CHAIN TRANSFER DURING THE AQUEOUS RING-OPENING METATHESIS POLYMERIZATION OF 7-OXANORBORNENE DERIVATIVES
CHAIN TRANSFER DURING THE AQUEOUS RING-OPENING METATHESIS POLYMERIZATION OF 7-OXANORBORNENE DERIVATIVES
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DOI：
10.1021/ma00070a002
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发表时间：
1993-08-30
期刊：
影响因子：
5.5
通讯作者：
PACIELLO, RA
中科院分区：
文献类型：
--
作者：
FRANCE, MB;GRUBBS, RH;PACIELLO, RA
以Ru（II）（H_2O）_6（tos）_2（1）为催化剂，在末端无环烯烃（如3-丁烯-1-醇和丙烯酸甲酯）存在下，进行外，外-5，6-双（甲氧基甲基）-7-氧杂双环[2.2.1]庚-2-烯（3）的开环易位聚合（ROMP），得到低分子量聚合物材料。通过一维和二维H-1 NMR光谱分析这些低聚物样品，将其鉴定为来自真正的复分解链转移机制。这些数据和通过高分辨率质谱法鉴定具有对应于无环链转移剂的亚烷基端基的开环单体单元证实了本研究是通过1.一系列的无环酯的链转移活性的比较产生的反应顺序的末端烯烃>失活的末端烯烃>内烯烃>失活的内烯烃，与良好表征的均相亚烷基络合物的行为一致。
Ring-opening metathesis polymerization (ROMP) of exo,exo-5,6-bis(methoxymethyl)-7-oxabicyclo[2.2.1]hept-2-ene (3) catalyzed by Ru(II)(H2O)6(tos)2 (tos = p-toluenesulfonate) (1) in the presence of terminal acyclic olefins such as 3-buten-1-ol and methyl acrylate affords low molecular weight polymeric materials. Analysis of these oligomer samples by one- and two-dimensional H-1 NMR spectroscopy identifies them as resulting from a true metathesis chain transfer mechanism. These data and the identification of the ring-opened monomer units with alkylidene end groups corresponding to the acyclic chain transfer agent by high resolution mass spectrometry confirm this study as the first example of metathesis of an acyclic olefin by 1. A comparison of the chain transfer activities of a series of acyclic esters yields a reactivity order of terminal olefins > deactivated terminal olefins > internal olefins > deactivated internal olefins, consistent with the behavior of well-characterized homogeneous alkylidene complexes.