CN1306080C - Chemical fibre containing organic metal catalyst, production and use thereof - Google Patents

Abstract

The invention relates to a chemical fiber containing an organometallic catalyst, a manufacturing method and an application thereof. Fibers containing organometallic catalysts. The weight ratio of organometallic catalyst and polymer compound is (0.5～8): (92～99.5), and described polymer compound is acrylic fiber, vinylon or cellulose fiber; Described organometallic catalyst is selected from following iron , cobalt or manganese organic compounds: a) porphyrin iron, cobalt or manganese, or their water-soluble or water-dispersible derivatives; b) porphyrin iron, cobalt or manganese, or their water-soluble or water-dispersible derivatives thing. The organic metal catalyst is dissolved or dispersed in the spinning slurry, and the fiber is obtained by spinning by conventional wet spinning technology. The fiber has the function of deodorizing or deodorizing. Deodorized or deodorized textiles can be prepared.

Description

Chemical fiber containing organometallic catalyst, production method and use thereof

technical field

The present invention relates to a chemical fiber containing an organometallic catalyst, a manufacturing method and an application thereof.

Background technique

With the continuous improvement of people's living standards, people have higher and higher requirements for clothing and home textiles in terms of aesthetics, comfort, and hygiene. It is hoped that some textiles can have the effect of removing odor. People have done a lot of work on this side. At present, basically some just add antibacterial substances in the process of chemical fiber production, and some add antibacterial substances in the method of finishing, so that fibers or fabrics have bactericidal and deodorizing effects. Relevant reports on bactericidal and deodorant effects include: Xiao Yaonan, Zeng Hanmin's research progress on antibacterial and deodorant functional fibers (2): Preparation, Materials Science and Engineering, 2001, 2, 80-88; Huang Hansheng, Recent developments in Japanese antibacterial and deodorant fibers, Modern Chemical Industry 2000, September, 54-59; Xue Fulian, Development and application of antibacterial and deodorant fiber, Guangxi Chemical Fiber Communication 2003, 2, 46-48; Zhao Bo, Antibacterial and deodorant fiber properties and product development, Sichuan Silk, 2004, 4 , 27-28; Wang Jianping, The Latest Development of Antibacterial Fibers, Industrial Textiles, 1998, November, 6-10; Zhou Yupeng, Application of Silicone Surfactants in Daily Chemicals and Textile Industry, Silicone Materials, 2002, 01, 24 -26; Fan Yao, Ge Naixiang, Mao Mingfu, etc., Properties of Modified Fabrics, Printing and Dyeing, 1999, May, 12-14; Cai Xiang, Liu Kan, Su Kaidi, Research on the Synthesis and Application of Antibacterial Finishing Agent CL, Guangxi Textile Science and Technology, 2000, March, 2-5; Yu Zhicheng, Chen Wenxing, Preparation, structure and properties of deodorizing and antibacterial cellulose fibers, Journal of Functional Polymer Sciences, 2002, 4, 461-465; Yang Dongliang, Antibacterial and deodorant finishing agents for fibers, printing and dyeing, 2001, 3, 47-52; Yang Mingying, Zhu Liangjun, Research Overview of Antibacterial and Deodorizing Fibers, Modern Textile Technology, 2000, 2, 39-41; Song Zhaotang, Shi Xiaofang, Progress in Antibacterial and Deodorizing Fibers and Antibacterial Processing, Printing and Dyeing Auxiliaries, 2000 , 5, 1-5, etc. The Chinese patents of antibacterial and deodorant fibers and fabrics have patent application numbers of 01109549.0, 92108481.1, 94112079.1, 92109930.4, 87100231, and 92108488.9. But the method of so-called antibacterial deodorization, deodorization, and deodorization treatment can only prevent the generation of bad smell in fact, and can't eliminate or remove the bad smell that already exists. It can only prevent bacteria from decomposing the protein in sweat to release odor, but it cannot remove the odor secreted by the human body itself and the reducing odor in the surrounding environment.

Iron, cobalt, manganese phthalocyanines, porphyrins and their porphin compounds and their water-soluble or water-dispersible derivatives have redox catalysis. There have been many articles describing its application research in the synthesis of organic compounds and wastewater treatment. Such as: Zhang Yingju, Liang Bin, etc. Catalytic activation of tetra-tert-butyl metal phthalocyanine for the cycloaddition reaction of CO2 and propylene oxide, Journal of Catalysis, 2003, 10, 765-768; Li Huaming, Wang Yan, palladium acetate/iron phthalocyanine Research on catalytic oxidation of cyclopentene to cyclopentanone, Acta Chemicals, 2001, 8, 417-420; Ye Xingkai, Research on hydroquinone oxidation catalyzed by iron phthalocyanine, Journal of Hainan University: Natural Science Edition, 1997, 4, 280-284; Wang Zaosheng, Synthesis of Sulfonated Iron Phthalocyanine and Photocatalytic Degradation of Dye Wastewater, Shanghai Environmental Science, 2001, 10, 480-481; Dai Qing, Zhang Xinlei, etc. "MPcTS-H2O2" System Catalysis of Organic Pollutants in Water Degradation, Chemical Times, 1998, 10, 3-6 and Lu Chun'e Dai Qing, Catalytic degradation of sodium dodecylbenzenesulfonate in water by supported phthalocyanine, Journal of Nanjing University of Chemical Technology 1999, 6, on the degradation of sodium dodecylbenzenesulfonate in wastewater The decomposition of amino compounds, azobenzene and sodium dodecylbenzenesulfonate was studied. Shirai Wangfang, a professor at Shinshu University in Japan, has studied the deodorization of iron phthalocyanine used in viscose fiber, which is reported below: Utilizing the oxidation-reduction catalytic activity of iron phthalocyanine, Chemical Industry (Japan) 1996 , 12, 19-25; Fiber deodorizing finishing, Journal of Textile Machinery Society (Journal), 2001(11): 434-443. Yu Zhicheng from China has studied the deodorizing properties of iron phthalocyanine adsorbed on cellulose, and the deodorizing properties and mechanism of phthalocyanine-loaded cellulose fibers, Journal of Textile Science, 2002, 6, 450-451.

There are no papers that use iron, cobalt, manganese phthalocyanine, porphyrin and its porphyrin compound and its water-soluble or water-dispersible derivatives to make acrylic fiber, vinylon or Tencel fiber that eliminates odor. and patents.

Contents of the invention

The object of the present invention is to provide a chemical fiber containing an organometallic catalyst.

The object of the present invention is also to provide a method for producing the above-mentioned chemical fiber containing an organometallic catalyst.

Another object of the present invention is to provide a use of the above-mentioned chemical fiber containing an organometallic catalyst.

The redox catalysis of iron, cobalt and manganese phthalocyanine, porphyrin and its porphin compound and its water-soluble or water-dispersible derivatives can effectively eliminate the existing odor. The mechanism of deodorization is: iron, cobalt, manganese phthalocyanine, porphyrin and its porphyrin compounds and their water-soluble or water-dispersible derivatives can oxidize the odorous substances containing ammonia and sulfur or formaldehyde to lose the odor. It is reduced to a low-priced compound in this life, and it can be oxidized to a high-priced metal compound in the air, and has the function of oxidizing odorous substances. It has a function of automatic regeneration and repeated use, and is a catalyst with high-performance enzyme properties. It is a brand-new concept of chemical fiber deodorization.

The chemical fiber containing the organometallic catalyst of the present invention is a chemical fiber in which the weight ratio of the organometallic catalyst to the polymer compound is (0.5-8):(92-99.5). The high molecular compound is acrylic fiber, vinylon or cellulose fiber. The organometallic catalyst is selected from the following organic compounds of iron, cobalt or manganese: a) iron phthalocyanine, cobalt or manganese, or their water-soluble or water-dispersible derivatives; b) porphyrin iron, cobalt or Manganese, or their water-soluble or water-dispersible derivatives; c) porphine iron, cobalt or manganese, or their water-soluble or water-dispersible derivatives.

The manufacturing method of the chemical fiber containing the above-mentioned organometallic catalyst of the present invention is to dissolve the above-mentioned polymer compound in a solvent, make a slurry with a concentration required for spinning, and then disperse the above-mentioned organometallic catalyst uniformly in the In the slurry, the weight ratio of the organometallic catalyst to the polymer compound in the slurry is (0.5～8): (92～99.5), and then spinning and pulling are carried out according to conventional acrylic fiber, vinylon or cellulose fiber spinning equipment and techniques. Acrylic, vinylon or Tencel fibers containing organometallic catalysts can be obtained by stretching.

The high molecular compound for spinning is polyacrylonitrile, polyvinyl alcohol or cellulose.

The organometallic catalyst is as mentioned above, selected from the following organic compounds of iron, cobalt or manganese: a) iron phthalocyanine, cobalt or manganese, or their water-soluble or water-dispersible derivatives; b) porphyrin porphine iron, cobalt or manganese, or their water-soluble or water-dispersible derivatives; c) porphine iron, cobalt or manganese, or their water-soluble or water-dispersible derivatives.

The method for producing deodorizing fibers has the advantages of good effect, less investment, no modification of raw fiber production equipment, and continuous industrial production. This kind of fiber can be used in the manufacture of underwear, cotton sweater trousers, bed sheets, quilt lining, pillow cover or interior decoration cloth. The fabric or fiber itself can eliminate the body odor discharged from the human body or various indoor odors, and solve the problem. Deodorization and deodorization during the use of textiles and the surrounding environment. .

Detailed ways:

The following examples will help to understand the present invention, but do not limit the content of the present invention.

The polymer compounds used in the examples are all commercial products, the polymer slurry is the raw material for spinning in chemical fiber factories, and the organometallic catalysts are commercial products or prepared by the laboratory itself. For the preparation method, see: Synthesis of Sulfonated Iron Phthalocyanine and Photocatalytic Degradation of Dye Wastewater, Shanghai Environmental Science, 2001, 20, 480-481; Synthesis of Octacarboxy Metal Phthalocyanine Derivatives and Research on Their Catalytic Oxidation Properties, Zhejiang Engineering Academic Journal, 2002, 3, 141-144; Synthesis of tetra-tert-butyl metal phthalocyanine compounds, Dyestuff Industry, 2001, 10, 34-36.

Example 1

Use 6 grams of commercially available iron phthalocyanine to evenly disperse in 1000 grams of 15% polyvinyl alcohol aqueous solution by weight, then defoam, and extrude the slurry into a 50°C Glauber's salt coagulation bath on a small spinning machine through a spinneret hole It is coagulated into silk, then wet-heat stretched in Glauber's salt liquid at 90°C, then dry-heat stretched, acetalized, washed, oiled, and dried to obtain vinylon fiber containing iron phthalocyanine. The ammonia elimination rate of the fiber is 77%, and the hydrogen sulfide elimination rate is above 90%.

Detection method: Put 2 grams of fibers containing this catalyst in a 10-liter plexiglass sealed box with a latex injection window, fill it with odorless fresh air and seal it, and inject ammonia or vulcanization through the latex window with a syringe Hydrogen gas so that its concentration is around 100 PPM. Analyze the concentration of ammonia or hydrogen sulfide by gas chromatography. After half an hour, analyze the ammonia or hydrogen sulfide content in the gas in the box. Odor elimination rate: (W ₁ -W ₂ )/W ₁

W ₁ : Odor concentration before reaction, W ₂ : Odor concentration after reaction

The detection methods of the following examples are the same.

Example 2

Disperse 2.5 grams of manganese porphyrin in 1000 grams of polyacrylonitrile by weight in 14% sodium thiocyanate aqueous solution (the sodium thiocyanate in sodium thiocyanate aqueous solution is 50% by weight), static defoaming , squeeze the solution into 10% sodium thiocyanate aqueous solution at 10°C through the spinneret hole to solidify into a precursor, then pre-stretch through the second coagulation bath, the coagulation bath is 3% sodium thiocyanate aqueous solution, and the bath temperature is 50°C. Then it is stretched by steam, the stretching temperature is 100°C, then washed with water, oiled and dried. The dried fibers are crimped at 85° C., heat-set at 130° C., oiled again, and dried at 120° C. to obtain acrylic fibers containing manganese porphyrin. The ammonia elimination rate of the cloth is 65%, and the hydrogen sulfide elimination rate is 84%.

Example 3

Dissolve 1000 grams of 15.4% polyvinyl alcohol aqueous solution with 4.5 grams of tetracarboxyphthalocyanine cobalt sodium salt, and extrude the slurry into a 52° C. mirabilite coagulation bath on a small spinning machine to coagulate into silk. Then wet heat stretching in Glauber's salt solution at 88°C, dry heat stretching at 210°C, acetalization, water washing, oiling, and drying to obtain vinylon fibers containing cobalt phthalocyanine and covalently bonded fiber macromolecules. The ammonia elimination rate of the fiber is 73%, and the hydrogen sulfide elimination rate is over 90%.

Example 4

12 grams of commercially available manganese porphin are dispersed in 1000 grams of polyacrylonitrile by weight of 14% sodium thiocyanate aqueous solution (the sodium thiocyanate weight percent of sodium thiocyanate aqueous solution is 50%), by spraying Squeeze the solution into the 12°C 10% sodium thiocyanate aqueous solution to solidify into the original silk through the silk hole, and then pre-stretch through the second coagulation bath, the coagulation bath is 3% sodium thiocyanate aqueous solution, and the bath temperature is 50°C. Then it is stretched by steam, the stretching temperature is 100°C, then washed with water, oiled and dried. The dried fibers are crimped at 85° C., heat-set at 125° C., oiled again, and dried at 120° C. to obtain acrylic fibers containing porphine iron. The ammonia elimination rate of the fiber is 81%, and the hydrogen sulfide elimination rate is above 90%.

Example 5

Use 0.8 grams of tetrahydroxyphthalocyanine iron to disperse in 1000 grams of cellulose weight percentage in the methyl morpholine oxide aqueous solution (wherein the methyl morpholine oxide and water weight ratio are 12.5: 1), by spraying The solution is extruded through the silk hole and stretched in a small section of air layer, and then enters the first bath of 15 to solidify into silk, and then enters the second bath for washing, oiling, and drying to obtain Tencel fibers containing iron tetrahydroxyphthalocyanine. The ammonia elimination rate of the fiber is 38%, and the hydrogen sulfide elimination rate is 57%.

Example 6

Disperse 5 grams of commercially available porphyrin iron in 1000 grams of polyacrylonitrile by weight in 15% sodium thiocyanate aqueous solution (the sodium thiocyanate in sodium thiocyanate aqueous solution is 50% by weight), static Degassing, squeeze the solution into 11% sodium thiocyanate aqueous solution at 9°C through the spinneret hole to solidify into raw silk, and then pre-stretch through the second coagulation bath, the coagulation bath is 3% sodium thiocyanate aqueous solution, bath The temperature is 48°C. Then it is stretched by steam, the stretching temperature is 100°C, then washed with water, oiled and dried. The dried fibers are crimped at 85° C., heat-set at 135° C., oiled again, and dried at 120° C. to obtain porphyrin-iron-containing acrylic fibers. The ammonia elimination rate of the fiber is 75%, the hydrogen sulfide elimination rate is 89%, and the formaldehyde elimination rate is 81%.

Claims (4)

1, a kind of chemical fibre that contains organo-metallic catalyst, it is characterized in that containing the chemical fibre of organo-metallic catalyst and macromolecular compound, the weight ratio of organo-metallic catalyst and macromolecular compound is (0.5～8): the chemical fibre of (92～99.5), described macromolecular compound are acrylic fibers, polyvinyl or cellulose fibre; Described organo-metallic catalyst is selected from the organic compound of following iron, cobalt or manganese: a) PORPHYRIN IRON, cobalt or manganese or their water-soluble or water-dispersible derivative; B) porphines iron, cobalt or manganese or their water-soluble or water-dispersible derivative.

2, the preparation method of chemical fibre according to claim 1, it is characterized in that organo-metallic catalyst with the organic compound of chosen from Fe, cobalt, manganese dissolves equably or is dispersed in the spinning slurry that contains macromolecular compound, the weight ratio of macromolecular compound is (0.5～8) in organo-metallic catalyst and the slurries: (92～99.5), the fiber that the wet spinning technology spinning by routine obtains; Described spinning is used macromolecular compound and organo-metallic catalyst according to claim 1.

3, the preparation method of chemical fibre according to claim 2 is characterized in that adopting the spinning equipment of conventional acrylic fibers, polyvinyl or cellulose fibre and technology to carry out acrylic fibers, polyvinyl or Tencel fiber that spinning, drawing-off obtain containing organo-metallic catalyst.

4, the purposes of chemical fibre according to claim 1 is characterized in that preparing the textiles of smelly or deodorizing of disappearing.