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Thermoplastic elastomers with mechanical properties of vulcanized rubber and soft plastics processing technology performance. No longer, as did the rubber after heat curing, which uses a simple plastic processing machinery can be easily made into the final product. It's this characteristic, so that the rubber industry production processes to shorten the l / 4, save 25% ~ 40% of energy consumption and improve efficiency 10 to 20 times, once called the Rubber Industry materials and process technology revolution. Thermoplastic elastomer is between the rubber and resin, a new type of polymer material between, not only can replace part of the rubber, can be modified to make plastics. Thermoplastic elastomer which has double the performance of rubber and plastic properties and broad, so broad in the rubber industry for the manufacture of rubber shoes, plastic sheets and other household products and hose, belt, tape, plastic sheet, plastic parts, and adhesives and other industrial supplies. Meanwhile, the thermoplastic elastomer can also be used in place of a large number of rubber PVC, PE, PP, PS, and other common thermoplastic resin or PU, PA, CA and other modified engineering plastics above, so that the plastic industry has emerged a new situation.
First, the types of thermoplastic elastomers and performance characteristics of thermoplastic elastomer (TPE) can be summarized as two general types of TPE TPE and engineering, has now grown to more than 30 varieties of l0 categories. Bayer of Germany from 1938 first discovered the polyurethane TPE, 1963 and 1965 the United States Phillips and Shell, the development of styrene - butadiene - styrene block copolymer TPE, to 70 U.S. and European countries started mass production of olefins at Since TPE, technical innovation, new varieties are emerging TPE, TPE today constitute a huge system, so that combination of rubber and plastics industry took a step forward in marriage greatly. The world's industrial production has been TPE are: styrene (SBS, SIS, SEBS, SEPS), olefin (TP0, TPV), diene (TPB, TPI), vinyl chloride type (TPVC, TCPE), urethane class (TPU), esters (TPEE), amide (TPAE), organic fluorine (TPF), silicone and vinyl, etc., synthetic rubber is now covering almost all areas with the synthetic resin. They are made in the main chain through the formation of hard segments of the resin phase and the soft segment of the rubber phase, each made of solid together. TPE manufacturing methods, chemical polymerization and can be divided into two major types of mechanical blending. The former is a separate form of the polymer occurs, there is the main chain copolymerization, grafting copolymerization and cationic polymerization of the points. The latter are mainly blends of rubber and resin, which also appears in the dynamic cross-linking curing vulcanizates (TPE-TPV) and interpenetrating polymer networks (TPE-IPN). Now, TPE to TPS and TPO as the center, around the world access to the rapid development of the production of both consumption has accounted for about 80% of all TPE. Diene and vinyl chloride type TPE TPE TPE has also become an important general-purpose varieties. Others, such as TPU, TPEE, TPAE, TPF, etc. is shifted to the main project. Currently in the world trade market, the general purpose of the TPS, TPO, and TPVC of tonnes of plastic cost about 500 to 1400 dollars; and heat resistance, oil resistance, high strength, high wear resistance of the TPU, TPEE, TPAE is higher than other TPE about 50% to universal double; high-performance TPE class or even up to 2 ~ $ 30,000 a ton. TPE advantages mainly in the following aspects: (1) generally available thermoplastic molding machine processing, such as injection molding, extrusion molding, blow molding, compression molding, hand molding, etc.; (2) can be used rubber injection vulcanization molding machine, the time to be reduced from 20min or so, reduced to less than lmin; (3) can be vulcanized extruder, extrusion speed, curing time is short; (4) the waste generated in the production process (escape edges, squeeze the waste plastic), and culminating in the waste, can return to re-use: (5) TPE old product can be used again after a simple use of recycled, reducing environmental pollution, expanding sources of renewable resources; (6) without curing, to save energy to high-pressure hose production of energy as an example: rubber 188MJ/kg, TPE is 144MJ/kg, may be saving more than 25%; (7) Since the reinforcement of large, simplified formula, so with the agent on the polymer greatly reduce the impact of constraints, quality of performance easier to master; (8) for the rubber industry to explore new ways to expand the rubber applications. The disadvantage is the heat resistance of TPE as rubber, with the temperature rise properties decreased greatly, and thus the scope is limited. Meanwhile, the compressive deformation, bounce, durability, less than the same rubber, the price is often higher than the same kind of rubber. Overall, however, TPE advantage is still very prominent, but the disadvantage is constantly being improved, as a new energy-saving environmental protection, rubber raw materials, the development is very promising.
Second, the major development status of a thermoplastic elastomer. Styrene, also known as TPE Styrene TPE TPS, as butadiene or isoprene and styrene block copolymer type, the performance of the nearest SBR rubber. TPS production in the world reached 70 million t, accounting for about half of all TPE. Representative of the species is a styrene butadiene styrene block copolymer (SBS), widely used in the footwear industry, has largely replaced the rubber; while in tape, sheet and other industrial rubber products in use is also widening. SBS is also a large number of PS plastic used as impact modifier, but also wear-resistant asphalt paving of the asphalt pavement, cracking, excellent anti-skid soft modifier. PS by SBS modified plastics, not only as far as improving the impact resistance of rubber, and transparency is also very good. SBS modified asphalt with than SBR rubber, WRP powder, more easily dissolved in asphalt. Thus, although more expensive, still get a lot of use. Today, more to further promote the waterproofing membrane to the roof of a building, subway, tunnels, and grooves of waterproof, moisture-proof top. SBS and S-SBR, NP and use made of rubber sponge, than the original PVC, EVA rubber plastic foam is more full of touch, and lighter than the vulcanized rubber, bright colors, a clear pattern. Thus, not only for manufacturing shoes in the bottom of the sponge, but also shoes, sports shoes, fashion shoes and other one-time great at the end of the ideal material. In recent years, replacing isoprene styrene butadiene block polymers (S ENGINEERING S) has developed rapidly, the amount of its production accounts for TPS 1 / 3, about 90% used in the adhesives. SIS is not only made of hot melt adhesive with excellent adhesive and heat resistance Ye Hao, on countries in the U.S. and Europe has become the main material of hot melt adhesive. SBS and SIS are not the biggest problem is heat, temperature generally can not exceed 80 ℃. At the same time, its strength and elongation, weather resistance, oil resistance, abrasion resistance, also can not be compared with the rubber. To this end, the U.S. and Europe and other countries in recent years, it conducted a series of performance improvements, has appeared in SBS and SIS SEBS by the hydrogenation of saturated and SEPS. SEBS (hydrogenated BR for the soft segments) and SEPS (to IR hydrogenation as soft segments) can significantly improve impact strength, weather resistance and heat aging resistance 也好. Japan's Mitsubishi Chemical in 1984 and again in SEBS, SEPS as the base material made of a mixture of better performance, and the saturated TPS named "Rubberron" listed. Therefore, SEBS and SEPS are not only common, but also weather-resistant plastic used to improve abrasion resistance and heat aging resistance of the blend and therefore quickly developed into nylon (PA), polycarbonate (PC) and other projects plastic "alloy" of the compatibilizer. In addition, the development of epoxy resin with high transparency, TPS and the public health body with non-toxic raw TPS, and many new varieties. SBS or SEBS with PP plastic melt blend, etc., can also form a IPN-type TPS. The so-called IPN, is actually two networks with each other throughout the polymer, it is also known as IPN compounds. Although most of them are thermosetting resins, but there are a lot like the TPE of the cross shape shown by the continuous phase of thermoplastic elastomer. SES with SBS or other engineering plastics for the substrate and the formation of the IPN-TPS, you can not directly pre-coating. Not easy to scratch coating, and has some oil resistance, low coefficient of elasticity in a wide temperature range does not change; greatly increased cold and heat resistance of engineering plastics. Styrene rubber compounds and grafting copolymerization can be thermoplastic TPE, has developed a EPDM / styrene, BR / styrene, CI-IIR / styrene, NP / styrene. TPS is the world's largest manufacturer of American Shell Chem. The Kraton, Carifles and other commodities were a total of more than 40 brands, marketing around the world, only the capacity of the local device, which amounts to 23.2 million in 1998 t, reportedly have increased in recent years, in France, Germany, also have 30 000 t, production plant. U.S. Phillips Petro. The production of brand name Solprene, capacity 35,000 t, Asahi Kasei, elastomers, Italy Enichem, Belgium, Spain, Mexico, Australia and other countries also use its technical production capacity from 0.5 million to 2.8 million t range. JSR of Japan and Russia, each with their own technology 25,000 t of production enterprises. Taiwan's Chi Mei has 90 000 t of the SBS (including S-SBR) plant. China is the world's largest consumer of TPS from 1980 to SBS as the center, along with the footwear industry in China (annual output of 60 billion pairs of shoes production accounts for half of the world), construction (13 years with a waterproofing membrane 0,000,000 m, SBS and APP modified asphalt in which 80 million M2, largest in the world) and Highway Business (Highway 25 000 km, the world's second) on the need for TPS in 1999 25 million t, 2000 years 300 000 t, 2001 35 million year t, estimated that up to 40 million in 2002 t. While the national production in 1999, 88,000 t, 2000 years 133 000 t, 2001 years 168 000 t, 2002 reached 216,000 t, an average annual growth rate of 12% or more. Still unable to meet growing market needs. More than half of imports from overseas, including Taiwan l0 million t, 80% for footwear, and the remaining 80 000 t from South Korea, Japan, Russia and other imports. In 2001, the domestic shoe-making aspects of SBS for a 270,000 t, accounting for 78%, road bitumen 45,000 t, accounting for 13%, other adhesives, waterproofing membranes, plastic modified each 3.8%, 3.2% and 2%. 1982 by the Research Institute of Beijing Yanshan Petrochemical successfully developed its own after SBS, there are three petrochemical enterprises in the production. The scale of Beijing Yanshan Petrochemical with an annual output 6 million t, production of 40,000 t; annual production scale of 100,000 Yueyang Petrochemical t, production of 130,000 t; Maoming Petrochemical with an annual output size 50000 t, production of 50,000 t. In addition to SBS, but also a small amount of production of SIS and the SESS. Production of up to 25 grades, covering the footwear product applications, road bitumen, plastic modification, waterproof materials, adhesives and other fields. China now has become one of the world's three major production bases TPS, TPS production technologies have been introduced to Taiwan and Italy. 2. Olefin olefin TPE TPE Department of the PP as the hard segment and soft segment EPDM blends, referred to as TPO. Because of its light weight than other TPE's (only O.88), heat-resistant up to 100 ℃, resistance to weather and ozone resistance Ye Hao, thereby becoming another TPE in the rapid development of the species. Since 1972, companies in the United States by the UniroyaI TPR trade names first on the market, years of double-digit growth in 2000 production reached 3 50 000 t, 2002 is estimated to be 400,000 t. Now, TPO has become the United States and Japan and other key areas of automotive and home appliance rubber material. In particular, have been accounted for in the car and its total 3 / 4, with its manufacture of car bumpers, has replaced the original metal and PU. Appeared in 1973, the dynamic part of the vulcanization of the TPO, in particular the United States in 1981, the company developed to Santoprere Mansanto named TPO fully dynamic vulcanization type, the performance has greatly changed, the maximum temperature can reach 120 ℃. This dynamic vulcanization type of TPO referred to as TPV, TPO is mainly in the PP and EPDM blends in the molten mixture, the curing of the crosslinking agent added to it, using mixer, a high shear screw machines and other machinery strength, so that full curing of the crosslinked EPDM rubber fine particles fully dispersed into the PP matrix. In this cross-linked rubber of the "particle effect", leading to TPO deformation resistance, heat aging resistance, oil resistance are all significantly improved, even to the level of CR rubber, which in turn referred to as thermoplastic vulcanizates people gel. Use of TPV oil resistance, has been replaced by the NBR, CR manufacture various rubber products. PE can also be blended with TPV, TPE with SBS and use other, complementary to improve performance. Now, in the car has been widely used as a gear, rack, ignition wires foreskin, oil hose, air duct and shiny high-rise building of the crack seal, as well as wire and cable, food and medical areas, the growth rate much higher than the TPS . In recent years, Germany and the TPV based on the introduction of the polymerization TPO, TPV toughness and resistance to low temperature performance of the emergence of new breakthroughs. United States has also developed a better overall performance IPN-type TPO. Appeared in 1985, fully dynamic vulcanization type of PP / NBR-TPV, it is part of PP with maleic anhydride grafted to deal with some of NBR with amine to form amine end seal NBR. The dynamic vulcanization process to form a small amount of grafting and block copolymer, can replace the NBR used in aircraft, automobiles, machinery, and other aspects of seals, hoses and so on. This blends the two materials with different polarities, are incompatible with each other, which must be added in the blend MAC compatibilizer. Such compatibilizers are: ethylene polyamine compounds such as diethylenetriamine or triethylenetetramine amine, as well as liquid NBR and polypropylene maleic anhydride compounds. Malaysia's successful development of the 1988 PP / NR TPV, it is high tensile and tear strength, compression deformation greatly improved, heat-resistant up to 100-125 ℃. The same period, also developed a PP / ENR - TPV, which is to NR is made first with the peracetic acid epoxidation reaction of NR, and then melt blending with the PP obtained. Performance is better than PP / NR-TPV and PP / NBR - TPV, for automotive parts and wire and cable and so on. In the meantime, the United Kingdom has emerged PP / IIR-TPV, PP / CI an IIR-TPV, the United States developed the PP / SBR, PP / BR, PP / CSM, PP / ACM, PP / ECO and a series of melt blending materials, the German made the PP / EVA, the PP blends with a variety of rubber have been successful. In addition, there is seen in the market to ET Polvmer, Rucodur and other commodities appears EPDM / PVC, IIR / PE and so on. Currently, in order to blend in the form prepared by dynamic vulcanization technology all the TPE has covered 9 of 11 rubber and resins, rubber and plastics can be made out of 99 blends. The vulcanized rubber crosslink density reached 7 × 10-5mol/ml (swelling method), that is, 97% of vulcanized rubber is cross-linked, more than 100% tensile elongation, tensile permanent deformation does not exceed 50 %. Now AES Corporation (Monsanto) representation of the production of varieties of Santoprene (EPDM / pp-TPV) and Geolast (NBR / PP-TPV) based, is widely used in mechanical, electrical, construction, food, medical room and other areas. Especially in the car above, has accounted for 30% to 40%, the amount of foreign TPE each car's already 10kg, about car parts lO%. TPV can be processed using a common plastic blow molding, injection molding and extrusion molding, etc. the production of parts. Blow molding products are car air purifier tube, gear cover protective cover, coupling jacket and so on. Injection products are plug head gasket, mirror pad, foot brake pads, brake by power plant catheter sheath, crank cover jacket and so on, can create belt. Extrusion products are wire and cable sheathing, fuel, rubber and all kinds of outer seal. In particular the seal on the car, the use of TPV has become fashionable, including solid and foam products, and quasi-static sealing action / dynamic sealing products, etc., have replaced the rubber. Present in the olefin-based TPE, TPO about 80% a 85%, TPV accounted for l5% -20%. For this reason, the other major world-renowned manufacturer of EPDM synthetic rubber, have introduced their own characteristics TPO, TPV production grades. To adapt to different processing methods and uses, generally more than 10-20. Although their specific production methods and production are mostly unpublished, but are nothing more than a variety of melt olefin blends. TPV is a melt blending of the rubber, plastics manufacturers striving to develop a new type of rubber and plastic materials and the most popular research and development topics. There are all kinds of TPO-TPV blend between, such as EPDM / PP TPV and NBR / PP - TPV, ACM / PP TPV and EPDM / PA-TPV, etc., are also modified into a new blend. The production of TPO-TPV in 1990 used a half from the beginning, especially with the rapid development of automobile industry, TPO-TPV annual amount of 1 O% -20% of the rate of rapid increase. In 2002 production of 325 million cars, at least half of the cars have to spend a TPO-TPV manufacturing bumpers and external decorative panels and parts. National EPDM consumption reached 5.5 million in 2002 t (2.2 million domestic product, t), which accounted for the polyolefin modifier 18% -22%, as projected production of TPO-TPV, when 2 million t over. In addition, foreign production is not included in the statistics, has been unable to ascertain the exact number. In the TPO-TPV, TPV accounted for about l 5% -20%. Consumption in 2001 is estimated at 3000t, of which 80% from the U.S. AES, TRS. Royal DSM and the Dutch companies such as Taiwan, South imports. Main domestic manufacturers are 8-10, are small and medium sized production plants around 1000t, due to performance quality issues, but the total sales of 500 ~ 600t. From 80 years, Tsinghua University, Chinese Academy of Sciences and Beijing Changchun of Chemistry, Beijing University of Chemical Technology, Shanghai Jiaotong Six, Beijing Research Institute of Chemical and Petrochemical Group, the Yangtze, Jinling, Yanshan and other companies have developed a TPO. Which should be based in Changchun, Shanghai Jiaotong University and the Yangtze, Jinling Petrochemical also developed a TPV, and the trial in the wire and cable, construction waterproofing, auto seal, shield, and various pipes and belt areas. Qingdao University has also applied for the PP / NBR-TPV national patent, the South China Institute of Tropical Crops track to carry out PP / NR - TPV research. However, due to various reasons, in addition to EPDM / PP-TPV thermoplastic vulcanizate, the other truly, little industrialization, so far there is no domestic manufacturer of large-scale professional. TPE TPV is the world's fastest-growing family, the annual growth rate of 10% -20% or more. Because of its processing methods and performance of the most close to the vulcanized rubber, the United States, mainly in cars and other products cover a very broad, great development potential. Currently, foreign sealing, sheathing, gaskets, and other large foreskin transferred to TPV, TPO-TPV global consumption has reached 36 million t. The amount of less than 25,000 now t (TPV 3000t), only the world TPO-TPV's 7%, lt foreign goods prices up to 4000-5000 dollars quirky, limited promotional use. In the future if the price dropped to normal levels, comparable or slightly higher than the same rubber prices, demand will grow exponentially. Only a rubber seal products, the present, there are more than 40 production lines, 12 major manufacturing enterprises with an annual output of rubber seal 90 million m, capacity 180 million m, such as half of the switch to TPE, the lm total weight 0.4kg , that is to be TPO-TPV 1.8 萬 t, which TPV between at least 3000-4000t. Along with other products to expand use of TPO-TPV, TPO TPV next five years, the demand for the country will be possible to reach 3.5-4.5 million t, which TPV to the 0.7-O.9 million t. As the performance of TPV poor quality of domestic and import prices of TPV remains high, experts predict that the domestic consumption by 2005 can only reach 5000-6000t, 2010 year of 1.0 ~ 1.8 million t. 3. TPE TPE diene diene rubber, mainly for the natural isomer, it is also known as the trans-thermoplastic natural rubber (1-NR). As early as 400 years ago, as a natural rubber that is found in this material, but with its fruits of the different gutta Hevea and Balata and other wild trees, which is called gutta rubber, Pakistan Latta rubber. The T-NR as submarine cables and leather golf history, etc. Although there have been 100 years, but showed a thermoplastic state, crystallization and strong, availability is limited, the expansion of long-term use. After 1963, the United States, Canada, Japan and other countries have made of the metal organic synthesis catalyst T-NR-trans-polyisoprene rubber, called TPI. Its the same microstructure of isoprene rubber (IR) is just the opposite, with 99% trans, 40% crystallinity, melting point 67 ℃, with the production of natural rubber, gutta, and Balata is very similar. So, has begun to gradually replace the natural products, and further development of the apparatus used in plastic surgery, plaster substitutes and sports protection equipment. In recent years, the use of TPI excellent crystallinity and temperature sensitivity, and the successful development of a shape memory rubber material, much of it ages. Structurally speaking, TPI is a high trans-formed crystalline structure as the hard segment, and then with the rest of arbitrary shape elastic phase state was part of the combination of soft segments consisting of thermoplastic rubber. Compared with other TPE, the advantage of mechanical strength, good resistance to injury, but also cure the disadvantage of softening temperature is very low, generally only 40-70 ℃, use is restricted. Currently, only Canada Polysar international and Japanese Kurary two in production, production is estimated that thousands of t so. Qingdao University of Science and Technology recently developed TPI, and carried out using the test, the State Technology Invention. In addition, China is developing a large number in the middle third in Hunan, Hubei, Sichuan, the area of ??your tree Eucommia Eucommia rubber, it is also a trans-l, 4 polyisoprene rubber, often rich in abundance, considerable development potential. In 1974, the company successfully developed in Japan JSR BR rubber (cis 1,4-polybutadiene a) of the isomers - between the same l, 2 polybutadiene, referred to as TPB. It contains more than 90% l, 2 位 between the same combination of polybutadiene rubber, trade name RB. Microstructure between the hard segments by the crystalline structure of some of the same soft segment and a soft part of each other constitute any form of block polymers. Currently there is only a Japanese production, although its heat resistance, mechanical strength than rubber, but with a good transparency, weather resistance and electrical insulation, and photolysis, widely used in the footwear, sponge, film and light other industrial rubber products, the annual demand has more than 27,000 t. Lee TPB other TPE TPI biggest difference is that it can be vulcanized. TPE can not be used to solve the general sulfur, peroxide curing. But must use electronic waves, radiation and other special devices only. Can be modified to mention the quality problems, thus improving the TPE heat resistance, oil resistance and durability of poor and other shortcomings. TPB in the 75-1 10 ℃ within the melting point of any process, both for the production of injection molding of non-vulcanized slippers, sandals, vulcanized foam manufacturers can also use the sports shoes, sneakers, etc. in the end. It is not easy compared with EVA foam midsole collapse deformation, wear comfortable, help to improve athletic results. TPB-made film, with good ventilation, water and transparency, easy-to-light decomposition, very safe, especially for families and vegetables, fresh fruit packaging purposes. 4. Vinyl chloride type thermoplastic PVC and TPE thermoplastic CPE is divided into two categories, the former is called TPVC, the latter known as TCPE. TPVC mainly the flexibility of the modified PVC material, is divided into chemical polymerization and mechanical blending two forms. Mechanical blending NBR main part of the cross-linked to form mixed with PVC blends (PVC / NBR). TPVC actually said to just an extension of soft PVC resin, but greatly improved because of compression deformation, thereby forming a rubber-like PVC. This TPVC modified products can be regarded as PVC and rubber substitutes, mainly in its manufacturing rubber hose, rubber, tape and some plastic parts. Currently over 70% of consumption in the automotive field, such as car steering wheel, windshield wipers, etc. section. Other purposes, wires about 75%, 10% waterproof film is about. In recent years, began to expand into home appliances, gardening, industrial and daily operations raincoat and so on. Currently, a large number of sales on the international market, mainly PVC and NBR, and cross-linked NBR modified PVC blends, rubber and plastic blends has become the most successful models. United States, Japan, Canada, Germany and other countries, nitrile rubber manufacturer Jieyou mass production in industry has formed a separate PVC / NBR material, with its mass production of rubber hose, rubber, plastic sheets and other rubber products. PVC and other polymer blends such as PVC / EPDM, PVC / PU, PVC / EVA blends, PVC and vinyl, acrylic grafting materials and so on, also have come into production. With the stringent environmental requirements of the said benefits, TPVC escape of acid gas, etc. is still difficult to solve, environmental pollution, the recent growth rate in the world has declined, the use of the range has been greatly affected. China's production and use of TPVC are HPVC, research from the 90s, only a small amount of production and supply. Present in PVC / NBR and PVC / EVA blends in the form of majority, except for certain commodities, a total of mixing, most of the self-reference by the rubber mixing plant, widely used in the manufacture tanks, hose, shoes, etc., have been partially replaced by CR and NBR, and NR, SBR, very good results, the amount has expanded each year. At present, the production of nitrile rubber Lanzhou Petrochemical Company has PVC / NBR blends to market. Nanjing University and Beijing University of Chemical Technology has further developed the PVC / NBR and WRP (crumb rubber), PVC / NBR / CPE / WRP blend of thermoplastic elastomer. Zhejiang University, systematically carried out PVC / PE, PVC / PS blends research. Today China has become the world after the United States to use the country's largest production TCPE, 2001, annual sales have left should be the right of 10 million t (capacity of 1 60 000 t), the largest Weifang Yaxing Chemical has 70,000 t of the world class production equipment. In addition, more than 10 Hangzhou Mercury chemical production. Which, CPE rubber 1.5-2 million t, is widely used in cables, hoses, auto parts and waterproofing membrane and so on. CPE and CPE resins are blends of rubber with TPE function TCPE, began to be applied. In the future, TPVC and TCPE may become part of our place of NR, BR, CR, SBR, NBR rubber and PVC plastic, new rubber material. 5. TPE TPE polyurethane polyurethane and isocyanate by the reaction of urethane hard segments and soft segments of polyester or polyether block each other with the thermoplastic polyurethane rubber, referred to as TPU, the world's production and sales have more than 20 million t, accounting for PUR (CPU, MPU) of the l / 5. TPU most developed in Europe and America, with its output of each of 7-8 million t, about the world's 3 / 4, Japan and India each, 12000 t, China 9 000t. TPU has excellent mechanical strength, wear resistance, oil resistance and resistance to flex, especially the most outstanding wear resistance. The disadvantage is heat, heat water, poor compression resistance, appearance and easy to turn yellow, sticky and easy processing mold. Currently the major countries in Europe and America for the manufacture of ski boots, hiking boots and other sporting goods, and for the production of a large number of sports shoes, sneakers, consumption of many. TPU can also be formed by injection molding and extrusion methods such as automobile, machinery, and watches and other parts, and is used extensively for high-pressure hose (rubber outside), tubing, sheets, belts, conveyor belts, wire and cable, tape and other products. Which accounted for 40% of injection molding, extrusion molding is about 35%. In recent years, TPU technology to improve the performance increase of 7 workers, but also many new varieties of ease of processing. As for two-color molding, can increase transparency and high flow, high recovery can improve the processing efficiency of the shoe with TPU. For the manufacture of non-transparent plastic hose, low hardness and easy processing TPU. For large parts such as automobile bumpers dedicated to glass fiber reinforced to increase rigidity and impact of enhanced TPU and so on. Add especially in the TPU reactive component, after the thermoplastic molding, through aging, and the formation of not fully IPN (by the cross-linked polymer and the formation of crosslinked polymer IPN) developed very rapidly. The IPN TPU TPU further improve the physical and mechanical properties. In addition, TPU / PC blend alloy type TPU, but also raise the safety performance of automobile bumpers. In addition, the high permeability of the TPU, conductivity of TPU, and there have been dedicated to the living body, tape, safety glass and other aspects of TPU. Internationally, TPU manufacturer based in U.S., Japan and Europe has reached more than 30 much very rich variety of brands. Germany's Bayer, BASE, the United Kingdom ICl (in order to enjoy Ismail acquisition), An ch. r and other key focus mainly on the shoe, the United States of DDE, Mobay and Japan astoran, POIvurethane mechanical components such as a car-based, are common to the surrounding areas of expansion. The same family as the TPU PUR, in particular, liquid polyurethane rubber ('PU also known as CPU) is particularly rapid development, has been poured into the tape, shoe-making area, and has started to enter the bike Yi, industrial tires and so on. Instead of part of the LPU with TPU and rubber have been just around the corner, as in the engineering aspects of the development of rubber and plastic parts, not to be made. In addition, the health sector for the tube, film, sheet, special parts, condoms, electronic communications system for wire and cable sheathing used, aerospace manufacturing tank with its terms, balloons and so are the new growth point. China has become Asia's largest production and consumption country PU, 2000, annual production of 920,000 t, is now over one million tons more than 400 million t of the world's l / 4. Currently, the demand for PUR elastomers great, Yantai, Taiyuan, Nanjing, Shanghai and other places have more than 10 million t PUR production capacity. PUR 2000 production 85,000 t, of which there are 0.5 million TPU t. Footwear, synthetic leather industry and the automotive industry is the number one growth market TPR applications, coatings and adhesives industry is also promising. The next few years, Shanghai, Nanjing and other world-class 160 000 t or more after the completion of large-scale production base polyurethane. TPU production will grow into several times, when China will be the world's largest TPU sole manufacturing and rapid development of the auto parts industry, as the center to form a variety of TPU world.
First, the types of thermoplastic elastomers and performance characteristics of thermoplastic elastomer (TPE) can be summarized as two general types of TPE TPE and engineering, has now grown to more than 30 varieties of l0 categories. Bayer of Germany from 1938 first discovered the polyurethane TPE, 1963 and 1965 the United States Phillips and Shell, the development of styrene - butadiene - styrene block copolymer TPE, to 70 U.S. and European countries started mass production of olefins at Since TPE, technical innovation, new varieties are emerging TPE, TPE today constitute a huge system, so that combination of rubber and plastics industry took a step forward in marriage greatly. The world's industrial production has been TPE are: styrene (SBS, SIS, SEBS, SEPS), olefin (TP0, TPV), diene (TPB, TPI), vinyl chloride type (TPVC, TCPE), urethane class (TPU), esters (TPEE), amide (TPAE), organic fluorine (TPF), silicone and vinyl, etc., synthetic rubber is now covering almost all areas with the synthetic resin. They are made in the main chain through the formation of hard segments of the resin phase and the soft segment of the rubber phase, each made of solid together. TPE manufacturing methods, chemical polymerization and can be divided into two major types of mechanical blending. The former is a separate form of the polymer occurs, there is the main chain copolymerization, grafting copolymerization and cationic polymerization of the points. The latter are mainly blends of rubber and resin, which also appears in the dynamic cross-linking curing vulcanizates (TPE-TPV) and interpenetrating polymer networks (TPE-IPN). Now, TPE to TPS and TPO as the center, around the world access to the rapid development of the production of both consumption has accounted for about 80% of all TPE. Diene and vinyl chloride type TPE TPE TPE has also become an important general-purpose varieties. Others, such as TPU, TPEE, TPAE, TPF, etc. is shifted to the main project. Currently in the world trade market, the general purpose of the TPS, TPO, and TPVC of tonnes of plastic cost about 500 to 1400 dollars; and heat resistance, oil resistance, high strength, high wear resistance of the TPU, TPEE, TPAE is higher than other TPE about 50% to universal double; high-performance TPE class or even up to 2 ~ $ 30,000 a ton. TPE advantages mainly in the following aspects: (1) generally available thermoplastic molding machine processing, such as injection molding, extrusion molding, blow molding, compression molding, hand molding, etc.; (2) can be used rubber injection vulcanization molding machine, the time to be reduced from 20min or so, reduced to less than lmin; (3) can be vulcanized extruder, extrusion speed, curing time is short; (4) the waste generated in the production process (escape edges, squeeze the waste plastic), and culminating in the waste, can return to re-use: (5) TPE old product can be used again after a simple use of recycled, reducing environmental pollution, expanding sources of renewable resources; (6) without curing, to save energy to high-pressure hose production of energy as an example: rubber 188MJ/kg, TPE is 144MJ/kg, may be saving more than 25%; (7) Since the reinforcement of large, simplified formula, so with the agent on the polymer greatly reduce the impact of constraints, quality of performance easier to master; (8) for the rubber industry to explore new ways to expand the rubber applications. The disadvantage is the heat resistance of TPE as rubber, with the temperature rise properties decreased greatly, and thus the scope is limited. Meanwhile, the compressive deformation, bounce, durability, less than the same rubber, the price is often higher than the same kind of rubber. Overall, however, TPE advantage is still very prominent, but the disadvantage is constantly being improved, as a new energy-saving environmental protection, rubber raw materials, the development is very promising.
Second, the major development status of a thermoplastic elastomer. Styrene, also known as TPE Styrene TPE TPS, as butadiene or isoprene and styrene block copolymer type, the performance of the nearest SBR rubber. TPS production in the world reached 70 million t, accounting for about half of all TPE. Representative of the species is a styrene butadiene styrene block copolymer (SBS), widely used in the footwear industry, has largely replaced the rubber; while in tape, sheet and other industrial rubber products in use is also widening. SBS is also a large number of PS plastic used as impact modifier, but also wear-resistant asphalt paving of the asphalt pavement, cracking, excellent anti-skid soft modifier. PS by SBS modified plastics, not only as far as improving the impact resistance of rubber, and transparency is also very good. SBS modified asphalt with than SBR rubber, WRP powder, more easily dissolved in asphalt. Thus, although more expensive, still get a lot of use. Today, more to further promote the waterproofing membrane to the roof of a building, subway, tunnels, and grooves of waterproof, moisture-proof top. SBS and S-SBR, NP and use made of rubber sponge, than the original PVC, EVA rubber plastic foam is more full of touch, and lighter than the vulcanized rubber, bright colors, a clear pattern. Thus, not only for manufacturing shoes in the bottom of the sponge, but also shoes, sports shoes, fashion shoes and other one-time great at the end of the ideal material. In recent years, replacing isoprene styrene butadiene block polymers (S ENGINEERING S) has developed rapidly, the amount of its production accounts for TPS 1 / 3, about 90% used in the adhesives. SIS is not only made of hot melt adhesive with excellent adhesive and heat resistance Ye Hao, on countries in the U.S. and Europe has become the main material of hot melt adhesive. SBS and SIS are not the biggest problem is heat, temperature generally can not exceed 80 ℃. At the same time, its strength and elongation, weather resistance, oil resistance, abrasion resistance, also can not be compared with the rubber. To this end, the U.S. and Europe and other countries in recent years, it conducted a series of performance improvements, has appeared in SBS and SIS SEBS by the hydrogenation of saturated and SEPS. SEBS (hydrogenated BR for the soft segments) and SEPS (to IR hydrogenation as soft segments) can significantly improve impact strength, weather resistance and heat aging resistance 也好. Japan's Mitsubishi Chemical in 1984 and again in SEBS, SEPS as the base material made of a mixture of better performance, and the saturated TPS named "Rubberron" listed. Therefore, SEBS and SEPS are not only common, but also weather-resistant plastic used to improve abrasion resistance and heat aging resistance of the blend and therefore quickly developed into nylon (PA), polycarbonate (PC) and other projects plastic "alloy" of the compatibilizer. In addition, the development of epoxy resin with high transparency, TPS and the public health body with non-toxic raw TPS, and many new varieties. SBS or SEBS with PP plastic melt blend, etc., can also form a IPN-type TPS. The so-called IPN, is actually two networks with each other throughout the polymer, it is also known as IPN compounds. Although most of them are thermosetting resins, but there are a lot like the TPE of the cross shape shown by the continuous phase of thermoplastic elastomer. SES with SBS or other engineering plastics for the substrate and the formation of the IPN-TPS, you can not directly pre-coating. Not easy to scratch coating, and has some oil resistance, low coefficient of elasticity in a wide temperature range does not change; greatly increased cold and heat resistance of engineering plastics. Styrene rubber compounds and grafting copolymerization can be thermoplastic TPE, has developed a EPDM / styrene, BR / styrene, CI-IIR / styrene, NP / styrene. TPS is the world's largest manufacturer of American Shell Chem. The Kraton, Carifles and other commodities were a total of more than 40 brands, marketing around the world, only the capacity of the local device, which amounts to 23.2 million in 1998 t, reportedly have increased in recent years, in France, Germany, also have 30 000 t, production plant. U.S. Phillips Petro. The production of brand name Solprene, capacity 35,000 t, Asahi Kasei, elastomers, Italy Enichem, Belgium, Spain, Mexico, Australia and other countries also use its technical production capacity from 0.5 million to 2.8 million t range. JSR of Japan and Russia, each with their own technology 25,000 t of production enterprises. Taiwan's Chi Mei has 90 000 t of the SBS (including S-SBR) plant. China is the world's largest consumer of TPS from 1980 to SBS as the center, along with the footwear industry in China (annual output of 60 billion pairs of shoes production accounts for half of the world), construction (13 years with a waterproofing membrane 0,000,000 m, SBS and APP modified asphalt in which 80 million M2, largest in the world) and Highway Business (Highway 25 000 km, the world's second) on the need for TPS in 1999 25 million t, 2000 years 300 000 t, 2001 35 million year t, estimated that up to 40 million in 2002 t. While the national production in 1999, 88,000 t, 2000 years 133 000 t, 2001 years 168 000 t, 2002 reached 216,000 t, an average annual growth rate of 12% or more. Still unable to meet growing market needs. More than half of imports from overseas, including Taiwan l0 million t, 80% for footwear, and the remaining 80 000 t from South Korea, Japan, Russia and other imports. In 2001, the domestic shoe-making aspects of SBS for a 270,000 t, accounting for 78%, road bitumen 45,000 t, accounting for 13%, other adhesives, waterproofing membranes, plastic modified each 3.8%, 3.2% and 2%. 1982 by the Research Institute of Beijing Yanshan Petrochemical successfully developed its own after SBS, there are three petrochemical enterprises in the production. The scale of Beijing Yanshan Petrochemical with an annual output 6 million t, production of 40,000 t; annual production scale of 100,000 Yueyang Petrochemical t, production of 130,000 t; Maoming Petrochemical with an annual output size 50000 t, production of 50,000 t. In addition to SBS, but also a small amount of production of SIS and the SESS. Production of up to 25 grades, covering the footwear product applications, road bitumen, plastic modification, waterproof materials, adhesives and other fields. China now has become one of the world's three major production bases TPS, TPS production technologies have been introduced to Taiwan and Italy. 2. Olefin olefin TPE TPE Department of the PP as the hard segment and soft segment EPDM blends, referred to as TPO. Because of its light weight than other TPE's (only O.88), heat-resistant up to 100 ℃, resistance to weather and ozone resistance Ye Hao, thereby becoming another TPE in the rapid development of the species. Since 1972, companies in the United States by the UniroyaI TPR trade names first on the market, years of double-digit growth in 2000 production reached 3 50 000 t, 2002 is estimated to be 400,000 t. Now, TPO has become the United States and Japan and other key areas of automotive and home appliance rubber material. In particular, have been accounted for in the car and its total 3 / 4, with its manufacture of car bumpers, has replaced the original metal and PU. Appeared in 1973, the dynamic part of the vulcanization of the TPO, in particular the United States in 1981, the company developed to Santoprere Mansanto named TPO fully dynamic vulcanization type, the performance has greatly changed, the maximum temperature can reach 120 ℃. This dynamic vulcanization type of TPO referred to as TPV, TPO is mainly in the PP and EPDM blends in the molten mixture, the curing of the crosslinking agent added to it, using mixer, a high shear screw machines and other machinery strength, so that full curing of the crosslinked EPDM rubber fine particles fully dispersed into the PP matrix. In this cross-linked rubber of the "particle effect", leading to TPO deformation resistance, heat aging resistance, oil resistance are all significantly improved, even to the level of CR rubber, which in turn referred to as thermoplastic vulcanizates people gel. Use of TPV oil resistance, has been replaced by the NBR, CR manufacture various rubber products. PE can also be blended with TPV, TPE with SBS and use other, complementary to improve performance. Now, in the car has been widely used as a gear, rack, ignition wires foreskin, oil hose, air duct and shiny high-rise building of the crack seal, as well as wire and cable, food and medical areas, the growth rate much higher than the TPS . In recent years, Germany and the TPV based on the introduction of the polymerization TPO, TPV toughness and resistance to low temperature performance of the emergence of new breakthroughs. United States has also developed a better overall performance IPN-type TPO. Appeared in 1985, fully dynamic vulcanization type of PP / NBR-TPV, it is part of PP with maleic anhydride grafted to deal with some of NBR with amine to form amine end seal NBR. The dynamic vulcanization process to form a small amount of grafting and block copolymer, can replace the NBR used in aircraft, automobiles, machinery, and other aspects of seals, hoses and so on. This blends the two materials with different polarities, are incompatible with each other, which must be added in the blend MAC compatibilizer. Such compatibilizers are: ethylene polyamine compounds such as diethylenetriamine or triethylenetetramine amine, as well as liquid NBR and polypropylene maleic anhydride compounds. Malaysia's successful development of the 1988 PP / NR TPV, it is high tensile and tear strength, compression deformation greatly improved, heat-resistant up to 100-125 ℃. The same period, also developed a PP / ENR - TPV, which is to NR is made first with the peracetic acid epoxidation reaction of NR, and then melt blending with the PP obtained. Performance is better than PP / NR-TPV and PP / NBR - TPV, for automotive parts and wire and cable and so on. In the meantime, the United Kingdom has emerged PP / IIR-TPV, PP / CI an IIR-TPV, the United States developed the PP / SBR, PP / BR, PP / CSM, PP / ACM, PP / ECO and a series of melt blending materials, the German made the PP / EVA, the PP blends with a variety of rubber have been successful. In addition, there is seen in the market to ET Polvmer, Rucodur and other commodities appears EPDM / PVC, IIR / PE and so on. Currently, in order to blend in the form prepared by dynamic vulcanization technology all the TPE has covered 9 of 11 rubber and resins, rubber and plastics can be made out of 99 blends. The vulcanized rubber crosslink density reached 7 × 10-5mol/ml (swelling method), that is, 97% of vulcanized rubber is cross-linked, more than 100% tensile elongation, tensile permanent deformation does not exceed 50 %. Now AES Corporation (Monsanto) representation of the production of varieties of Santoprene (EPDM / pp-TPV) and Geolast (NBR / PP-TPV) based, is widely used in mechanical, electrical, construction, food, medical room and other areas. Especially in the car above, has accounted for 30% to 40%, the amount of foreign TPE each car's already 10kg, about car parts lO%. TPV can be processed using a common plastic blow molding, injection molding and extrusion molding, etc. the production of parts. Blow molding products are car air purifier tube, gear cover protective cover, coupling jacket and so on. Injection products are plug head gasket, mirror pad, foot brake pads, brake by power plant catheter sheath, crank cover jacket and so on, can create belt. Extrusion products are wire and cable sheathing, fuel, rubber and all kinds of outer seal. In particular the seal on the car, the use of TPV has become fashionable, including solid and foam products, and quasi-static sealing action / dynamic sealing products, etc., have replaced the rubber. Present in the olefin-based TPE, TPO about 80% a 85%, TPV accounted for l5% -20%. For this reason, the other major world-renowned manufacturer of EPDM synthetic rubber, have introduced their own characteristics TPO, TPV production grades. To adapt to different processing methods and uses, generally more than 10-20. Although their specific production methods and production are mostly unpublished, but are nothing more than a variety of melt olefin blends. TPV is a melt blending of the rubber, plastics manufacturers striving to develop a new type of rubber and plastic materials and the most popular research and development topics. There are all kinds of TPO-TPV blend between, such as EPDM / PP TPV and NBR / PP - TPV, ACM / PP TPV and EPDM / PA-TPV, etc., are also modified into a new blend. The production of TPO-TPV in 1990 used a half from the beginning, especially with the rapid development of automobile industry, TPO-TPV annual amount of 1 O% -20% of the rate of rapid increase. In 2002 production of 325 million cars, at least half of the cars have to spend a TPO-TPV manufacturing bumpers and external decorative panels and parts. National EPDM consumption reached 5.5 million in 2002 t (2.2 million domestic product, t), which accounted for the polyolefin modifier 18% -22%, as projected production of TPO-TPV, when 2 million t over. In addition, foreign production is not included in the statistics, has been unable to ascertain the exact number. In the TPO-TPV, TPV accounted for about l 5% -20%. Consumption in 2001 is estimated at 3000t, of which 80% from the U.S. AES, TRS. Royal DSM and the Dutch companies such as Taiwan, South imports. Main domestic manufacturers are 8-10, are small and medium sized production plants around 1000t, due to performance quality issues, but the total sales of 500 ~ 600t. From 80 years, Tsinghua University, Chinese Academy of Sciences and Beijing Changchun of Chemistry, Beijing University of Chemical Technology, Shanghai Jiaotong Six, Beijing Research Institute of Chemical and Petrochemical Group, the Yangtze, Jinling, Yanshan and other companies have developed a TPO. Which should be based in Changchun, Shanghai Jiaotong University and the Yangtze, Jinling Petrochemical also developed a TPV, and the trial in the wire and cable, construction waterproofing, auto seal, shield, and various pipes and belt areas. Qingdao University has also applied for the PP / NBR-TPV national patent, the South China Institute of Tropical Crops track to carry out PP / NR - TPV research. However, due to various reasons, in addition to EPDM / PP-TPV thermoplastic vulcanizate, the other truly, little industrialization, so far there is no domestic manufacturer of large-scale professional. TPE TPV is the world's fastest-growing family, the annual growth rate of 10% -20% or more. Because of its processing methods and performance of the most close to the vulcanized rubber, the United States, mainly in cars and other products cover a very broad, great development potential. Currently, foreign sealing, sheathing, gaskets, and other large foreskin transferred to TPV, TPO-TPV global consumption has reached 36 million t. The amount of less than 25,000 now t (TPV 3000t), only the world TPO-TPV's 7%, lt foreign goods prices up to 4000-5000 dollars quirky, limited promotional use. In the future if the price dropped to normal levels, comparable or slightly higher than the same rubber prices, demand will grow exponentially. Only a rubber seal products, the present, there are more than 40 production lines, 12 major manufacturing enterprises with an annual output of rubber seal 90 million m, capacity 180 million m, such as half of the switch to TPE, the lm total weight 0.4kg , that is to be TPO-TPV 1.8 萬 t, which TPV between at least 3000-4000t. Along with other products to expand use of TPO-TPV, TPO TPV next five years, the demand for the country will be possible to reach 3.5-4.5 million t, which TPV to the 0.7-O.9 million t. As the performance of TPV poor quality of domestic and import prices of TPV remains high, experts predict that the domestic consumption by 2005 can only reach 5000-6000t, 2010 year of 1.0 ~ 1.8 million t. 3. TPE TPE diene diene rubber, mainly for the natural isomer, it is also known as the trans-thermoplastic natural rubber (1-NR). As early as 400 years ago, as a natural rubber that is found in this material, but with its fruits of the different gutta Hevea and Balata and other wild trees, which is called gutta rubber, Pakistan Latta rubber. The T-NR as submarine cables and leather golf history, etc. Although there have been 100 years, but showed a thermoplastic state, crystallization and strong, availability is limited, the expansion of long-term use. After 1963, the United States, Canada, Japan and other countries have made of the metal organic synthesis catalyst T-NR-trans-polyisoprene rubber, called TPI. Its the same microstructure of isoprene rubber (IR) is just the opposite, with 99% trans, 40% crystallinity, melting point 67 ℃, with the production of natural rubber, gutta, and Balata is very similar. So, has begun to gradually replace the natural products, and further development of the apparatus used in plastic surgery, plaster substitutes and sports protection equipment. In recent years, the use of TPI excellent crystallinity and temperature sensitivity, and the successful development of a shape memory rubber material, much of it ages. Structurally speaking, TPI is a high trans-formed crystalline structure as the hard segment, and then with the rest of arbitrary shape elastic phase state was part of the combination of soft segments consisting of thermoplastic rubber. Compared with other TPE, the advantage of mechanical strength, good resistance to injury, but also cure the disadvantage of softening temperature is very low, generally only 40-70 ℃, use is restricted. Currently, only Canada Polysar international and Japanese Kurary two in production, production is estimated that thousands of t so. Qingdao University of Science and Technology recently developed TPI, and carried out using the test, the State Technology Invention. In addition, China is developing a large number in the middle third in Hunan, Hubei, Sichuan, the area of ??your tree Eucommia Eucommia rubber, it is also a trans-l, 4 polyisoprene rubber, often rich in abundance, considerable development potential. In 1974, the company successfully developed in Japan JSR BR rubber (cis 1,4-polybutadiene a) of the isomers - between the same l, 2 polybutadiene, referred to as TPB. It contains more than 90% l, 2 位 between the same combination of polybutadiene rubber, trade name RB. Microstructure between the hard segments by the crystalline structure of some of the same soft segment and a soft part of each other constitute any form of block polymers. Currently there is only a Japanese production, although its heat resistance, mechanical strength than rubber, but with a good transparency, weather resistance and electrical insulation, and photolysis, widely used in the footwear, sponge, film and light other industrial rubber products, the annual demand has more than 27,000 t. Lee TPB other TPE TPI biggest difference is that it can be vulcanized. TPE can not be used to solve the general sulfur, peroxide curing. But must use electronic waves, radiation and other special devices only. Can be modified to mention the quality problems, thus improving the TPE heat resistance, oil resistance and durability of poor and other shortcomings. TPB in the 75-1 10 ℃ within the melting point of any process, both for the production of injection molding of non-vulcanized slippers, sandals, vulcanized foam manufacturers can also use the sports shoes, sneakers, etc. in the end. It is not easy compared with EVA foam midsole collapse deformation, wear comfortable, help to improve athletic results. TPB-made film, with good ventilation, water and transparency, easy-to-light decomposition, very safe, especially for families and vegetables, fresh fruit packaging purposes. 4. Vinyl chloride type thermoplastic PVC and TPE thermoplastic CPE is divided into two categories, the former is called TPVC, the latter known as TCPE. TPVC mainly the flexibility of the modified PVC material, is divided into chemical polymerization and mechanical blending two forms. Mechanical blending NBR main part of the cross-linked to form mixed with PVC blends (PVC / NBR). TPVC actually said to just an extension of soft PVC resin, but greatly improved because of compression deformation, thereby forming a rubber-like PVC. This TPVC modified products can be regarded as PVC and rubber substitutes, mainly in its manufacturing rubber hose, rubber, tape and some plastic parts. Currently over 70% of consumption in the automotive field, such as car steering wheel, windshield wipers, etc. section. Other purposes, wires about 75%, 10% waterproof film is about. In recent years, began to expand into home appliances, gardening, industrial and daily operations raincoat and so on. Currently, a large number of sales on the international market, mainly PVC and NBR, and cross-linked NBR modified PVC blends, rubber and plastic blends has become the most successful models. United States, Japan, Canada, Germany and other countries, nitrile rubber manufacturer Jieyou mass production in industry has formed a separate PVC / NBR material, with its mass production of rubber hose, rubber, plastic sheets and other rubber products. PVC and other polymer blends such as PVC / EPDM, PVC / PU, PVC / EVA blends, PVC and vinyl, acrylic grafting materials and so on, also have come into production. With the stringent environmental requirements of the said benefits, TPVC escape of acid gas, etc. is still difficult to solve, environmental pollution, the recent growth rate in the world has declined, the use of the range has been greatly affected. China's production and use of TPVC are HPVC, research from the 90s, only a small amount of production and supply. Present in PVC / NBR and PVC / EVA blends in the form of majority, except for certain commodities, a total of mixing, most of the self-reference by the rubber mixing plant, widely used in the manufacture tanks, hose, shoes, etc., have been partially replaced by CR and NBR, and NR, SBR, very good results, the amount has expanded each year. At present, the production of nitrile rubber Lanzhou Petrochemical Company has PVC / NBR blends to market. Nanjing University and Beijing University of Chemical Technology has further developed the PVC / NBR and WRP (crumb rubber), PVC / NBR / CPE / WRP blend of thermoplastic elastomer. Zhejiang University, systematically carried out PVC / PE, PVC / PS blends research. Today China has become the world after the United States to use the country's largest production TCPE, 2001, annual sales have left should be the right of 10 million t (capacity of 1 60 000 t), the largest Weifang Yaxing Chemical has 70,000 t of the world class production equipment. In addition, more than 10 Hangzhou Mercury chemical production. Which, CPE rubber 1.5-2 million t, is widely used in cables, hoses, auto parts and waterproofing membrane and so on. CPE and CPE resins are blends of rubber with TPE function TCPE, began to be applied. In the future, TPVC and TCPE may become part of our place of NR, BR, CR, SBR, NBR rubber and PVC plastic, new rubber material. 5. TPE TPE polyurethane polyurethane and isocyanate by the reaction of urethane hard segments and soft segments of polyester or polyether block each other with the thermoplastic polyurethane rubber, referred to as TPU, the world's production and sales have more than 20 million t, accounting for PUR (CPU, MPU) of the l / 5. TPU most developed in Europe and America, with its output of each of 7-8 million t, about the world's 3 / 4, Japan and India each, 12000 t, China 9 000t. TPU has excellent mechanical strength, wear resistance, oil resistance and resistance to flex, especially the most outstanding wear resistance. The disadvantage is heat, heat water, poor compression resistance, appearance and easy to turn yellow, sticky and easy processing mold. Currently the major countries in Europe and America for the manufacture of ski boots, hiking boots and other sporting goods, and for the production of a large number of sports shoes, sneakers, consumption of many. TPU can also be formed by injection molding and extrusion methods such as automobile, machinery, and watches and other parts, and is used extensively for high-pressure hose (rubber outside), tubing, sheets, belts, conveyor belts, wire and cable, tape and other products. Which accounted for 40% of injection molding, extrusion molding is about 35%. In recent years, TPU technology to improve the performance increase of 7 workers, but also many new varieties of ease of processing. As for two-color molding, can increase transparency and high flow, high recovery can improve the processing efficiency of the shoe with TPU. For the manufacture of non-transparent plastic hose, low hardness and easy processing TPU. For large parts such as automobile bumpers dedicated to glass fiber reinforced to increase rigidity and impact of enhanced TPU and so on. Add especially in the TPU reactive component, after the thermoplastic molding, through aging, and the formation of not fully IPN (by the cross-linked polymer and the formation of crosslinked polymer IPN) developed very rapidly. The IPN TPU TPU further improve the physical and mechanical properties. In addition, TPU / PC blend alloy type TPU, but also raise the safety performance of automobile bumpers. In addition, the high permeability of the TPU, conductivity of TPU, and there have been dedicated to the living body, tape, safety glass and other aspects of TPU. Internationally, TPU manufacturer based in U.S., Japan and Europe has reached more than 30 much very rich variety of brands. Germany's Bayer, BASE, the United Kingdom ICl (in order to enjoy Ismail acquisition), An ch. r and other key focus mainly on the shoe, the United States of DDE, Mobay and Japan astoran, POIvurethane mechanical components such as a car-based, are common to the surrounding areas of expansion. The same family as the TPU PUR, in particular, liquid polyurethane rubber ('PU also known as CPU) is particularly rapid development, has been poured into the tape, shoe-making area, and has started to enter the bike Yi, industrial tires and so on. Instead of part of the LPU with TPU and rubber have been just around the corner, as in the engineering aspects of the development of rubber and plastic parts, not to be made. In addition, the health sector for the tube, film, sheet, special parts, condoms, electronic communications system for wire and cable sheathing used, aerospace manufacturing tank with its terms, balloons and so are the new growth point. China has become Asia's largest production and consumption country PU, 2000, annual production of 920,000 t, is now over one million tons more than 400 million t of the world's l / 4. Currently, the demand for PUR elastomers great, Yantai, Taiyuan, Nanjing, Shanghai and other places have more than 10 million t PUR production capacity. PUR 2000 production 85,000 t, of which there are 0.5 million TPU t. Footwear, synthetic leather industry and the automotive industry is the number one growth market TPR applications, coatings and adhesives industry is also promising. The next few years, Shanghai, Nanjing and other world-class 160 000 t or more after the completion of large-scale production base polyurethane. TPU production will grow into several times, when China will be the world's largest TPU sole manufacturing and rapid development of the auto parts industry, as the center to form a variety of TPU world.
