PolyurethaneOne of the main raw materials of resin is isocyanate, 蕞Alkyl isocyanate was prepared by the German chemist Wurtz in 1849 by metathesis reaction of alkyl sulfate and potassium cyanate. In 1850, Hofmann used diphenyloxamide to perform dehydrogenation reaction to obtain phenyl isocyanate. In 1884, Hentschel reacted amines or (ammonium) salts with phosgene to prepare isocyanates, thus laying the foundation for the industrialization of isocyanates.
In 1937, the German I.G. Farben Company (Bayer Company) Professor O. Bayer and his colleagues first studied the addition polymerization reaction of diisocyanate and found that various polyurethane and polyurea compounds could be generated, but they did not find its practical value. Later, Professor Bayer and others used the addition polymerization reaction of 1,6-hexamethylene diisocyanate and 1,4-butanediol to produce linear polyurethane resin. This resin has thermoplasticity, spinnability, and can be made into plastics and fibers. This polyurethane resin was named Igamid U, and the fiber made from this resin was called Perlon U. The output of this fiber only reached 25t/month in 1944.
Germany font>Bayer Company inWorld War IIDuring this period, the reaction between diisocyanate and hydroxyl compounds was further studied, and products such as rigid foam plastics, coatings and adhesives were produced. Between 1941 and 1942, a 10t/month polyurethane resin product test workshop was built.
Polyurethane foam was developed first. World War IIAfter that, from 1945 to 1947, relevant American companies read the reports about polyurethane resin in the PB report and began to pay attention to polyurethane. Resin material emphasis. Especially companies related to the Air Force are more interested. In 1947, DuPont and Monsanto built 2,4-toluene diisocyanate test plants, and the manufacturing of rigid polyurethane foam began at Good Year Aircraft and Lockheed Aircraft.
In 1952, Bayer Company reported the soft polyester type Research results on polyurethane foam. Soft polyester polyurethane foam has the advantages of light weight, low density, and high specific strength, laying the foundation for the industrial application of polyurethane. From 1952 to 1954, Bayer Company used a continuous method to produce flexible polyester polyurethane foam, named the flexible foam Moltoprene, applied for a patent, and sold this proprietary technology around the world. It uses toluene diisocyanate and polyadipate polyol as raw materials, tertiary amine as catalyst, ionic emulsifier as foam stabilizer, and water as foaming agent. The soft polyester polyurethane foam has excellent It has excellent mechanical properties and oil and solvent resistance, but its resistance to moisture and heat aging is poor, and the cost of raw materials is also high.
In 1954, the American Monsanto Company and Bayer Company entered into technical cooperation , established Mobay Chemical Company, and since then began the production of polyurethane raw materials in the United States, and the foam market began to slowly develop. In 1957, Wyandotte Chemical Company successfully prepared polyurethane foam using propylene oxide-ethylene oxide block copolyether as raw material and realized industrialization. Since the petroleum industry provided low-priced propylene oxide polyether polyol raw materials, it prompted The cost of polyether polyurethane foam is greatly reduced, and the aging resistance of the product is significantly improved compared to polyester polyurethane foam. It is also a breakthrough in the industrialization of polyurethane foam. In 1958, Mobay Company and Union Carbide Company used highly active triethylenediamine and organotin as catalysts for polyurethane foam materials, changing the polyurethane foaming process from a two-step method to a one-step method, which further promoted the development of polyurethane foam. In the development of plastics, in the same year DuPont successfully prepared rigid polyurethane foam using monofluorochloroform (CFC-11) as a blowing agent. Therefore, the American polyurethane industry occupies an important position in the world.
Japan inIn 1955, technology was introduced from the German Bayer Company and the American DuPont Company and the production of polyurethane resin began. The British ICI Company developed polyester-type rigid polyurethane foam using diphenylmethane diisocyanate (MDI) as raw material in 1957, and later used MDI to make polyester-type flexible polyurethane foam and polyether-type polyurethane foam. plastic.
In 1961, polymeric polyisocyanate, namely polyphenyl polymethylene polyisocyanate (PAPI), was used to prepare hard High-quality polyurethane foam improves product performance and reduces toxicity during construction. In addition, PAPI was used to prepare polyurethane-modified polyisocyanurate rigid foam, which had excellent heat resistance and was put on the market in 1967. In 1969, Bayer Company first reported the use of high-pressure collision mixing method to produce polyurethane foam, and exhibited苐 A reaction injection molding machine with self-cleaning and circulating mixing head (RIM) device. In 1974, the United States had adopted the RIM process to produce large-scale polyurethane parts. In 1979, the glass fiber reinforced polyurethane RIM process was used to produce automobile fenders and body panels. In 1980, glass fiber reinforced structural reaction injection molding (SRIM) polyurethane products were introduced. After the United Nations formulated the Montreal Protocol on Substances that Deplete the Ozone Layer in 1987, the issue of replacing chlorofluorocarbon (CFC) blowing agents used in polyurethane foams arose. After years of efforts, significant progress has been made.
About polyurethane elasticity In 1950, Professor Bayer published a paper on mixing polyurethane elastomer. In 1953, Muler successfully studied liquid casting polyurethane elastomer. These elastomers are made by reacting a polyester polyol with naphthalene diisocyanate (NDI), called Vulkollan. In 1953, DuPont performed ring-opening polymerization of tetrahydrofuran to produce polyoxytetramethylene glycol, an important polyether raw material that can produce polyurethane elastomers with excellent hydrolysis resistance and low temperature resistance. In 1958, Schollenberger of Goodyear Tire & Rubber Company in the United States reported thermoplastic polyurethane elastomer. This kind of elastomer particles can be made into parts using plastic injection molding and extrusion molding processing methods. Industrial production was achieved in 1960, making polyurethane elastomers more popular. More versatile.
In 1940, researchers from I.G. Farben Company introduced triphenyl Methane-4,4′,4″-triisocyanate has been successfully used to bond metal to sodium butadiene rubber. Used on tank tracks during World War II , laying the foundation for the polyurethane adhesive industry. In 1951, the United States used drying oil and its derivatives to react with toluene diisocyanate to prepare oil-modified polyurethane coatings. Later, they successfully developed two-component catalytic curing polyurethane coatings. With one-component moisture-curing coatings.
Polyurethane elastic fiber was successfully researched in 1958. In 1959, DuPont Company began to produce polyether-type polyurethane elastic fiber with the brand name Lycra. This brand is still in use today. In June 1963, DuPont Company successfully researched polyurethane fiber. Synthetic leather, whose appearance and feel is similar to natural leather, has the brand name Corfam. In 1964, Japan’s Kurashiki Rayon Company also successively produced polyurethane synthetic leather with the brand name Clarino.
In the mid-1960s, various countries have successfully researched polyurethane paving materials and waterproof materials, thus making polyurethane resin Applied in civil construction engineering.
According to a report by the British IAL consulting company, the total global production of polyurethane products was approximately 10 million tons in 2000, approximately 13.7 million tons in 2005, and is estimated to reach 17 million tons in 2010. From 2000 to 2005 The average growth rate was 6.7%, and the average annual growth rate from 2005 to 2010 was 4.2%. The specific output data of several major categories of polyurethane products estimated by IAL are shown in Table 1-1. The development of various regions is uneven. The development in Europe and the United States is close to saturation and the annual growth rate is low. In developing countries, the application of polyurethane materials has developed rapidly in recent years. The estimated polyurethane output and average annual growth rate by region from 2000 to 2010 are shown in Table 1-2.
In 2005, the output of polyurethane materials in each region accounted for the total global polyurethane production Volume share: Asia-Pacific 14%, Eastern Europe 4%, Western Europe 24%, China (mainland) 21%, NAFTA 28%, South America 3%, Middle East and Africa 6%. In 2007, China’s total PU consumption accounted for 28.5% of global total consumption, second only to North America (31%). It is expected that after 2010, China will become the world’s mostlarge polyurethane consumer market. The global PU product consumption overview and forecast from 2005 to 2012 are shown in Table 1-3.
From polyurethane In terms of material product form, polyurethane foam has always been the main polyurethane product. For example,The types and proportions of polyurethane products in Europe, the Middle East and Africa in 2004: soft foam 39%, hard foam 26%, coatings 13%, elastomers 12%, adhesives 4%, adhesives 4%, Sealant2%.
��Proportion: soft foam 39%, hard foam 26%, coating 13%, elastomer 12%, adhesive 4%, adhesive 4%,Sealant2%.
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