Thermoplastic Rubber (TPR)
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Thermoplastic Rubber-TPR, also known as Thermoplastic Elastomer (TPE), is a material that combines the properties of rubber and thermoplastics. Thermoplastic elastomers have a variety of possible configurations. The most fundamental one is the need for at least two mutually dispersed polymer phases. At normal use temperatures, one phase is a fluid (making the temperature above its Tg-glass transition temperature). The other phase is a solid (so that the temperature is below its Tg or equal to Tg) and there is an interaction between the two phases. That is, the rubber material exhibits rubber elasticity at normal temperature and can be plasticized at a high temperature. It has rubber-like mechanical properties and performance properties, and can be processed and recovered according to thermoplastics. It is set up between plastic and rubber. a bridge. Thus, thermoplastic elastomers can process rubber articles as quickly, efficiently, and economically as thermoplastics. In terms of processing, it is a kind of plastic; in terms of nature, it is a kind of rubber. Thermoplastic elastomers have many advantages over thermoset rubber. At present, there is no uniform naming of thermoplastic elastomers. It is customary to use the English acronym TPR for thermoplastic rubber and TPE for thermoplastic elastomers, both of which are used in related materials. For the sake of consistency, they are referred to as TPE or thermoplastic elastomers.
I. Types and performance characteristics of thermoplastic elastomers Thermoplastic elastomers (TPE) can be summarized into two types, general-purpose TPE and engineering TPE. At present, they have developed into more than 30 varieties of l0 categories. From 1938, Bayer, Germany, first discovered polyurethane TPE. In 1963 and 1965, Phillips and Shell of the United States developed styrene-butadiene-styrene block polymer TPE. In the 1970s, the United States, Europe and Japan began mass production of olefins. Since TPE, the technology has been continuously innovated, and new varieties of TPE have emerged, which constitutes a huge system of TPE today, which makes the rubber industry and the plastics industry take a step forward. The world's industrially produced TPEs are: styrene (SBS, SIS, SEBS, SEPS), olefins (TP0, TPV), dienes (TPB, TPI), vinyl chloride (TPVC, TCPE), urethane Classes (TPU), esters (TPEE), amides (TPAE), organofluorines (TPF), silicones and vinyls cover almost all areas of synthetic rubber and synthetic resins. They are formed by a rubber phase which forms a hard segment and a soft phase in the main chain, and is firmly combined with each other. The manufacturing method of TPE can be roughly divided into two types: chemical polymerization and mechanical blending. The former is formed separately in the form of a polymer, and has a main chain copolymerization, a coupling copolymerization, and an ion polymerization. The latter is mainly a blend of rubber and resin, among which is a dynamic vulcanizate (TPE-TPV) and an interpenetrating network polymer (TPE-IPN) which are present by cross-linking vulcanization. Nowadays, TPE is centered around TPS and TPO and has developed rapidly around the world. The production and consumption of TPE has accounted for about 80% of all TPE. Diene TPE and vinyl chloride TPE have also become important varieties of general purpose TPE. Others such as TPU, TPEE, TPAE, TPF, etc. turned to engineering. At present, in the world trade market, the price of general-purpose TPS, TPO and TPVC is about 500-1400 US dollars; while TPE, TPEE, TPAE and other TPEs with high heat resistance, oil resistance, high strength and high wear resistance are higher. The versatility is about 50% to double; the high-performance TPE class can even reach 20,000 to 30,000 US dollars a ton. The advantages of TPE are mainly reflected in the following aspects: (1) It can be processed by general thermoplastic molding machines, such as injection molding, extrusion molding, blow molding, compression molding, transfer molding, etc.; Vulcanization of the molding machine, the time can be shortened to less than 1min from the original 20min; (3) The vulcanization can be formed by the extruder, the extrusion speed is fast, and the vulcanization time is short; (4) The waste generated during the production process (escapes the burrs, squeezes Waste plastics and the final waste products can be directly returned for reuse: (5) Used TPE old products can be reused after simple regeneration, reducing environmental pollution and expanding sources of resource regeneration; (6) No need for vulcanization, saving energy For example, the energy consumption of high-pressure hose production is 188 MJ/kg for rubber and 144 MJ/kg for TPE, which can save more than 25% of energy; (7) The self-reinforcing property is large, and the formulation is greatly simplified, so that the compounding agent is polymerized. The influence restriction is greatly reduced, and the quality performance is easier to master; (8) Opening up new ways for the rubber industry and expanding the application field of rubber products. The disadvantage is that the heat resistance of TPE is not as good as that of rubber. As the temperature rises, the physical properties decrease greatly, so the scope of application is limited. At the same time, the compression deformation, springback, and durability are equivalent to rubber, and the price is often higher than that of similar rubber. But in general, the advantages of TPE are still very prominent, and the shortcomings are constantly improving. As a new energy-saving and environmentally friendly raw material for rubber, the development prospects are very promising. Second, the development status of the main thermoplastic elastomers 1. Styrene TPE Styrene TPE, also known as TPS, is a copolymer of butadiene or isoprene with styrene block type, and its properties are closest to SBR rubber. At present, the output of the world TPS has reached more than 700,000 tons, accounting for about half of all TPE. The representative variety is styrene-butadiene-styrene block copolymer (SBS), which is widely used in the footwear industry and has mostly replaced rubber; it is also used in industrial rubber products such as tapes and rubber sheets. Constantly expanding. SBS is also widely used as an impact modifier for PS plastics, and is also an excellent modifier for asphalt pavement asphalt pavements for wear resistance, crack resistance, softness and slip resistance. The PS plastic modified with SBS not only greatly improves the impact resistance like rubber, but also has excellent transparency. Compared with SBR rubber and WRP rubber powder, SBS modified asphalt pavement is more soluble in asphalt. Therefore, although the price is more expensive, it is still used in large quantities. Nowadays, waterproof membranes are further promoted to waterproof and moisture-proof roofs, subways, tunnels, trenches, etc. SBS is made of S-SBR and NP rubber. It is more rubbery than PVC and EVA plastic sponge. It is lighter than vulcanized rubber, with bright colors and clear patterns. Therefore, it is not only suitable for the sponge of the rubber sole, but also an ideal material for the disposable outsole such as sneakers, sports shoes and fashion shoes. In recent years, the block styrene polymer (SIS) of isoprene-substituted butadiene has developed rapidly, and its production has accounted for about 1/3 of the amount of TPS, and about 90% is used for the binder. The hot melt adhesive made of SIS is not only excellent in viscosity but also good in heat resistance, and has become the main material of hot melt adhesives in the United States, Europe and Japan. The biggest problem with SBS and SIS is that it is not heat resistant, and the use temperature generally cannot exceed 80 °C. At the same time, its strength, weather resistance, oil resistance, wear resistance, etc. are also not comparable to rubber. To this end, in recent years, the United States and Europe have carried out a series of performance improvements, and there have been SEBS and SEPS of saturated hydrogenation of SBS and SIS. SEBS (hydrogenation of BR as a soft segment) and SEPS (with IR hydrogenation as a soft segment) can greatly improve the impact strength, weather resistance and heat aging resistance. In 1984, Mitsubishi Chemical of Japan made a better performance mixture based on SEBS and SEPS, and named the saturated TPS as “Rubberronâ€. Therefore, SEBS and SEPS are not only general-purpose, but also blending materials for engineering plastics that improve weather resistance, wear resistance and heat aging resistance, so they quickly developed into nylon (PA), polycarbonate (PC) and other projects. A compatibilizer for plastic "alloys". In addition, many new varieties such as high-transparency TPS for epoxy resin and bio-toxic TPS for medical and health use have been developed. SBS or SEBS and the like are melt blended with PP plastic, and can also form IPN type TPS. The so-called IPN is actually a polymer in which two networks are interpenetrated, so it is also called an interpenetrating network compound. Although most of them belong to thermosetting resins, there are many thermoplastic elastomers such as TPE which are expressed in a cross-continuous phase. IPN-TPS formed from SBS or SES as a substrate and other engineering plastics can be directly coated without pretreatment. The coating is not easy to scratch, and has certain oil resistance. The elastic modulus does not change in the wide temperature range of low temperature; the cold resistance and heat resistance of engineering plastics are greatly improved. The styrene compound and the rubber joint copolymer can also be made into thermoplastic TPE, and EPDM/styrene, BR/styrene, CI-IIR/styrene, NP/styrene and the like have been developed. The world's largest manufacturer of TPS is Shell Chemical. With more than 40 brands under the trade names of Kraton and Carifles, it is sold all over the world. Only the local installation capacity reached 232,000 tons in 1998. It is said to have increased in recent years. In France and Germany, there are also 30,000 tons. Production equipment. American Phillips Petro. The product name is Solprene, with a capacity of 35,000 tons. Japan's Asahi Kasei, elastomers, Italy's Enichem, Belgium, Spain, Mexico, Australia and other countries also use its technology to produce, ranging from 0.5 million to 28,000 tons. Japan's JSR and Russia each have their own technology with a production capacity of 25,000 tons. Taiwan Chimei has a 90,000 t SBS (including S-SBR) production unit. China is the world's largest consumer of TPS. Since 1980, it has been centered on SBS, along with China's footwear industry (with an annual output of 6 billion pairs, accounting for half of the world's rubber shoes production) and construction industry (annual waterproofing membranes of 130 million m, Among them, SBS and APP modified asphalt 80 million M2, ranking first in the world) and road industry (highway 25,000 km, the world's second) demand for TPS, in 1999 was 250,000 tons, 2000 was 300,000 tons, 2001 The annual amount is 350,000 tons, and it is estimated that it will reach 400,000 tons in 2002. The national production in 1999 was 88,000 tons, in 2000 it was 133,000 tons, in 2001 it was 168,000 tons, and in 2002 it reached 216,000 tons, with an average annual growth rate of more than 12%. At present, it is still unable to meet the expanding needs of the market. More than half of them are imported from abroad, of which Taiwan has 10 million tons, 80% of which is used for shoemaking, and the remaining 80,000 tons are imported from South Korea, Japan, Russia and other places. In 2001, domestic SBS used for 270,000 tons of shoes, accounting for 78%, road asphalt modified 45,000 tons, accounting for 13%, other adhesives, waterproof membranes, plastic modification accounted for 3.8%, 3.2% and 2%. After the successful development of SBS by Beijing Yanshan Petrochemical Research Institute in 1982, there are currently three petrochemical enterprises in production. Beijing Yanshan Petrochemical has an annual production capacity of 60,000 tons and a production capacity of 40,000 tons. Yueyang Petrochemical has an annual production capacity of 100,000 tons and a production capacity of 130,000 tons. Maoming Petrochemical has an annual production capacity of 50,000 tons and a production capacity of 50,000 tons. In addition to SBS, a small amount of SIS and SESS are produced. The production number is up to 25, and the product application covers many fields such as shoe making, road asphalt modification, plastic modification, waterproof coil and adhesive. Mainland China has become one of the world's three major TPS production bases, and TPS production technology has been introduced to Taiwan and Italy. 2. The olefinic TPE olefin TPE is a blend of PP as a hard segment and EPDM as a soft segment, abbreviated as TPO. Because it has a lighter specific gravity than other TPEs (only O.88), heat resistance up to 100 ° C, weather resistance and ozone resistance, it has become another fast-growing variety in TPE. Since its first listing in the United States by Uniroya I in the United States under the trade name of TPR in 1972, it has grown by double digits for many years. In 2000, the production volume reached 350,000 tons, and by 2002 it was estimated to reach 400,000 tons. Now, TPO has become the main rubber and plastic material in the field of automobiles and home appliances such as the United States, Japan and Europe. Especially in the car has accounted for 3/4 of its total, the car bumper made with it has basically replaced the original metal and PU. In 1973, the dynamic partially vulcanized TPO appeared. Especially after the successful development of the fully dynamic vulcanized TPO named by Santoprere in 1981, the performance of the company was greatly improved. The maximum temperature was 120 °C. This dynamic vulcanization type TPO is abbreviated as TPV, which is mainly used to add a cross-linking agent capable of vulcanizing a mixture of PP and EPDM in TPO during melt blending, and mechanically shearing using an internal mixer or a screw machine. The force is such that the particles of the fully vulcanized fine EPDM crosslinked rubber are sufficiently dispersed in the PP matrix. Through the "particle effect" of the crosslinked rubber, the compression deformation resistance, heat aging resistance, oil resistance, etc. of the TPO are significantly improved, even reaching the level of the CR rubber, and thus it is called thermoplastic vulcanization. gum. Utilizing the oil resistance of TPV, it has been used to replace NBR and CR to manufacture various rubber products. TPV can also be blended with PE and used in combination with other TPEs such as SBS to complement performance. Nowadays, it has been widely used in automobiles as gears, racks, ignition wire sheaths, oil-resistant hoses, air ducts, and crack-resistant gloss seals for high-rise buildings, as well as wire and cable, food and medical fields, and its growth rate greatly exceeds TPS. In recent years, Germany has introduced a polymeric TPO based on TPV, which has made a new breakthrough in the toughness and low temperature resistance of TPV. The United States has also developed a more comprehensive IPN type TPO. In 1985, a fully dynamic vulcanized PP/NBR-TPV appeared, which was grafted with maleic anhydride and partially PP, and partially treated with NBR to form an amine terminated NBR. This kind of copolymer which can form a small amount of joints and blocks in the dynamic vulcanization process can replace NBR for seals, hoses, etc. in aircraft, automobiles, machinery and the like. This blend is incompatible with each other due to the polarity of the two materials, so a MAC compatibilizer must be added during blending. Such compatibilizers are mainly: ethylene polyamine compounds such as diethylenetriamine or triethylenetetramine, as well as liquid NBR and polypropylene maleic anhydride compounds. In 1988, Malaysia successfully developed PP/NR TPV, which has high tensile and tear strength, and greatly improved compression deformation. The heat resistance can reach 100-125 °C. In the same period, PP/ENR--TPV was also developed, which is obtained by reacting NR with peracetic acid to form epoxidized NR and then melt blending with PP. Performance is better than PP/NR-TPV and PP/NBR--TPV for automotive parts and wire and cable. During this period, PP/IIR-TPV, PP/CI-IIR-TPV appeared in the UK, and the United States developed a series of melt blending of PP/SBR, PP/BR, PP/CSM, PP/ACM, PP/ECO, etc. Material, Germany made PP / EVA, making PP and various rubber blends have been successful. In addition, EPDM/PVC, IIR/PE, etc. appearing in ET Polvmer, Rucodur and other products are also seen in the market. At present, TPE prepared by blending in the form of dynamic full vulcanization technology has covered 11 rubbers and 9 resins, and 99 rubber-plastic blends can be produced. The vulcanized rubber has a crosslink density of 7×10-5 mol/ml (determined by swelling method), that is, 97% of the rubber is crosslinked and vulcanized, the tensile elongation is more than 100%, and the tensile permanent deformation is less than 50%. . Currently, the representative varieties of Santoprone (EPDM/pp-TPV) and Geolast (NBR/PP-TPV) produced by AES (Monsanto) are widely used in various fields such as machinery, electrical, construction, food, and medical halls. Especially in the car, it has accounted for 30% to 40%, and the TPE consumption of each car in foreign countries has reached 10kg, accounting for about 10% of auto parts. TPV can produce a wide range of parts in the form of general blow molding, injection molding and extrusion molding of plastics. Blow molded products include automotive air purifier ducts, gear cover guards, coupling jackets, and the like. Injection molded products include plug gaskets, mirror gaskets, pedal brake pads, brake booster conduit jackets, crankcase jackets, etc., and can also be manufactured with timing belts. The extruded product has a wire and cable sheath, a fuel tube outer layer of glue and various sealing strips. Especially for automotive sealing strips, the use of TPV has become fashionable, including solid and foamed products, static seals and quasi-dynamic/dynamic sealing products, etc., which have basically replaced rubber. At present, in the olefin-based TPE, TPO accounts for about 80% to 85%, and TPV accounts for 15% to 20%. For this reason, the world's other well-known EPDM synthetic rubber manufacturers have launched their own characteristics of TPO, TPV production grades. In order to adapt to different processing methods and uses, generally more than 10-20 kinds. Although they are mostly unpublished for specific production methods and throughput, they are all various melt blends of olefins. Melt blended TPV is becoming a new rubber and plastic material and the most popular research and development topic for various rubber and plastic manufacturers. There are also various blends of various TPO-TPVs, such as EPDM/PP TPV and NBR/PP--TPV, ACM/PP TPV and EPDM/PA-TPV, etc., which are also becoming new modified blends. The production and use of TPO-TPV in China began in the second half of 1990, especially with the rapid development of the automobile industry. The TPO-TPV consumption increased rapidly by 1%-20% per year. At least half of the 3.25 million cars produced in 2002 have used bumpers and interior and exterior trim panels and parts made of TPO-TPV. The national consumption of EPDM has reached 55,000 tons in 2002 (22,000 tons of domestic production), of which 18%-2 2% is used for polyolefin modifiers, so as to calculate the production volume of TPO-TPV. Ten thousand above. In addition, if the production of foreign-funded enterprises is not included in the statistics, it is impossible to ascertain the exact amount. In TPO-TPV, TPV accounts for approximately 5%-20%. The consumption in 2001 is estimated to be 3,000 tons, 80% of which is from the US AES, TRS. Imports from Dutch DSM and Taiwan Nandi. There are 8-10 domestic main manufacturers, all of which are small and medium-sized factories with a capacity of about 1000t. Due to performance and quality problems, the total sales are only 500-600t. Since the 1980s, Tsinghua University, Beijing Institute of Chemistry of the Chinese Academy of Sciences and Changchun Yinghua Institute, Beijing University of Chemical Technology, Shanghai Jiaotong University, Beijing Chemical Industry Research Institute and Petrochemical Group's Yangzi, Jinling, Yanshan and other companies have developed TPO. Among them, Changchun Yinghua Institute, Shanghai Jiaotong University, Yangzi and Jinling Petrochemical also developed TPV, and tried it in wire and cable, building waterproofing membranes, automotive sealing strips, protective covers, and various pipes and toothed belts. Qingdao University of Science and Technology also applied for PP/NBR-TPV national patents, and the South China Tropical Crops Research Institute tracked the P P/NR--TPV research project. However, due to various reasons, in addition to the EPDM/PP-TPV thermoplastic vulcanizate, there are still very few other industrializations. So far, there are no large-scale professional manufacturers in China. TPV is the fastest growing family in the TPE world with an annual growth rate of 10%-20%. Because its processing method and performance are the closest to vulcanized rubber, it is mainly in the United States, and its coverage on automobiles and other products is very broad and has great development potential. At present, foreign seals, sheaths, liners, foreskins, etc. are transferred to TPV in large quantities, and the global consumption of TPO-TPV has reached 360,000 tons. However, China's current consumption is less than 25,000 tons (TPV 3000t), only 7% of the world's TPO-TPV, and the price of lt external goods is as high as 4,000-5,000 dollars, which limits the promotion. If the price can be lowered to the normal level in the future, it is equivalent to or slightly higher than the price of similar rubber, and the demand will increase exponentially. In terms of rubber sealing strips, there are currently more than 40 production lines in the country. The 12 major rubber sealing strip manufacturers have an annual output of 90 million m and a capacity of 180 million m. For example, half of the TPE is used, and the weight is 0.4 kg. That is, TPO-TPV is required to be 18,000 tons, and the TPV is at least between 3000 and 4000 tons. Coupled with the expansion of TPO-TPV for other products, the demand for TPO TPV in the next five years will likely reach 3.5-45 million tons, of which TPV will reach 0.7-90,000 tons. Due to the poor performance quality of domestic TPV and the high price of imported TPV, experts predict that domestic consumption will only reach 5000-6000t in 2005 and 1.0-18,000t in 2010. 3. The diene TPE diene TPE is mainly an isomer of natural rubber, so it is also called thermoplastic trans natural rubber (1-NR). As early as 400 years ago, people discovered this material as natural rubber, but because it is produced from wild trees such as Gutapo and Balata, which are different from the Hevea tree, it is called Gutabo Rubber and Ba. Lata rubber. Although T-NR has been used as a submarine cable and golf ball for more than 100 years, it has a thermoplastic state, strong crystallinity, limited availability, and its use has not been extended for a long time. After 1963, the United States, Canada, Japan and other countries have made synthetic T-NR-trans polyisoprene rubber, called TPI, with organometallic catalyst. Its microstructure is exactly the opposite of that of isoprene rubber (IR). The trans combination is 99%, the crystallinity is 40%, and the melting point is 67 °C. It is very similar to the natural Guttapo and Balata rubber. As a result, natural products have begun to be gradually replaced and further developed for use in orthopedic appliances, gypsum substitutes and sports protection equipment. In recent years, the use of TPI's excellent crystallinity and temperature sensitivity has been successfully developed as a shape memory rubber material, which has been favored by people. Structurally, TPI is a thermoplastic rubber formed by combining a crystal structure formed by a high trans structure as a hard segment and a soft segment of any remaining portion in an elastic phase state. Compared with other TPEs, the advantages are mechanical strength, good scratch resistance and vulcanization. The disadvantage is that the softening temperature is very low, generally only 40-70 ° C, and the use is limited. At present, only Canada Polysar and Japan Kurary are in production, and the output is estimated to be about 10,000 tons. Qingdao University of Science and Technology in China has also successfully developed TPI in the near future, and has conducted trials using it to obtain the second prize of the National Technology Invention. In addition, there are a large number of Eucommia rubbers produced in the Eucommia ulmoides in the areas of Hunan, Hubei, Sichuan and Guizhou. It is also a kind of trans l, 4 polyisoprene natural rubber with abundant resources. , has considerable development potential. In 1974, JSR Corporation of Japan developed the isomer of BR rubber (cis-1,4 polybutadiene) - the same as 1,2 polybutadiene, referred to as TPB. It is a syndiotactic polybutadiene rubber containing more than 90% of the combination of l and 2, and the trade name is RB. The microstructure is a block polymer composed of a crystalline portion of the same structure between the hard segments and an arbitrarily soft portion of the soft segment. At present, only one Japanese manufacturer in the world, although its heat resistance and mechanical strength are not as good as rubber, it is widely used in shoes, sponges, light films, etc. due to its good transparency, weather resistance, electrical insulation and photodecomposition. In other industrial rubber products, the annual demand has exceeded 27,000 tons. The biggest difference between TPB and TPI is that it can be vulcanized. Solved the general TPE can not be sulfided with sulfur, peroxide. It is necessary to use special devices such as electronic waves and radiation. It can improve the quality of the TPE, thus improving the heat resistance, oil resistance and durability of the TPE. TPB can be arbitrarily processed within the melting point range of 75-1 10 ° C. It can be used to produce non-vulcanized injection molded slippers, casual shoes, or vulcanized foam to make midsole for sports shoes, travel shoes, etc. Compared with the bottom of the EVA sponge, it is not easy to collapse and deform, and it is comfortable to wear, which is beneficial to improve sports performance. The film made by TPB has good gas permeability, water resistance and transparency, is easy to be decomposed by light, and is very safe. It is especially suitable for household and vegetable and fruit fresh-keeping packaging. 4. Vinyl chloride TPE is divided into two categories: thermoplastic PVC and thermoplastic CPE. The former is called TPVC and the latter is called TCPE. TPVC is mainly an elastic modification of PVC, which is divided into chemical polymerization and mechanical blending. Mechanical blending is primarily a blend of partially crosslinked NBR blended into PVC (PVC/NBR). TPVC is actually an extension of soft PVC resin, just because the compression deformation is greatly improved, thus forming a rubber-like PVC. This kind of TPVC can be regarded as a modified product of PVC and a substitute for rubber. It is mainly used to manufacture hoses, rubber sheets, tapes and some rubber parts. At present, more than 70% are consumed in the automotive field, such as the steering wheel of the car, the wiper strip and so on. For other purposes, wire accounts for about 75%, and building waterproof film accounts for about 10%. In recent years, it has begun to expand into home appliances, gardening, industry, and raincoats for daily use. At present, a large number of products sold in the international market are mainly blends of PVC and NBR, modified PVC and crosslinked NBR, and have become the most successful typical blend of rubber and plastic. The nitrile rubber manufacturers in the United States, Japan, Canada, Germany and other countries have a large number of production. In the industry, PVC/NBR materials have been formed separately, and a variety of rubber products such as hoses, rubber sheets and tapes are manufactured. Blends of PVC with other polymeric materials, such as PVC/EPDM, PVC/PU, PVC/EVA blends, PVC and ethylene, acrylate grafts, etc., have also been put into production. With the strict requirements of environmental protection requirements, the sour gas emitted by TPVC has been difficult to completely solve, polluting the environment, and the growth rate in the world has recently declined, and the scope of use has been greatly affected. The TPVC produced in China mainly has HPVC. Since the 1990s, only a small amount of production has been supplied. At present, most of PVC/NBR and PVC/EVA blends are used. Apart from individual commodity blends, most of them are mixed by rubber processing plants. They are widely used in the manufacture of oil tanks, hoses, rubber shoes, etc., which have partially replaced CR and NBR, NR, SBR, the effect is very good, the amount of use is expanding year by year. At present, Lanzhou Petrochemical Company, which produces nitrile rubber, also has PVC/NBR blend materials on the market. Nanjing University of Technology and Beijing University of Chemical Technology have further developed thermoplastic elastomers blended with PVC/NBR and WRP (rubber powder) and PVC/NBR/CPE/WRP. Zhejiang University systematically carried out research on PVC/PE and PVC/PS blends. Nowadays, China has become the world's largest producer of TCPE after the United States. In 2001, the production and sales volume reached 100,000 tons (capacity of 166,000 tons), and the largest Weifang Yaxing Chemical has a world of 70,000 tons. Production equipment. In addition, there are more than 10 companies such as Hangzhou Keli Chemical. Among them, CPE rubber is 1.5-2 million tons, widely used in cables, hoses, auto parts and waterproof membranes. The TPE-enabled TCPE blended with CPE rubber and CPE resin is also beginning to be used. In the future, TPVC and TCPE may become new rubber and plastic materials for replacing some NR, BR, CR, SBR, NBR rubber and PVC plastics in China. 5. Polyurethane TPE Polyurethane TPE is a thermoplastic polyurethane rubber which is bonded to the isocyanate-reacted urethane hard segment and polyester or polyether soft segment. For short, TPU, the world's production and sales have exceeded 200,000 tons, accounting for about PUR. l/5 of (CPU, MPU). The TPUs in Europe and the United States are the most developed, with output ranging from 70,000 to 80,000 tons, accounting for 3/4 of the world, 12,000 tons for Japan and India, and 9 000 tons for China. TPU has excellent mechanical strength, wear resistance, oil resistance and flex resistance, especially wear resistance. Disadvantages are poor heat resistance, hot water resistance, compression resistance, easy to yellow appearance, easy to stick mold during processing. At present, it is mainly used in the manufacture of ski boots, hiking boots and other sporting goods in Europe and the United States, and is used in a large number of sports shoes and sneakers. TPU can also produce parts such as automobiles, machinery and watches through injection molding and extrusion molding, and is widely used in high-pressure hoses (external rubber), pure rubber hoses, sheets, drive belts, conveyor belts, wire and cable, tapes and other products. Among them, injection molding accounts for more than 40%, and extrusion molding is about 35%. In recent years, in order to improve the TPU process, there are many new easy-to-process varieties. If it is suitable for two-color molding, it can increase the transparency and high flow, and high recovery TPU for shoes that can improve the processing efficiency. A plastic-free, low-hardness, easy-to-process TPU for the manufacture of transparent hoses. An enhanced TPU that is designed to be used for large parts such as automobile bumpers and is enhanced by glass fiber to improve rigidity and impact. In particular, the addition of a reactive component to the TPU, after the thermoplastic molding, by ripening, formation of incomplete IPN (IPN formed from a crosslinked polymer and a non-crosslinked polymer) develops very rapidly. This IPN TPU further improves the physical and mechanical properties of the TPU. In addition, the TPU/PC blended alloy TPU improves the safety performance of the car bumper. In addition, there are high moisture permeability TPUs, conductive TPUs, and TPUs dedicated to raw materials, magnetic tapes, safety glass, and the like. In the international arena, TPU manufacturers mainly have more than 30 products in the United States, Japan and Europe, and the varieties are very rich. Germany Bayer, BASE, UK ICl (acquired for the acquisition of Ansmai), An ch. The focus of r and the like is on shoe-making. DDE, Mobay in the United States, and astoran and POIvurethane in Japan are mainly automotive mechanical parts, all of which are expanding to the surrounding areas. As a PUR of the same family of TPU, especially liquid polyurethane rubber ('PU), the development of the CPU is particularly rapid, and has entered the field of tape and shoemaking in large quantities, and has begun to enter bicycle rafts, industrial tires and the like. It is just around the corner to replace some of the rubber with TPU and LPU. As for the development of engineering rubber and plastic parts, it goes without saying. In addition, in the medical and health aspects of catheters, films, sheets, shaped parts, condoms, electronic wire and cable sheathing, aerospace use of its storage tanks, balloons, etc. are new growth points. China has now become the largest PU production and consumption country in Asia. In 2000, its output was 920,000 tons, which is now over one million tons, accounting for 1/4 million of the world's 4 million tons. At present, the demand for PUR elastomers is also very large, and Yantai, Taiyuan, Nanjing, Shanghai and other places have a PUR production capacity of more than 100,000 tons. In 2000, the PUR output was 85,000 tons, of which the TPU was 0.5 million tons. The footwear, synthetic leather and automotive industries are the number one market for TPR application growth, and the coatings and adhesives industry is also promising. In the next few years, Shanghai, Nanjing and other world-class large-scale polyurethane production bases of more than 160,000 tons will be built. The output of TPU will increase several times. At that time, China will form a colorful TPU world centered on the world's largest TPU sole manufacturing industry and the fast-developing auto parts industry.
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