I. The origin of high-performance fiber 
Thousands of years ago, humans only used natural materials. At that time, cowhide was cut into straps for bow and arrow strings, providing enough tension and elasticity, which may be called "high-performance straps". Since the industrial revolution, with the rapid advancement of science and technology, especially in the past century, artificial materials have gradually entered people's field of vision, and high-performance fibers have also emerged.

As early as 1860, the British scientist Sir Joseph Wilson Swan (1828-1914) invented a semi-vacuum carbon filament electric lamp with carbon paper strips as the illuminant, which is also known as the incandescent lamp. prototype. In 1879, Edison invented the incandescent lamp with carbon fiber as the light source. He shapes materials rich in natural linear polymers, such as linden inner bark, jute, abaca or hemp, into the desired size and shape and bakes them at high temperatures. When heated, these cellulose fibers, which are composed of continuous glucose units, are carbonized into carbon fibers. In 1892, Edison's incandescent light bulb carbon fiber filament manufacturing technology (Manufacturing of Filaments for Incandescent Electric Lamp) obtained a US patent (USP470925).
The rapid development of organic high-performance fibers began in the mid-20th century. With the development of organic synthetic chemistry and fiber forming technology, scientists can synthesize rigid or semi-rigid polymers with molecular chains through molecular structure design, with high strength and high modulus. It provides raw materials for the spinning of high-performance fibers, and the emergence of liquid crystal spinning technology provides technical support for the large-scale preparation of high-performance fibers. A typical example is that polyparaphenylene terephthalamide (PPTA) is easy to form liquid crystals in concentrated sulfuric acid, and PBO can also form liquid crystals in polyphosphoric acid. It is highly oriented along the fiber axis to obtain high-strength and high-modulus para-aramid fibers (PPTA) and PBO fibers; while polyarylate fibers use the thermotropic liquid crystal characteristics of the bulk to orient their molecular chains to obtain high-strength fibers.

The rapid development of organic high-performance fibers began in the mid-20th century. With the development of organic synthetic chemistry and fiber forming technology, scientists can synthesize rigid or semi-rigid polymers with molecular chains through molecular structure design, with high strength and high modulus. It provides raw materials for the spinning of high-performance fibers, and the emergence of liquid crystal spinning technology provides technical support for the large-scale preparation of high-performance fibers. A typical example is that polyparaphenylene terephthalamide (PPTA) is easy to form liquid crystals in concentrated sulfuric acid, and PBO can also form liquid crystals in polyphosphoric acid. It is highly oriented along the fiber axis to obtain high-strength and high-modulus para-aramid fibers (PPTA) and PBO fibers; while polyarylate fibers use the thermotropic liquid crystal characteristics of the bulk to orient their molecular chains to obtain high-strength fibers. .

Figures 1-3 show the number of global patents and publications for high-performance fibers and specialty fibers searched by SciFinder. Obviously, the research of high-performance fibers has developed rapidly since the 21st century, especially the continuous development of application fields and the increase in the amount of use have promoted the technological progress and large-scale production of high-performance fibers, and reduced the production cost of fibers. Expanded the application market.

II. Development of organic high-performance fibers

As mentioned in the previous section, the development of organic fibers benefited from the synthesis of spinnable polymers and the advancement of fiber processing technology. The 1950s and 1970s were the golden age for the synthesis and development of high-performance polymers. During this Cold War The development of high-performance polymers and fibers in this period is mainly to meet the needs of weapons and special protection.

American DuPont discovered the lyotropic liquid crystal phenomenon of aromatic polyamides in the late 1960s, and realized the industrial production of poly(p-phenylene terephthalamide) fibers in 1972, with the trade name Kevlar. Subsequently, Akzo Nobel of the Netherlands, Teijin of Japan, Cologne of South Korea and Hyosung also developed their own products one after another. In 2000, Japan's Teijin Corporation acquired Twaron in the Netherlands and carried out production and large-scale expansion. Russia has been committed to the research and development and production of high-strength aramid, and has made great breakthroughs in the research of heterocyclic aramid, and developed a series of products, such as SVM, Terlon, Armos, Rusar, etc. The research and development of para-aramid in my country is not too late. The main research units include the Institute of Chemistry, Chinese Academy of Sciences, Shanghai Institute of Synthetic Fiber, Sichuan Chenguang Chemical Research Institute, Donghua University (formerly China Textile University) and Tsinghua University. From 1972 to 1991, it went through the stages of laboratory research, small test and pilot test, and was listed as a major national scientific and technological research project and the "863" plan of the Ministry of Science and Technology, and achieved a number of research results. The limitations of the overall level of science and technology have affected the industrialization of this fiber. At the beginning of the 21st century, para-aramid in my country ushered in a new development boom, and made major breakthroughs in engineering research, forming large-scale industries in Yantai, Shandong, Dongying, Shandong and other places.

Also in the 1960s, the materials laboratory of SRI (Stanford Research International) in the United States designed and synthesized a variety of special polymers to meet the requirements of the US Air Force for high temperature polymer materials, mainly including PBO, polyphenylene benzo Dithiazole (PBZT), polyphenylene benzimidazole (PBI). Among them, PBI is the earliest fiber developed (in 1961). It has excellent flame retardant properties, and the LOI value reaches 40, but its mechanical properties are general. Then in 1977, PBZT fiber was also prepared, and its breaking strength reached 2.4GPa and modulus was 250GPa. The company that first invested in the research and development of PBO fiber was Dow Chemical Company, but Dow did not succeed in the industrialization of PBO fiber, and transferred the patent to Japan's Toyobo in the early 1990s, and Toyobo succeeded in the small test in 1995. , In 1998, a pilot line was established and commercial production began under the trade name Zylon. Since the 1990s in China, East China University of Science and Technology, Donghua University, Shanghai Jiaotong University, Harbin Institute of Technology, the 43rd Institute of the Fourth Academy of China Aerospace Science and Technology Corporation, and the Harbin FRP Research Institute have successively carried out PBO monomer, polymerization process, Fiber preparation and research on fiber-reinforced composite materials.
The research on polyimide fibers also began in the 1960s. In 1965, DuPont reported the preparation of polyimide fibers by wet spinning, namely, pyromellitic anhydride (PMDA) and 4,4′. - Diaminodiphenylmethane (MDA) to synthesize polyamic acid in DMF, and then wet spinning with water as coagulation bath at room temperature to obtain polyamic acid fiber, and dimethylformyl fiber obtained after spun silk is stretched and dried The mechanical properties are poor, the breaking strength is 9.7cN/dtex, the initial modulus is 38.8cN/dtex, and the elongation at break is 6.5%. In the 1980s, with the improvement of synthesis technology, some polyimides could be dissolved in phenolic solvents, which laid the foundation for the preparation of high-strength and high-model polyimide fibers by one-step method. Among them, Akron University in the United States has prepared polyimide fibers from synthesis, published many research papers, and applied for patents, but no related products have been put on the market. At the same time, there have also been literature reports on one-step spinning of polyimide fibers in Japan. In addition to high temperature resistance and radiation resistance, its mechanical properties have also reached the characteristics of high strength and high modulus [6]. In the 1990s, Russian scientists added pyrimidine units to the polymer, and the strength of the polyimide fiber obtained by the two-step spinning method reached 4.2GPa and the modulus was 144GPa [7]. But the real polyimide fiber is not industrialized.At the beginning of the 21st century, Donghua University, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Sichuan University, Beijing University of Chemical Technology and other units successively carried out research on polyimide fibers. , National Development and Reform Commission Strategic Emerging Industry Special Project, National Natural Science Foundation of China and other projects have provided strong support, and currently two thousand-ton industrial production lines have been formed.
The basic theory of UHMWPE fibers was first mentioned in the 1930s. In the late 1970s, the Dutch DSM company successfully used the gel spinning method (Gel spinning) to spin UHMWPE fibers, and began industrial production in 1990, with the trade name Dyneema. The company is the founding company of UHMWPE fiber and the manufacturer of the fiber with the highest output and best quality in the world, with an annual output of about 5000t. In the 1980s, the American Allied-Singal Company purchased the patent of the Dutch DSM Company, developed its own production process and industrialized it. In 1990, Allied Signal was merged by Honeywell and continued to produce ultra-high molecular weight polyethylene fibers with an annual output of about 3000t[8]. The Chinese Academy of Textiles started the research and development of the fiber production process in the 1980s. In the 1990s, Donghua University also joined the research and development work. It was successfully developed in 1999 and entered the commercial production stage in 2000. At present, the dry and wet spinning process is generally used in China. The main manufacturers are Beijing Tongyizhong, Hunan Zhongtai, Ningbo Dacheng and other companies. The equipment cost is 10% of the decalin method, and the output is 95%. The overall manufacturing cost Low;A small number of enterprises use the decalin method, which requires high equipment investment, high manufacturing costs, and imports of resin solvents. At the end of 2008, Sinopec Yizheng Chemical Fiber Co., Ltd., based on the complete set of high-performance polyethylene fiber dry spinning technology jointly developed by China Textile Research Institute and Sinopec Nanhua Group Corporation Research Institute, built the first domestic production line. 300t dry spinning high performance polyethylene fiber industrial production line.

Another high-temperature resistant fiber is polytetrafluoroethylene (PTFE) fiber, which was first developed by DuPont and includes a variety of specifications, such as monofilament, multifilament, staple fiber and membrane split fiber, and began production in 1953, trade name For "Teflon" [9, 10]. In the 1970s, Austrian Lenzing Company successfully prepared PTFE membrane split fibers by membrane splitting method, and its strength was similar to the strength of fibers obtained by emulsion spinning method. In 1979, Germany developed polyvinylidene fluoride fiber. In 2000, Japan's Toyo Polymer Company developed fine fluorine fibers composed of perfluororesin, with diameters of 15 μm and 20 μm, respectively.

At the same time as the development of these main high-performance fibers, other organic high-performance fibers have also developed rapidly, such as aramid fibers (typically Tanlon), polyarylate fibers (typically Vectran), polybenzoyl Imidazole fiber, PIPD fiber (M5), polyetheretherketone fiber, etc. These special fibers have played an irreplaceable role in some high-tech fields with their special properties (such as corrosion resistance, high temperature resistance, high compressive strength, etc.).