热塑性弹性体发展简史

 

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热塑性弹性体发展简史  

 

A Brief History of Thermoplastic Elastomers

PVC热塑性弹性体

    最早的热塑性弹性体是B.F. Goodrich Company于1926年生产PVC/NBR合金，类似我们现在称作热塑性弹性体预聚物。

聚氨酯弹性体

    到了1937年杜邦和英国帝国化学工业集团生产了聚氨酯弹性体（PU）。直到上世纪60年代，在美国是B.F.Goodrich, Mobay 以及 Upjohn公司实现聚氨酯弹性体的商业化，在欧洲Bayer A.G. 和Elastogran公司而完成的。

苯乙烯类热塑性弹性体

    苯乙烯-二烯类的共聚物是由美国的科腾Kraton公司于1966年首先生产出来的，包括SBS（苯乙烯、丁二烯）和SIS（苯乙烯、异戊二烯）用阴离子聚合制得。菲利普斯石油公司(Phillips Petroleum Co.)于1968年生产了星形苯乙烯嵌段共聚物，进入了SBS弹性体领域。在1972年，壳牌公司生产了SEBS共聚物，EB是指乙烯-丁烯共聚物嵌段。聚丁二烯中间段的氢化消除了氢键，提高了制品耐氧化降解和耐臭氧攻击。该产品的商品名为Kraton G®.。

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聚酯型热塑性弹性体

    聚酯型热塑性弹性体也在上世纪60年代开始研发，杜邦公司于1972年推出，商品名为Hytrel®.。类似的产品如GAF公司在70年代后期的Pelprene®，伊斯曼化学（Eastman Chemical Co.）1983推出的 Ecdel®，GE公司1985年的的(Lomod®)。

聚烯烃热塑性弹性体TPOs

    聚烯烃热塑性弹性体TPOs研发工作持续了整个60年代，Hercules Inc公司第一个申请了这方面的专利，产品是由结晶的聚丙烯PP和乙丙共聚物EPM制得的。

热塑性硫化胶TPVs

    70和80年代，孟山都公司（Monsanto Company）深入研究了热塑性硫化胶TPVs，于1981年首先推出了商品名为Santoprene的EPDM和PP共混物（合金）。类似的产品如1985年丁腈橡胶NBR，商品名为Geolast®。

聚酰胺热塑性弹性体

    聚酰胺热塑性弹性体于1982年由法国Ato Chemie 公司首先生产，商品名为Grilamid®，后面有瑞士Emser Industries公司的Grilon，以及陶氏化学公司（Dow Chemical Company’s）的Estamid®。

单相热熔性橡胶

    杜邦公司于80年代早期发明了单相热熔性橡胶，并且于1985年实现是商品化，为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 翻译@粤高分子 2010年）

 

 

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