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纸质出版日期:1965-2-20,
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冯新德, 邱南飞, 蒋德彰. 乙烯类单体的负离子聚合研究——第三丁基乙烯基酮的聚合[J]. 高分子学报, 1965,7(1):48-55.
Voong Sing-tuh, CHIU NAN-FEI, CHIANG TEH-CHANG. STUDIES ON ANIONIC POLYMERIZATION OF VINYL MONOMERS --POLYMERIZATION OF t-BUTYL-VINYLKETONE[J]. Acta Polymerica Sinica, 1965,7(1):48-55.
本文报导了第三丁基乙烯基酮在不同溶剂中应用各种负离子引发剂的聚合研究。以正丁基锂为引发剂
吡啶或四氢呋喃为溶剂时
都是均相聚合
得到无定形聚合物
它们的软化温度为40—180°之间
如果以苯、甲苯、二甲苯或正庚烷为溶剂
则都是非均相聚合
得到结晶性聚合物
有着高达260—280°之间的熔点。上述结晶性与无定形聚第三丁基乙烯基酮的红外光谱有着显著的不同
结晶性聚合物具有特征的吸收峯
以1100厘米-1与1330厘米-1二处最为明显。还研究了不同比例的混合物的红外光谱
当结晶性聚合物含量降至 87%以下时
则 1100厘米-1
1290厘米-1及 1330厘米-1三处吸收峯逐渐减弱
当减少至13%时则与无定形聚合物的光谱一致。此外金属锂、钠与钾都能引发聚合第三丁基乙烯基酮
也试用了NaH
LiAlH4
RONa
ROK
RMgX
二苯酮以及二苯酮钠等引发剂进行非均相聚合。
This papcr presents the effect of different initiators and solvents on the anionic polymerization of tert-butyl-vinylketone.An amorphous polymer was obtained with softening point at 140—180°when the title monomer was polyrmerized with n-butyl lithium as anionic initiator in a homogenous phase with pyridine or tetrahydrofuran as solvent,while that in a heterogenous phase such as benzene,toluene,xylene or n-heptane it would give crystalline and probably isotactic polymer with melting point between 260—280℃.The crystalline form showed the characteristic bands at 1 100 cm-1 and 1330 cm-1.which were both absent in those of the amorphous form.A series of IR spectra were obtained from mixture of crystalline polymer with various amounts of amorphous form.It was found that bands of 1100 cm-1
1290 cm-1
and 1330 cm-1 would weaken gradually as the content of crystalline form dropped below 87%,and the spectra would be actually identical with those of the amorphous one of the crystalline part dropped below 14%. Alkali metals as Li.Na,K as well as their organometallic com-pounds as NaH,LiAlH4,RoNa,ROK,RMgX and diphenylketone-Na were also able to initiate heterogenous polymerization.
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