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Dipole Moments of Poly(ethylene oxide) and Poly(vinylcrown ether)

聚环氧乙烷和聚乙烯基冠醚的偶极矩

基本信息

批准号：
03650731
负责人：
YAMAGUCHI Noriko
金额：
$ 1.15万
依托单位：
Tokyo Woman's Christian University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

1 Dipole moment of poly(ethylene oxide)The dipole moments of poly(ethylene oxide) with different molecular weights were determined from dielectric constant and density measurements performed on their dilute benzene solutions over the temperature range from 25 to 55ﾟC.The Values of average dipole moment per repeat unit, mu, at 25ﾟC were 1.037D (M_W=4.6X10^4), 1.039D(M_W=9.5X10^4), 1.038D(M_W=27X10^4), 1.041D(M_W=57X10^4) and 1.042D (M_W=86X10^4)(D ; debye unit, Mw ; weight average molecular weight). mu for the PEO chains was constant to within 0.5% for the cited range of molecular weight. The dipole moment ratio was calculated as <mu^2>/nm^2=0.47_2*0.00_2(at 25ﾟC), where n and m are number of bond dipoles and their dipole moment. Temperature coefficient averaged for five polymer samples was dln<mu^2>/dT=(1.9_4*0.2_7)X10^<-3>K^<-1>.2 Synthesis and dielectric property of polyvinylbenzo-15-crown-5The preparation of the macromer, 4'-vinylbenzo-15-croun-5(I), is as follows. Catechol was converted to catechol diacetate, followed by a Fries rearrangement which produced 3,4-dihydroxyacetophenone(VI). VI was reacted with 1,11-dichloro-3,6,9-trioxaundecane to form 4'-acetobenzo-15-crown-5(VIII). VIII was reduced with NaBH4 and the resulting alcohol was dehydrated with a trace of p-toluene sulfonic acid to form I. Polyvinylbenzo-15-crown-5 was prepared by radical polymerization using azobis(isobutylonitrile) as initiator at 70 ﾟC. The dipole moment measured in benzene by use of the three terminal platinum cell (cell capacitance : 26.485pF) was 2.2773D(25ﾟC). Temperature coefficient was dln<mu^2>/dT=1.54X10^<-3>K^<-1>.

1聚乙烯的偶极矩聚（环氧乙烷）的偶极矩在25 ~ 55 ℃的温度范围内，通过对不同分子量的环氧乙烷的稀苯溶液进行介电常数和密度测量，确定了它们的分子量。在25 ℃时，每个重复单元的平均偶极矩μ为1.037 D（M_W= 4.6 × 10^4）、1.039 D（M_W= 9.5 × 10^4）、1.038 D（M_W= 27 × 10^4）、1.041 D（M_W= 57 × 10^4）和1.042 D（M_W= 86 × 10^4）（D ;德拜单位，Mw ;重均分子量）。对于所述分子量范围，PEO链的μ恒定在0.5%以内。偶极矩比计算为<mu^2>/nm^2=0.47_2*0.00_2（在25 ℃时），其中n和m是键偶极的数量和它们的偶极矩。5个聚合物样品的平均温度系数为dln μ 2/dT=（1.9_4*0.2_7）× 10 - 5 <-3>K ~<-1>（-2）聚乙烯基苯并-15-冠-5的合成和介电性质大分子单体4 ′-乙烯基苯并-15-冠-5（I）的制备如下。邻苯二酚被转化为邻苯二酚二乙酸酯，然后通过Fries重排产生3，4-二羟基苯乙酮（VI）。VI与1，11-二氯-3，6，9-三氧杂十一烷反应生成4 '-乙酰苯并-15-冠-5（VIII）。VIII用NaBH 4还原，所得醇用痕量对甲苯磺酸脱水形成I。以偶氮二异丁腈为引发剂，在70 ℃下进行自由基聚合，制备了聚乙烯基苯并-15-冠-5.用三端铂电池（电池电容：26.485pF）在苯中测得的偶极矩为2.2773D（25 ℃）。温度系数为dln<mu^2>/dT= 1.54 × 10 ~（-1）<-3>K ~（-1）<-1>。