烷基取代聚硅烷共聚物的侧基对螺旋构象的影响

doi:10.7503/cjcu20140577

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (11): 2481.doi: 10.7503/cjcu20140577

烷基取代聚硅烷共聚物的侧基对螺旋构象的影响

唐贤慧, 季猩猩, 钱凯, 李宝宗, 李艺(), 杨永刚

苏州大学材料与化学化工学部, 苏州 215123

收稿日期:2014-06-25 出版日期:2014-11-10 发布日期:2014-10-14
作者简介:联系人简介: 李艺, 女, 博士, 副教授, 主要从事功能纳米材料研究. E-mail:liyi@suda.edu.cn
基金资助:
国家自然科学基金(批准号: 21274098)资助

Effect of the Alkyl Side Chain on the Helical Conformation of Dialkylpolysilane Copolymers^†

TANG Xianhui, JI Xingxing, QIAN Kai, LI Yi^*(), YANG Yonggang

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

Received:2014-06-25 Online:2014-11-10 Published:2014-10-14
Contact: LI Yi E-mail:liyi@suda.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21274098)

摘要/Abstract

摘要：

以手性化合物n-癸基-(S)-(+)-2-甲基丁基二氯硅烷(Si1)和非手性化合物n-癸基-2-乙基丁基二氯硅烷(Si2)为单体合成了聚硅烷共聚物[P(Si1-co-Si2)]. 通过改变Si1和Si2的投料比, 聚合得到一系列P(Si1-co-Si2). 通过核磁表征P(Si1-co-Si2)为无规共聚物. 利用圆二色谱(CD)和紫外吸收光谱研究系列共聚物的手性传递行为. 研究发现, Si2的均聚物在其对应的紫外吸收带324 nm处没有CD信号. 当加入Si1共聚后, 产生CD信号, 随着Si1含量的增加, 共聚物的CD信号迅速增强, 当Si1摩尔分数为2%时可诱导共聚物形成单手螺旋优势构象. 当Si1含量达到70%时, 信号强度最大. 在P(Si1-co-Si2)中Si1含量增加的过程中, 共聚物的紫外吸收带同时发生蓝移. 当Si1含量达到50%时, 分子量较低的样品具有较强的光学活性, 并且随着分子量的增大, 紫外吸收红移. 研究结果初步表明, 聚硅烷共聚物的螺旋结构由手性侧基决定, 但非手性侧基的奇偶性却没有体现.

关键词: 光学活性高分子, 聚硅烷, 螺旋构象, 手性放大, “军官-士兵”效应

Abstract:

Silane copolymers [P(Si1-co-Si2)] were synthesized using (S)-2-methylbutyl-n-decyldichlorosilane(Si1) and 2-ethylbutyl-n-decyldichlorosilane(Si2) monomers. A series of P(Si1-co-Si2) was synthesized by varying the ratio of Si1 and Si2. The random copolymer was confirmed by nuclear magnetic resonance. The chirality transfer behaviour of polysilane samples was characterized by circular dichroism spectrum(CD) and ultraviolet absorption spectrum(UV). It was found that homopolymer of achiral monomer Si2 exhibited no CD signal, but intense and sharp UV absorption at 324 nm. When the chiral monomer Si1 was added into the main chain of polymer molecules, the obtained copolymer molecules were induced with a marked CD signal. When the mole fraction of Si1 increased, the intensity of CD signal became higher rapidly, even as little as 2.0%(molar fraction) of enantiopure Si1 could induce a marked single-handed helical conformation in these copolymers. After that, the intensity of CD signal increased slightly and then decreased slightly. Moreover, the λ_max value tended to blueshift progressively with increasing the molar fraction of the chiral moiety in the copolymers. For P(Si1-co-Si2) of 50%Si1(P50) with diffierent molecular weight, the λ_max tended to redshift with increasing molecular weight, and the lower molecular weight P50 possessed a stronger optical activity. The result indicated that the handedness of the copolymers was controlled by the chiral alkyl chain and the odd-even effect of the achiral alkyl chain was not reflected.

Key words: Optically active polymer, Polysilane, Helical conformation, Chiral amplification, “Sergeants and Soldiers”, principle

中图分类号:

O631

TrendMD:

唐贤慧, 季猩猩, 钱凯, 李宝宗, 李艺, 杨永刚. 烷基取代聚硅烷共聚物的侧基对螺旋构象的影响. 高等学校化学学报, 2014, 35(11): 2481.

TANG Xianhui, JI Xingxing, QIAN Kai, LI Yi, YANG Yonggang. Effect of the Alkyl Side Chain on the Helical Conformation of Dialkylpolysilane Copolymers^†. Chem. J. Chinese Universities, 2014, 35(11): 2481.

图/表 6

Fig.1 Molecular structures of the silane monomers and polymers

Fig.2 29Si NMR spectra of P0(a), P50(b) and P100(c)

Table 1 Selected samples for UV and CD measurements

Sample	n	m	10^-4M_w	M_w/M_n
P0	0	1	2.5	1.24
P02	0.02	0.98	2.5	1.12
P05	0.05	0.95	2.1	1.05
P30	0.3	0.7	2.4	1.10
P50	0.5	0.5	2.5	1.12
P70	0.7	0.3	2.2	1.06
P90	0.9	0.1	2.5	1.09
P100	1	0	2.3	1.08

Fig.3 UV(A) and CD(B) spectra of polysilane copolymers containing(S)-2-methylbutyl and 2-ethylbutyl side groups in THF at 25 ℃

Fig.4 CD signal of different copolymers with increase of chiral substituents

Fig.5 UV(A) and CD(B) spectra of various molecular weights of copolymer with 50%(molar fraction) of Si1

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烷基取代聚硅烷共聚物的侧基对螺旋构象的影响

Effect of the Alkyl Side Chain on the Helical Conformation of Dialkylpolysilane Copolymers^†

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烷基取代聚硅烷共聚物的侧基对螺旋构象的影响

Effect of the Alkyl Side Chain on the Helical Conformation of Dialkylpolysilane Copolymers†

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Effect of the Alkyl Side Chain on the Helical Conformation of Dialkylpolysilane Copolymers^†