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熱塑性彈性體發展簡史  

A Brief History of Thermoplastic Elastomers

PVC熱塑性彈性體

    最早的熱塑性彈性體是B.F. Goodrich Company于1926年生產PVC/NBR合金，類似我們現在稱作熱塑性彈性體預聚物。

聚氨酯彈性體

    到了1937年杜邦和英國帝國化學工業集團生產了聚氨酯彈性體（PU）。直到上世紀60年代，在美國是B.F.Goodrich, Mobay 以及 Upjohn公司實現聚氨酯彈性體的商業化，在歐洲Bayer A.G. 和Elastogran公司而完成的。

苯乙烯類熱塑性彈性體

    苯乙烯-二烯類的共聚物是由美國的科騰Kraton公司于1966年首先生產出來的，包括SBS（苯乙烯、丁二烯）和SIS（苯乙烯、異戊二烯）用陰離子聚合制得。菲利普斯石油公司(Phillips Petroleum Co.)于1968年生產了星形苯乙烯嵌段共聚物，進入了SBS彈性體領域。在1972年，殼牌公司生產了SEBS共聚物，EB是指乙烯-丁烯共聚物嵌段。聚丁二烯中間段的氫化消除了氫鍵，提高了制品耐氧化降解和耐臭氧攻擊。該產品的商品名為Kraton G®.。

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聚酯型熱塑性彈性體

    聚酯型熱塑性彈性體也在上世紀60年代開始研發，杜邦公司于1972年推出，商品名為Hytrel®.。類似的產品如GAF公司在70年代后期的Pelprene®，伊斯曼化學（Eastman Chemical Co.）1983推出的 Ecdel®，GE公司1985年的的(Lomod®)。

聚烯烴熱塑性彈性體TPOs

    聚烯烴熱塑性彈性體TPOs研發工作持續了整個60年代，Hercules Inc公司第一個申請了這方面的專利，產品是由結晶的聚丙烯PP和乙丙共聚物EPM制得的。

熱塑性硫化膠TPVs

    70和80年代，孟山都公司（Monsanto Company）深入研究了熱塑性硫化膠TPVs，于1981年首先推出了商品名為Santoprene的EPDM和PP共混物（合金）。類似的產品如1985年丁腈橡膠NBR，商品名為Geolast®。

聚酰胺熱塑性彈性體

    聚酰胺熱塑性彈性體于1982年由法國Ato Chemie 公司首先生產，商品名為Grilamid®，后面有瑞士Emser Industries公司的Grilon，以及陶氏化學公司（Dow Chemical Company’s）的Estamid®。

單相熱熔性橡膠

    杜邦公司于80年代早期發明了單相熱熔性橡膠，并且于1985年實現是商品化，為Alcryn® 。

以下是英文原文：

A Brief History of Thermoplastic Elastomers

PVC thermoplastic materials

    The development of thermoplastic materials having more or less elastic properties started in the early 1930s with the invention of plasticization of PVC at the B.F. Goodrich Company Thus, they can be considered as the precursors of thermoplastics elastomers, as we know them today.

Polyurethane thermoplastic

    A major breakthrough occurred with the discovery of the basic diisocyanate polyaddition reaction in 1937 [4], which was first applied to produce polyurethane fibers and then to the development of some elastomeric polyurethanes at DuPont and ICI. Commercial polyurethane thermoplastic elastomers were introduced in the 1960s by B.F. Goodrich, Mobay and Upjohn in the United States, and by Bayer A.G. and Elastogran in Europe.

Styrene-diene block copolymers

    Styrene-diene block copolymers were first developed by Shell utilizing anionic block copolymerization of styrene with butadiene (S–B–S) and styrene with isoprene (S–I–S) and were introduced commercially in 1966 as Kraton®. Phillips Petroleum Co. entered this field in 1968 with radial styrenic block copolymers. In 1972 Shell added the S–EB–S copolymer, where EB is the ethylene-butylene copolymer segment.S–EB–S copolymer is prepared by hydrogenation of the polybutadiene center block thus eliminating the double bonds and improving resistance of the product to oxidative scission and ozone attack . The product was introduced as Kraton G®.

Copolyetherester thermoplastic elastomers

    Copolyetherester thermoplastic elastomers were developed during the 1960s and were commercialized by DuPont in 1972 as Hytrel®. Similar products were commercialized by the GAF Corporation in the late 1970s (Pelprene®), by Eastman Chemical Co. in 1983 (Ecdel®), and by the General Electric Corporation in 1985 (Lomod®).

Thermoplastic polyolefin blends (TPOs)

    Thermoplastic polyolefin blends (TPOs) were developed throughout the 1960s. The first patent on record is that of Hercules Inc. covering blends of crystalline polypropylene and ethylene-propylene copolymers (EPM).

Thermoplastic vulcanizates (TPVs)

    Thermoplastic vulcanizates (TPVs) are materials based on an extensive research done at the Monsanto Company during the 1970s and 1980s.The first commercial product was Santoprene® based on a blend (or alloy) of EPDM and polypropylene introduced in 1981. A similar product based on a blend of butadieneacrylonitrile rubber (ASTM designation NBR) and polypropylene, Geolast® was introduced in 1985.

Polyamide thermoplastic elastomers

    Polyamide thermoplastic elastomers were introduced in 1982 by ATO Chemie followed by Grilamid® and Grilon produced by Emser Industries and by Dow Chemical Company’s Estamid®.

Melt-processable rubber (MPR)

    Single-phase melt-processable rubber (MPR) is based on work done at DuPont in the early 1980s and led to the commercialization of proprietary products under the name Alcryn® in 1985.

（Source：handbook of thermoplastic elastomers 翻譯@粵高分子 2010年）

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