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lucia_wuha

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The formation  of macrocyclic oligomers  in  tetrahydrofuran  polymerization systems  initiated with ethyl  trifluoromethanesulfonate (ethyl triflate) and with trifluoromethanesulfonic  acid (triflic acid) has been investigated.  In  polymerization systems initiated with ethyl  triflate,  linear and cyclic oligomers are  found by gas chromatography/chemical ionization mass spectrometry.  In systems initiated with triflic acid only cyclic oligomers are found under similar polymerization conditions. From these findings, as well as  from conversion and solution viscosity data,
a chain coupling-ring  opening mechanism is discussed for the polymerization of tetrahydrofuran with triflic acid.

    The mechanism of  the polymerization of  tetrahydrofuran (THF) has been  investigated recently  in great detai,  particularly  the polymerization  initiated with esters of  trifluoromethanesulfonic acid  (triflic acid).G9 An equilibrium  between an oxonium ion and a covalent ester at  the propagating chain head was found to  depend on the polarity of  the medium: In a medium of high polarity, the propagating species was the expected oxonium ion. In a medium of  low polarity, the predominant end  group was  found  to be a  covalent  ester, formed by attack of  the counterion  at the α-methylene carbons of  the oxonium  ion.Chain propagation occurs by nucleophilic attack of monomer at  the a-methylene of the oxonium ion or the ester to  form a new oxonium  ion, which may subsequently again be ring opened by the counterion.
    A series of polymerization—depolymerization equilibria thus exist in such a system,  and one would expect  the  formation  of  at least  some macrocyclic oligomers  through “back- biting” reactions. Such macrocycles have indeed been found recently.  In a previous publication, we reported the identification of “THF crown ethers”, formed during the polymerization of tetrahydrofuran  (THF) with trialkyl oxonium salts.We now wish to  report the  identification of such crown ethers in THF  polymerizations initiated by alkyl triflate and  triflic acid.
     The mechanistic implications of crown ether formation in acid-catalyzedpolymerizations are discussed, and a possible mechanism for such polymerizations is proposed.
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四十一度六

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lucia_wuha(金币+1, 翻译EPI+1): 2010-11-11 18:20:39
木子小木虫(翻译EPI-1):EPI发放错误 2010-11-11 19:48:12
lucia_wuha(金币+1, 翻译EPI+1):想帮忙就翻译,不想帮忙就别来,谢谢 2010-11-11 20:46:54
木子小木虫(翻译EPI-1): 2010-11-15 21:39:20
it is so long。
2楼2010-11-11 07:54:45
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lucia_wuha

金虫 (小有名气)


哪位高手帮忙翻译一下,谢谢!
3楼2010-11-11 17:31:31
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孙燕姿

至尊木虫 (正式写手)



cfk580713(金币-1):google翻译机译,警告一次。 2010-11-21 19:30:04
lucia_wuha(金币+8, 翻译EPI+1): 2010-11-23 19:00:31
在四氢呋喃聚合三氟乙酯(乙基三氟)启动系统,并与三氟甲磺酸(triflic酸)大环低聚物的形成进行了研究。在聚合系统开始与三氟乙酯,线性和环状低聚物的气相色谱发现/化学电离质谱。在与triflic酸系统只启动循环低聚物的聚合条件下找到类似。从这些调查结果,以及从数据转换和溶液粘度,链条联轴器,开环机理讨论了酸聚合四氢呋喃与triflic。机制的四氢呋喃的聚合(四氢呋喃),研究了最近在大德泰, 。特别是与三氟甲磺酸(triflic酸)酯引发聚合的G9的离子之间的oxonium以及在传播链头被发现共价酯平衡依赖于介质的极性:在高极性介质,传播物种的预期oxonium离子。在一个低极性介质中,主要的端基被认为是共价酯,由在该oxonium ion.Chain传播的α-亚甲基碳反离子所形成的单体攻击亲核攻击在A -亚甲基发生在oxonium离子或酯,形成一个新的oxonium离子,随后可能再次反离子开环。一种平衡系列聚合,解聚,从而存在着这样一个系统,一个期望的低聚物的形成至少有一些大环通过“背咬”的反应。这样的大环最近确实发现。在以往的出版物中,我们报道了“四氢呋喃冠醚”期间四氢呋喃(THF)与三烷基oxonium salts.We聚合而成的,现在想鉴定报告等冠醚的四氢呋喃聚合鉴定烷基三氟和triflic启动酸。酸catalyzedpolymerizations形成的机械冠醚的影响进行了讨论,这样一个聚合的可能机制的建议。
4楼2010-11-20 23:23:18
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wust67

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楼主考虑放80个金币吧,也就家当的四分之一而已。
5楼2010-11-21 19:29:16
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