Introduction to new progress in the development of flame-retardant fibers and flame-retardant fabrics in the world
In the 1980s, my country’s fire-resistant fabrics entered a new period of development. Many units developed fire-retardant agents and finishing technologies for cotton, polyester and blended chemical fiber fabrics and fire-resistant synthetic fibers. Research and development of fire-proof fibers – The research and development of fire-proof fibers in my country started in the 1970s; from the 1980s to the present, some scientific research units and institutes in Shanghai, Jilin, Shandong, Guangdong, Tianjin, Sichuan, Beijing, Jiangsu and other provinces and cities Schools and factories have successively conducted small-scale research on fire-resistant fibers. Polyester and polypropylene have formed mass production capabilities, but generally speaking, fire-resistant fiber products are still in the research and trial stage.
In recent years, fires caused by fabrics have been increasing in countries around the world. In the past ten years or so in our country, the average number of fires occurring each year has been 30,000 to 40,000, with 2000 to 3000 deaths, and fire losses of 200 to 300 million yuan. These accidents are caused by burning fabrics. my country’s fabric fireproofing technology began in the 1950s, starting with the study of temporary fireproofing finishing of cotton fabrics, but progress has been slow. Durable pure cotton fire-retardant fabrics only appeared in the 1960s. After the development of fire retardant agents in the 1970s, the research phase on fire protection technology for synthetic fibers and blended chemical fiber fabrics began.
2. Current status of fireproof modification of synthetic fibers
1. Fireproof modification of polyamide fiber
The main fire retardants that can be used as polyamide 6 and polyamide 66 copolymer fire retardant modification include red phosphorus and dicarboxylic acid ethyl methyl phosphate. Red phosphorus often works together with inert compounds, such as manganese hydroxide, aluminum hydroxide, etc., to perform fireproof modifications on polyamide 6 and polyamide 66. The better copolymer fire retardant used in the production of fire-resistant polyamide fibers in China is the NF-8702 polyamide fiber fire retardant produced by Shanxi Chemical Fiber Research Institute. Intumescent fire protection systems have potential market application value in the fire protection modification of polyamide fibers. There are many fire retardants used for blend modification of polyamide, such as low molecular weight phosphorus-containing compounds, chlorinated polyethylene, brominated pentaerythritol and antimony trioxide. A ternary fire protection system composed of boron, antimony and bromine is used to modify polyamide for fire protection, and its fire protection effect is relatively good. Other synthetic fiber fabrics that use red phosphorus or microencapsulated red phosphorus and polyamide blends can also obtain fire-resistant polyamide fibers with self-extinguishing properties.
2. Fireproof modification of polyacrylonitrile fiber
The copolymerization fireproof modification method mainly introduces comonomers containing halogen or phosphorus elements into polyacrylonitrile fiber, such as vinyl chloride, vinylidene chloride, allyl phosphate alkyl, vinyl bis(2-chloro ethyl) phosphate and other comonomers. At present, most of the fire-resistant polyacrylonitrile fibers that have been industrially produced in the world are made by copolymerization. Since the content of fire retardant in the blended fire retardant polyacrylonitrile fiber cannot be too high, an efficient fire retardant must be selected, and the fire retardant must have good solubility and uniform and stable dispersion in the spinning solution, as well as good compatibility with polyacrylonitrile. Capacitance, retention rate during spinning, cleaning resistance and
Toxicity, etc., therefore, it is difficult to select fire retardant agents. Currently, there are very few varieties of industrialized blended fire retardant polypropylene fibers.
3. Fireproof modification of polypropylene fiber
The fireproof modification of polypropylene fiber is mainly prepared by adding modification and fireproof finishing. At present, polypropylene mainly obtains fire retardant effects by using synergists such as halogen fire retardants and antimony trioxide. Usually, high concentrations of fire retardants and other additives are first added to polypropylene slices, and then blended to create a fire retardant matrix. pellets are then melt-spun with conventional polypropylene sliced fibers to prepare fire-resistant polypropylene fibers. The phosphorus-bromine synergistic fire protection system has good fire protection effect when used for polypropylene fiber and has little environmental pollution, while the phosphorus-nitrogen synergistic fire protection system has better fire protection effect when used for polypropylene fiber, but in polypropylene fiber The application conditions are relatively high.
4. Fireproof modification of polyester
There are many additive fire retardants that can be used for polyester, and adding fire retardants is also the initial fire retardant modification method for polyester. Fire retardants mainly include halogen fire retardants and phosphorus fire retardants. Among halogen fire retardants, bromine fire retardants have the best fire retardant effect, and their fire retardant effects can be improved by forming a synergistic effect with antimony compounds (such as antimony trioxide). Among the phosphorus fire retardants, various organic phosphates, phosphate esters, phosphorus compounds, phosphorus oxides and other fire retardants can be used for fire retardant modification of polyester. Among them, aromatic phosphates have good thermal decomposition stability, and their addition to the polyester melt will have little effect on the thermal degradation of polyester, thus not affecting the spinning process and fiber performance.
Currently, additive fire retardants are widely used in some small polyester production companies. Reactive fire retardants for polyester refer to small molecule fire retardants containing fire retardant elements (phosphorus, chlorine, bromine, nitrogen) and active groups (carboxyl, hydroxyl, acid anhydride, etc.) in the molecule. Reactive fire retardants will gradually replace additive fire retardants. Usually adding a lower content (3%-8%) of fire retardant can make the fiber have good fire retardant effect. Reactive fire retardants that can be used on polyester include halogen and phosphorus fire retardants. Currently, phosphorus-based copolymer fire retardants are commonly used internationally. Phosphorus fire retardants have good fire retardant effects on polyester, and no toxic gases are generated during the combustion process.Environmentally friendly fire protection system. The phosphorus-based fire retardant carboxylic acid alkyl phosphate (SP-FR Ⅱ) developed by Qingdao University in Shandong, my country, is the first copolymerized phosphorus-based fire retardant for polyester successfully developed and commercially produced in my country. It has now reached the level of similar products in the world. technical standards. Japan uses the copolymerization of polyester and hypophosphodioic acid derivatives and the oxide of at least one metal element in groups II, III, and IV in the chemical element table to produce fire-resistant polyester.
3. The progress of research on fire-resistant fibers and fabrics by domestic and foreign companies
1. Shandong Hailong Company
Shandong Hailong Company’s Anfang fireproof fiber and Newdale fiber have achieved good results. Especially Anfang fireproof fiber, which is a new high-tech fiber material with fireproof and melt droplet resistance developed based on the research results of the national “863” program. This product adopts a new generation of fiber fire protection technology – sol-gel technology, which allows the inorganic polymer fire retardant to exist in the nano state or interpenetrating network state in the organic macromolecules of the viscose fiber, which not only ensures the excellent physical properties of the fiber, but also It achieves the characteristics of low smoke, non-toxic, no odor, no melting and dripping. In addition, viscose fiber itself has good moisture absorption and breathability and is easy to color, which greatly improves its application performance, safety performance and added value, and can be widely used in civil, industrial and military fields. The company’s products are very eye-catching. Last year, South Korea and other customers reached an order contract for Anfang fire-resistant fiber.
2. Tangshan Sanyou Group Company
Fireproof fiber, a natural fiber produced by purifying wood or cotton linters as raw materials, is a new product recently launched by Hebei Tangshan Sanyou Group Chemical Fiber Co., Ltd. The fiber adopts new slurry grinding equipment and advanced pre-spinning injection process during the production process. Therefore, the fiber has good spinnability and permanent fire resistance. It is suitable for blending chemical fiber fabrics with a variety of fibers and can be widely used in special operations. Environment, household items, industry, military and other fields.
3. Zhejiang Textile Workwear College
The Key Laboratory of Zhejiang Textile Workwear College has successfully developed high-temperature resistant, fireproof and thermal radiation protective fabrics. This is another successful experimental project of the institute after the successful development of antibacterial sanitary fabrics, oil-resistant and water-repellent fabrics, acid-proof breathable fabrics, multi-functional laminate fabrics, and nano-electromagnetic pulse protective fabrics.
High-temperature resistant, fireproof and thermal radiation protection fabrics are developed using high-temperature resistant high-tech fibers and have the characteristics of high strength, heat resistance, fire protection, arc protection, and thermal radiation resistance. After placing it under the welding flower for 5 minutes, the cloth surface only changed color without obvious damage. After making work clothes, it is suitable for labor protection supplies in fire protection, electric welding, metallurgy, steelmaking and other industries where there is contact with open flames and radiant heat sources.
4. Xinxiang Chemical Fiber Co., Ltd.
After years of experiments, Xinxiang Chemical Fiber Co., Ltd. has successfully developed new varieties of fire-resistant viscose fibers (including filaments and short filaments) and mass-produced them. The fiber has the characteristics of natural cotton, has good hygroscopicity, is comfortable to wear, is biodegradable, and has a limiting oxygen index of more than 29%. The product is suitable for pure spinning and blended chemical fiber fabrics, and can also be used as fireproof filler, especially suitable for aircraft. , cars, hotels, karaoke bars, Internet cafes and other public places and fire-fighting protective clothing. The successful development of this product will be of great benefit to public safety.
5. German fabric company
In fire accidents, it is common for fabrics to catch fire and spread. Fabrics, especially chemical fiber products, emit strong toxic fumes when burned. According to research by the European Fire Protection Association (EFRA), a large proportion of people who die in fires every year are suffocated by toxic smoke. The smoke emitted from burning fabrics contains, in addition to carbon monoxide and carbon dioxide, hydrogen cyanide, hydrogen chloride, chlorine, chlorine carbonate, etc. TreviraCS, a new fabric developed in Germany, emits carbon monoxide when burned, which is only equivalent to one-fifth of other fabrics (such as LSZ wool fabric, modified polyacrylonitrile). It does not emit cyanide, chlorine, sulfur dioxide, Hydrogen chloride, hydrogen fluoride and other gases. Generally, the fireproof performance of surface-treated fireproof fabrics gradually decreases over time. However, fireproof products made of TreviraCS fabrics contain phosphorus in the polymer chain when the fiber is synthesized. Since the fiber itself is fireproof, Its performance can be maintained for a long time. The fire resistance is neither affected by cleaning nor by fiber aging.
6. American General Company
Ann Marie Lak, global technical manager for fibers and fabrics at GE Plastics, a subsidiary of General Motors, and Youssef Fakhreddine, global market industrial manager, promoted its new Ultem fireproof material in International Fiber Magazine. It is reported that the state of California in the United States has announced extremely strict fire protection regulations for mattresses. This will undoubtedly promote progress in fireproof material production research. GE’s Ultem resin material is particularly suitable for meeting the California Technical Bulletin (TB) 603 standard regarding bedding fire protection requirements. Ultem polyetherimide (PEI) resin is widely used in materials that need to be fireproof and prevent the spread of smoke, helping manufacturers of mattresses, Simmons and other products to produce products that prevent accelerated combustion by open flames. GE has never used Ultem resin to produce fiber materials in the past, but its scientific and technical personnel are not afraid of the hardships and have begun to evaluate it with downstream manufacturers.� Its potential function in high-energy fabrics and research The imminent implementation of the California TB603 standard has issued a warning to bedding manufacturers, who commonly use polyurethane foam and polyester batting to make products. California standards set out technical requirements, including the use of high-performance materials and different mattress designs, to address this issue.
Another related issue is that halogen material fire retardants can release toxic fumes. EU regulations on Restriction of Hazardous Goods (RoHS) strictly prohibit the use of polybrominated diphenyl ethers (PBDE) often contained in fire retardants. It is estimated that California’s standards will be adopted by other regions, such as the national standards recently announced by the Consumer Safety Commission (CPSC), which require manufacturers to ensure that fireproof materials can meet various market regulatory requirements. GE Ultem resin is an unshaped high-performance polymer that exhibits outstanding high temperature resistance, good strength, large modulus, broad-spectrum chemical resistance, intrinsic combustion resistance and low smoke generation; the glass transition (transition) temperature is 217°C and a relative thermal index (RTI) of 170°C. This polymer can maintain strength and integrity at high temperatures. Ultem resin products have experienced long-term testing in safety facilities and situations requiring strict fire protection standards, such as firefighter helmets, interior decoration materials for airplanes and trains, etc. These are all materials that can be used for mattresses and bedding. key factors.
7. DuPont Company of the United States
The most famous fireproof fabric is Nomex produced by DuPont in the 1960s. It is permanently fireproof and has excellent thermal stability. The U.S. military uses this fiber in its protective workwear. With the wide application of this fiber, DuPont has successively developed a series of improved Nomex products, among which NomexIIIA is the most widely used, consisting of 93% Nomex, 5% Kevlar and 2% antistatic fiber. Kevlar is added to increase the heat, shrinkage and shock resistance of clothing under high-temperature flames and arc flash explosions. Antistatic fiber is added to reduce static electricity and improve wearing comfort.
Nomex has a limiting oxygen index of 28, has a high decomposition temperature, and will not melt under high temperature conditions. Nomex has good thermal stability. After 100 hours of continuous use at a high temperature of 260°C, its strength can still maintain 65% of its original strength. It can still maintain 50% of its original strength after being used for 7 days at a high temperature of 304°C. Nomex also has excellent chemical resistance, that is, resistance to acids, alkalis, oxidants, and organic solvents. It has excellent radiation resistance and has almost no loss of strength under the irradiation of a certain intensity of ultraviolet rays and Y-rays. NomexⅢA is available in white silk and original solution
Two kinds of colored silk. The white silk color has passed the test. It is currently used in industrial fire protection clothing, arc protection clothing, fire extinguishing protective clothing, racing clothing, and welding and furnace work clothing. The Japanese Self-Defense Force uses Nomex and cotton blended chemical fiber fabrics and performs fireproof post-treatment on the cotton.
In addition, DuPont, a leader in labor protection workwear and manufacturing companies, announced that the company has launched DuPont(TM) Protera(TM) products, a new natural fire-resistant fabric with a very functional design to protect people from arc damage. This new product provides a high degree of comfort compared to flame-resistant treated cotton and nylon blended synthetic fabrics, while also meeting the requirements of NFPA 70E Class 2 standards. Compared with work clothes made of cotton and nylon blended chemical fiber fabrics, DuPont Protera work clothes have a longer life cycle value. They are twice as strong as cotton and nylon blended chemical fiber fabrics. After being washed 100 times, they are still twice as strong. . In addition, DuPont Protera’s anti-corrosion protection is natural, and cleaning or wearing it will not affect its function, so it is not afraid of cleaning or bleaching, and does not require special cleaning procedures. Work clothes sewn with DuPont Protera were less damaged than work clothes made of cotton and nylon blended synthetic fabrics. DuPont Protera blended synthetic fabric fibers have a patented design that produces lightweight, comfortable NFPA 70E Class 2 workwear fabrics at a very competitive price in the market. DuPont is a science-based products and services company that applies science to practice to create better, safer, healthier, sustainable progress and critical solutions for people’s lives.
8. Japan’s Toray DuPont and other three companies
Japanese companies Toray DuPont, Ichimura Sangyo and Koyasu recently jointly announced that they have successfully developed a new type of non-woven fabric with high fire resistance and high sound absorption using Kevlar aromatic nylon fiber, which will be used as automotive interior materials. field to put into production and sell this new type of nonwoven fabric. Since this new type of nonwoven fabric does not undergo special fire-proofing, it can control the formaldehyde produced during combustion and can be recycled using simple methods. This new type of non-woven fabric has a double-layer structure and uses the bonding technology independently developed by the three companies to make the product self-extinguishing.
9. Tver Blue Chemical Fiber Co., Ltd.
Tver Blue developed and produced by Tver Blue Chemical Fibers Joint Stock Company is a new type of fire-resistant Nomex. Its production process was jointly studied by the All-Russian Polymer Fiber Scientific Research Institute and Tver Chemical Fibers Joint Stock Company, and a patent was applied for in the Russian Federation. .
Tver blue fiber not only has a high oxygen index, but also has good hygroscopic properties that can reduce static electricity in fabrics. Due to its good coloration, it is suitable for indoor fire-resistant decorative fabrics. When the temperature rises, the fiber does not shrink and has good wearing properties. Its fabrics are mainly used for fire-fighting protective clothing, rescueClothing, welding clothing, steelmaking clothing, military use
Uniforms can also be used for aircraft cabin fireproof decorative items, ocean-going ship fireproof items, interior decoration of high-end hotels, etc.; for purification and filtration of toxic hot gases in the metallurgical industry, and for heat-resistant ironing interlinings, etc. Tver Blue fiber is produced with Russian-made monomers, solvents, and equipment. As early as 2002, Tver Blue Chemical Fiber Co., Ltd. had already achieved more than 50 tons of industrial production of this fire-resistant Nomex.
10. Jinhui Chemical Fiber Company
A few days ago, the Torch Plan project undertaken by Taicang Jinhui Chemical Fiber Industrial Co., Ltd. – fire-resistant polyester fine denier air-textured yarn for home textiles passed the acceptance of the expert group of Taicang Science and Technology Bureau and Taicang Finance Bureau. The acceptance team unanimously agreed to pass the project acceptance and spoke highly of the project. According to reports, fire-resistant polyester fine-denier air-conditioned yarn for home textiles has permanent fire resistance, and the product has good physical and mechanical properties such as elasticity and wear resistance. The product is suitable for manufacturing imitation silk fabrics and imitation wool fabrics, and is an ideal material for fabrics such as decorations and high-end workwear.
The acceptance team carefully listened to and reviewed the project’s work summary, technical summary, economic and financial analysis report, investment implementation analysis of principal and interest repayment and other relevant information, and inspected the production site. They believed that this product currently fills a domestic gap. Substitute for imports, the quality reaches the level of imported products, and its technical performance indicators comply with the “Fireproof Polyester Air Jet Textured Yarn” Q/320585JHH001-2005 standard. In addition, the sales situation of the project products is good. In 2005, 380 tons were produced, with an output value of 10.46 million yuan, and a sales income of 11 million yuan. In 2006, 848 tons were produced, with an output value of 23.34 million yuan, a sales income of 23.31 million yuan, and a profit and tax of 5.12 million yuan. yuan, the quarterly production in 2007 was 1,532 tons, with an output value of 45.4 million yuan, and a sales revenue of 42.05 million yuan. This year, it is estimated that the annual production will be 6,000 tons, with an output value of 169 million yuan, sales of 165 million yuan, profits and taxes of 36 million yuan, and input-output The ratio reaches 1:4.1, and the profit tax rate is 21.8%. achieve expected economic indicators. It is reported that after the project passes acceptance, Taicang Jinhui Chemical Fiber Industrial Co., Ltd. is planning to build a technology research and development center.
11. Shandong Jinan Zhenghao Company
⑴ Fire-resistant polyester short fiber
Fire-resistant polyester short fiber is produced by Jinan Zhenghao Chemical Fiber New Materials Co., Ltd. using phosphorus-based fire-resistant polyester polyester chips as raw materials, with an annual production capacity of more than 7,500 tons. The main variety produced is 1.5D×38mm fire-resistant polyester staple fiber (Puqiang cotton type), and other types of fire-resistant medium-length staple fiber are also produced in various specifications.
The fire-resistant staple fiber produced by the company has good spinnability, stable quality, uniform and efficient fire-resistant performance, and can produce fire-resistant polyester yarns of different specifications from 6S to 40S. The company’s self-produced 24S fire-resistant polyester yarn and fire-resistant plain fabric have a limiting oxygen index of more than 33%. They have been exported to Europe and the United States and other countries, and are deeply loved by users at home and abroad.
⑵ Fireproof polyester filament
Jinan Zhenghao Chemical Fiber New Materials Co., Ltd. adopts German Bamarg’s patented technology and uses phosphorus-based fire-resistant polyester polyester chips as raw materials for indirect spinning to produce fire-resistant pre-oriented yarn (POY). Fireproof polyester low stretch yarn (DTY), product fineness range 55dtex/36f-330dtex/36f.
The fire-resistant filament produced by this company has stable performance, low fineness deviation, strength unevenness and elongation unevenness, uniform coloring, long-lasting fire-proof performance, good finishing performance, and is suitable for various types of weaving. Machines and finishing equipment are used to produce various decorative fabrics.
12. Taiwan Lili Enterprise Co., Ltd.
The Lili fireproof fiber of Taiwan Lili Enterprise Co., Ltd. is a newly developed environmentally friendly fire-resistant polyester. During the polymerization process, a non-halogen phosphorus-based reactive fire retardant is added to form a copolymer to modify the polymer: making the fiber It has permanent fireproof effect.
Product features:
●Non-toxic, non-smoking, and will not produce harmful substances;
●It is a permanent reactive type with good fire resistance and good effect;
● Halogen-free;
● Good colorability and good hand feel.
Inspection standards: CNS 10285 L3196-1995 A1, CNS 10285 L3196-1995 A4, CAL. TB 117 Section E, NFPA-701-1999 product applications: home furnishings, curtains, automotive interior decoration, bedding, medical curtains.
4. In terms of domestic post-finishing fire protection, Xinxiang Xinxing Special Fabric Co., Ltd., as the representative, has developed a variety of new products based on foreign PROBAN fire protection technology, and its performance fully meets or exceeds similar foreign products.
Fireproof performance: no smoldering, no afterburning, no dripping, good hand feel,
It can still meet strict fire protection standards after being washed more than 50 times
Fire protection standards: EN470-1, EN531, EN533, EN532, EN469, EN343, NFPA2112, NFPA70E, EN11611, EN11612
4. Conclusion
At present, there are dozens of varieties of fire-resistant fibers on the domestic and foreign markets. Traditionally finished fire-resistant fibers are mainly fire-resistant polyester, fire-resistant polyacrylonitrile fiber, and fire-resistant vinylon. With the advancement of science and technology, various countries have recently developed and produced a variety of fire-resistant fibers, such as polym-phenylene isophthalamide fiber, polyamide-imide fiber, polyimide 2080 fiber, heterocyclic polymer polyamide fiber, etc. Benzimidazole fiber (PIM2080), phenolic fiber, Basofil fiber. These fibers have relatively good fireproofing effects and are widely used in industrial and emergency fields.
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