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温度响应型手性Salen TiIV嵌段共聚物的可控制备及在硫醚不对称氧化反应中的应用
增强出版Controllable Preparation of Thermo-responsive Chiral Salen TiIV Block Co-polymers for Asymmetric Oxidation of Thioethers
- 高分子学报 2021年52卷第7期 页码：723-733
- 作者机构：
1.湖北工程学院化学与材料科学学院 孝感 432000
2.湖北大学材料科学与工程学院 武汉 430062
3.华中科技大学 生物无机化学与药物湖北省重点实验室 武汉 430074
- 作者简介：
Lei.zhu@hbeu.edu.cn
- 基金信息：国家自然科学基金(基金号 21774029);湖北省自然科学基金(基金号 ┣2019CFB237);2019CFB354┫;湖北省高等学校优秀中青年科技创新团队计划项目(T201816)
DOI：10.11777/j.issn1000-3304.2021.21016
中图分类号：纸质出版日期：2021-07-20，
网络出版日期：2021-05-26，
收稿日期：2021-01-17，
修回日期：2021-02-02，
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张瑶瑶,韩彪,周丽洁等.温度响应型手性Salen TiIV嵌段共聚物的可控制备及在硫醚不对称氧化反应中的应用[J].高分子学报,2021,52(07):723-733.
Yao-yao Zhang, Biao Han, Li-jie Zhou, Ming-yu Wang, Bo-jie Li, Lian-sheng Wang, Lei Zhu. Controllable Preparation of Thermo-responsive Chiral Salen TiIV Block Co-polymers for Asymmetric Oxidation of Thioethers[J]. ACTA POLYMERICA SINICA, 2021,52(7):723-733.
张瑶瑶,韩彪,周丽洁等.温度响应型手性Salen TiIV嵌段共聚物的可控制备及在硫醚不对称氧化反应中的应用[J].高分子学报,2021,52(07):723-733. DOI： 10.11777/j.issn1000-3304.2021.21016.
Yao-yao Zhang, Biao Han, Li-jie Zhou, Ming-yu Wang, Bo-jie Li, Lian-sheng Wang, Lei Zhu. Controllable Preparation of Thermo-responsive Chiral Salen TiIV Block Co-polymers for Asymmetric Oxidation of Thioethers[J]. ACTA POLYMERICA SINICA, 2021,52(7):723-733. DOI： 10.11777/j.issn1000-3304.2021.21016.
摘要
采用可逆加成-断裂链转移自由基聚合法(RAFT)，以
N
-异丙基丙烯酰胺和5-乙烯基手性salen Ti
IV
为反应单体，偶氮二异丁腈为链引发剂，硫代丙酸苄硫酯为链转移剂，可控制备出一系列温度响应型手性嵌段共聚物(聚
N
-异丙基丙烯酰胺-
co
-手性salen Ti
IV
，PN
x
S
y
). 通过红外表征证明该嵌段共聚物结构中含有温敏材料和salen Ti
IV
的特征峰，紫外表征揭示了亲疏水单元比例对嵌段共聚物临界温度LCST的影响，动态光散射证明亲疏水比例对嵌段共聚物水合动力学粒径影响规律. 透射电子显微镜和圆二色光谱表征温度对嵌段共聚物自组装的影响，结果表明，接近临界温度30 ℃时，嵌段共聚物的CD信号最强. 该类温度响应型手性嵌段共聚物可实现纯水相中高效不对称反应的进行，仅需0.5 mol%嵌段共聚物催化反应1.0 h，即可实现底物苯甲硫醚转化率达95%，选择性为97%，对映选择性高达98%. 实验证明嵌段共聚物在水中可自组装形成纳米反应器，加速反应进行，升温后，嵌段共聚物表现出疏水特性，从水相析出后直接回收，实现了材料可重复利用.
Abstract
A series of temperature-responsive chiral amphiphilic random copolymers poly(NIPAAm-
co
-chiral salen Ti
IV
PN
x
S
y
) were prepared by using
N
-isopropylacrylamide and 5-vinyl chiral salen Ti
IV
as the monomers
azodiisobutyronitrile as the chain initiator
and benzyl dithiopropionate as the chain transfer agent. The successful copolymerization of the chiral salen Ti
IV
moiety with NIPAAm was illustrated by FTIR. The water-solubility switching process and LCST were characterized by monitoring the optical transmittance of PN
x
S
y
solution at 450 nm using UV-Vis spectrophotometry. Dynamic light scattering (DLS) was used to further prove the influence of the ratio of hydrophilicity to hydrophobicity on the hydration kinetic particle size of amphiphilic random copolymers. Transmission electron microscopy (TEM) and circular dichroism (CD) spectroscopy were used to reveal the effect of temperature on the chirality of amphiphilic random copolymers. This kind of thermo-responsive chiral amphiphilic random copolymers can realize efficient asymmetric catalytic reaction in pure water phase. Only 0.1 mol% of PN
120
S
8
was sufficient to exhibit extremely high activity (conversion
>
95%) with up to 97% chemoselectivity and enantioselectivity (
>
98%) for a wide range of sulfides in water. After reaction
the PN
x
S
y
became hydrophobic upon heating above its LCST
and precipitated from aqueous system for recovery. It can be recycled and reused for seven times without significant loss of the activity.
关键词
温度响应型手性嵌段共聚物纯水相不对称反应循环回收利用
Keywords
Temperature-responsiveChiral copolymersPure water phaseAsymmetric reactionRecycle and reuse
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