrons, its antistatic properties have no humidity dependence; the half-life of the charge of the conductive fiber is short, and in any case, it can eliminate static electricity in a very short time, and the conductive fiber is used to prevent the generation and harm of static electricity. Wide environmental adaptability. According to the conductivity of the conductive fiber and the structure of the fabric, the antistatic effect can be achieved by mixing 0.05% to 5% conductive fiber in the general fiber. Work clothes with antistatic effect made of conductive fibers are suitable for oil fields, petroleum processing, coal mines, electronics industry, photosensitive material industry and other flammable and explosive occasions, and are also suitable as dust-free and sterile clothing or special filter materials Wait.

2. Anti-electromagnetic radiation textiles

Electromagnetic shielding is the use of low-resistivity conductive materials to reflect and guide electromagnetic currents, and generate current and magnetic polarization opposite to the original magnetic field inside the conductor material, thereby weakening the radiation effect of the original electromagnetic field. Conductive fibers used as anti-electromagnetic radiation require very low resistivity, usually only 10 ^-6 ~ 10 ^-2 Ω/cm. In recent years, due to the wide application of electronic and electrical equipment and communication equipment, the interference of electromagnetic radiation can cause misoperation of equipment, image and sound disturbance, and harm to human body, which has attracted people's attention to the development of electromagnetic shielding materials. The development of conductive fibers with low resistivity and the tight market are also triggered by this.

Utilizing the electromagnetic wave shielding properties of conductive fibers, it can be used to make electromagnetic wave shielding covers such as precision electronic components and high-frequency welding machines, and to make walls, ceilings and wall coverings that absorb radio waves for houses with special requirements. In Japan, conductive fibers coated with copper are blended or made into non-woven fabrics, which have been widely used in electromagnetic wave shielding and absorbing materials, such as electromagnetic wave absorbing covers for ships.

3. Sensor Textiles

Sensor textiles made of flexible conductive fibers using the principle of electronic sensors have the advantages of lightness and portability, and are widely used in various fields. Japan's Sun Industries has developed a sensor that detects the maximum strain with carbon fiber, which can be used for safety diagnosis of structures such as buildings, roads, factories, aircraft, and cableways.

4. The future war of military textiles will be an information war under high-tech conditions. In such a war, the pace of combat is fast, the frequency of offensive and defensive transitions is fast, and the situation of the war changes rapidly. The traditional combat equipment of soldiers appears to be seriously behind. In order to improve the comprehensive combat capability of soldiers in the modern battlefield, it is necessary to improve the ability of soldiers to acquire, process and transmit information, so that soldiers can have a higher level of understanding of the battlefield situation. Information clothing made of conductive fibers just meets this requirement. one request.

Most conductive fibers are sensitive to electricity and heat, and the fabric made of conductive fibers can prevent the detection of thermal imaging equipment, which can be made into thermal imaging protective clothing for individual soldiers. Conductive fibers are compounded with resin, rubber and other low-dielectric substrates to make electromagnetic wave absorbing materials. This material can absorb radar waves, avoid radar tracking, and achieve the purpose of stealth for weapons and equipment. The color-changing military uniform developed by the United States is to add a conducting circuit composed of conductive fibers to the fabric. By controlling the temperature, the thermal color-changing ink in the military uniform will change, so that the color of the military uniform will change according to the external environment. An environmental reactive camouflage.

5. Other applications

By selecting functional conductive additives, fiber materials with other functions besides conductive functions can also be prepared, such as antibacterial, far infrared, etc. Mitsubishi Corporation of Japan uses composite spinning technology to make the fiber conductive by mixing a high concentration of white conductive ceramic particles in the core. At the same time, because the added ceramic particles have light-to-heat conversion characteristics, after blending the fiber with 10% of the conventional fiber, the temperature of the fabric can rise to 28°C under the light source. Not only does this fiber keep the wearer warm, but after washing, its drying time in the sun is 2/3 that of conventional fibers, and quick drying is an additional characteristic of this fiber. Since the conductive particles of this fiber are in the core of the fiber, the usual processing, washing, dyeing, etc. will not affect the conductive durability of the fiber.

Claims (8)

1. a method for photocatalyzed maleic anhydride grafted linen, is characterized in that: comprise the steps: Step 1. Put the linen cloth in 16% sodium hydroxide aqueous solution for 30 seconds, wash it with distilled water until neutral, and dry it in a vacuum drying oven; Step 2. Soak the dried linen cloth in the maleic anhydride solution containing photocatalyst for 15 minutes and take it out, and then irradiate each side of the linen cloth with ultraviolet light for 2-4 minutes; Step 3: After the irradiation is completed, take out the linen cloth, wash it with distilled water until neutral, put it into a vacuum drying oven and dry it to obtain the linen cloth grafted with maleic anhydride. 2. The method for grafting linen with photocatalytic maleic anhydride according to claim 1, characterized in that: in step 1, the drying temperature is 60° C., and the drying time is 90 minutes. 3. a kind of method for photocatalytic maleic anhydride grafted linen according to claim 1, is characterized in that: in step 2, the solvent of maleic anhydride solution is N,N-dimethylformamide solution DMF. 4. A method for photocatalytic maleic anhydride grafted linen according to claim 1 or 3, characterized in that: in step 2, the mass concentration of maleic anhydride in the maleic anhydride solution is 10 to 50 %. 5. the method for a kind of photocatalytic maleic anhydride grafted linen according to claim 1, is characterized in that: in step 2, described photocatalyst is 2,4,6-trimethylbenzoyl-di Phenylphosphine oxide. 6. a kind of method for photocatalytic maleic anhydride grafted linen according to claim 1, is characterized in that: in step 2, the quality of photocatalyst is 2% of the maleic anhydride quality that takes by weighing. 7. a kind of method for photocatalytic maleic anhydride grafted linen according to claim 1, is characterized in that: the power of the ultraviolet lamp that irradiates ultraviolet light in step 2 is 112-280w, and wavelength is 395nm. 8 . A method for photocatalytically grafting linen with maleic anhydride according to claim 1 , characterized in that: in step 3, the drying temperature is 60° C., and the drying time is 90 minutes.