Synthesis and Microstructure Analysis of Stereoregular Poly(1,4-cyclohexadiene carbonate) Oligomers

Xia-di Wang; Xing-yu Sun; Jing Luo; Qing Zhu; Hui Zhou; Xiao-bing Lu

doi:10.11777/j.issn1000-3304.2021.21085

您当前的位置：

首页 >

文章列表页 >

Synthesis and Microstructure Analysis of Stereoregular Poly(1,4-cyclohexadiene carbonate) Oligomers

Research Article | 更新时间：2023-12-20

- Synthesis and Microstructure Analysis of Stereoregular Poly(1,4-cyclohexadiene carbonate) Oligomers
- ACTA POLYMERICA SINICA Vol. 52, Issue 10, Pages: 1316-1322(2021)
- 作者机构：
  
  精细化工国家重点实验室大连理工大学大连 116024
- 作者简介：
  
  E-mail: Hui Zhou, zhouhui@dlut.edu.cn E-mail:
  Xiao-bing Lu, xblu@dlut.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2021.21085
  CLC：
- Published：20 October 2021，
  
  Published Online：09 August 2021，
  
  Received：14 March 2021，
  
  Revised：06 April 2021，
扫描看全文
王霞弟,孙星宇,罗婧等.聚(1,4-环己二烯碳酸酯)立体低聚物的合成及微结构分析[J].高分子学报,2021,52(10):1316-1322.

Wang Xia-di,Sun Xing-yu,Luo Jing,et al.Synthesis and Microstructure Analysis of Stereoregular Poly(1,4-cyclohexadiene carbonate) Oligomers[J].ACTA POLYMERICA SINICA,2021,52(10):1316-1322.
王霞弟,孙星宇,罗婧等.聚(1,4-环己二烯碳酸酯)立体低聚物的合成及微结构分析[J].高分子学报,2021,52(10):1316-1322. DOI： 10.11777/j.issn1000-3304.2021.21085.

Wang Xia-di,Sun Xing-yu,Luo Jing,et al.Synthesis and Microstructure Analysis of Stereoregular Poly(1,4-cyclohexadiene carbonate) Oligomers[J].ACTA POLYMERICA SINICA,2021,52(10):1316-1322. DOI： 10.11777/j.issn1000-3304.2021.21085.

摘要

聚合物微结构控制是配位催化聚合领域最重要的目标之一. 而合成各种立构规整性低聚物及其核磁碳谱研究是聚合物微结构定性和定量分析的关键. 本文以手性环己-4-烯-1

2-二醇为原料，采用

'-羰基二咪唑和三光气作为羰化试剂，设计合成了CO

2-环氧-4-环己烯交替共聚物(聚(1

4-环己二烯碳酸酯)，PCEC)全同立构和间同立构的二聚体、四聚体、六聚体、八聚体和十二聚体模型化合物. 通过分析全同立构和间同立构模型化合物的核磁碳谱，完成了PCEC微结构的碳谱信息归属. 发现聚合物全同立构序列的羰基、次甲基和亚甲基区域的出峰位置分别在

=154.04、73.83和29.91；间同立构序列的羰基、次甲基和亚甲基区域的出峰位置分别在

=153.72、72.97和28.98.

Abstract

The alternating copolymerization of carbon dioxide (CO

) and epoxides to prepare degradable polycarbonates is an important green polymerization process

since CO

is an abundant

cheap and nontoxic renewable C1 resource. Because of their good environmental friendliness and degradability

these materials are expected to be widely used in disposable packaging

degradable agricultural films

foaming agents and adhesives. For the copolymerization of substituted epoxides with CO

the stereochemistry inherent to the epoxide monomer provides the possibility to synthesize stereoregular polycarbonates by establishing chiral centers in the main chain of the resultant copolymers with control of the absolute configuration. Indeed

there is a great correlation between the stereochemistry of polymer main chain and its physical properties. The precise control of polymer microstructure is one of the most important goals in the field of coordination catalysis polymerization. The synthesis of the corresponding model oligomers and analysis of their

C-NMR spectra play a critical role in qualitative and quantitative analysis of polymer microstructure. In the present contribution

(

)/(

)-cyclohex-4-ene-1

2-diols were used as starting materials to synthesize various isotactic and syndiotactic model compounds (oligomers with 2

8 and 12 degree of polymerization) of poly(1

4-cyclohexadiene carbonate) (PCEC)

using

‍N'

-carbonyldiimidazole and triphosgene as carbonylation reagents. By comparing the signals in the

C-NMR spectra of various steroregular oligomers

it can be concluded that the signals at

=154.04

73.83 and 29.91 are assigned to carbonyl

methine and methylene of isotactic PCEC

respectively

while the signals at

=153.72

72.97 and 28.98 are attributed to carbonyl

methine and methylene of syndiotactic polycarbonate

respectively.

关键词

二氧化碳聚碳酸酯全同结构间同结构核磁碳谱

Keywords

Carbon dioxidePolycarbonateIsotactic structureSyndiotactic structureNMR spectroscopy

references

Allen S D, Byrne C M, Coates G W. Carbon dioxide as a renewable C1 feedstock synthesis and characterization of polycarbonates from the alternating copolymerization of epoxides and CO2. In: Bozell J J, Patel M K, eds. Feedstocks for the Future: Renewables for the Production of Chemicals and Materials. American Chemical Society, 2006. 116-129. doi:10.1021/bk-2006-0921.ch009http://dx.doi.org/10.1021/bk-2006-0921.ch009

Aresta M, Dibenedetto A. Dalton Trans, 2007, (28): 2975-2992. doi:10.1039/b700658fhttp://dx.doi.org/10.1039/b700658f

Darensbourg D J. Chem Rev, 2007, 107(6): 2388-2410. doi:10.1021/cr068363qhttp://dx.doi.org/10.1021/cr068363q

Omae I. Catal Today, 2006, 115(1-4): 33-52. doi:10.1016/j.cattod.2006.02.024http://dx.doi.org/10.1016/j.cattod.2006.02.024

Qin Y, Wang X. Biotechnol J, 2010, 5(11): 1164-1180. doi:10.1002/biot.201000134http://dx.doi.org/10.1002/biot.201000134

Rayner C M. Org Process Res Dev, 2007, 11(1): 121-132. doi:10.1021/op060165dhttp://dx.doi.org/10.1021/op060165d

Aresta M. Carbon dioxide utilization: Greening both the energy and chemical industry: An overview. In: Liu C J, Mallinson R G, Aresta M, eds. Utilization of Greenhouse Gases. American Chemical Society, 2003. 2-39. doi:10.1021/bk-2003-0852.ch001http://dx.doi.org/10.1021/bk-2003-0852.ch001

Lv Xiaobing(吕小兵). Acta Polymerica Sinica(高分子学报), 2016, (9): 1166-1178. doi:10.11777/j.issn1000-3304.2016.16151http://dx.doi.org/10.11777/j.issn1000-3304.2016.16151

Wu G P, Zu Y P, Xu P X, Ren W M, Lu X B. Chem Asian J, 2013, 8(8): 1854-1862. doi:10.1002/asia.201300115http://dx.doi.org/10.1002/asia.201300115

Chisholm M H, Navarro-Llobet D, Zhou Z P. Macromolecules, 2002, 35(17): 6494-6504. doi:10.1021/ma020348+http://dx.doi.org/10.1021/ma020348+

Byrnes M J, Chisholm M H, Hadad C M, Zhou Z P. Macromolecules, 2004, 37(11): 4139-4145. doi:10.1021/ma049850fhttp://dx.doi.org/10.1021/ma049850f

Salmeia K A, Vagin S, Anderson C E, Rieger B. Macromolecules, 2012, 45(21): 8604-8613. doi:10.1021/ma301916rhttp://dx.doi.org/10.1021/ma301916r

Wu G P, Wei S H, Ren W M, Lu X B, Li B, Zu Y P, Darensbourg D J. Energy Environ Sci, 2011, 4(12): 5084-5092. doi:10.1039/c1ee02566jhttp://dx.doi.org/10.1039/c1ee02566j

Nakano K, Nozaki K, Hiyama T. Macromolecules, 2001, 34(18): 6325-6332. doi:10.1021/ma010732rhttp://dx.doi.org/10.1021/ma010732r

Liu Y, Li R R, Lu X B. Macromolecules, 2015, 48(19): 6941-6947. doi:10.1021/acs.macromol.5b01759http://dx.doi.org/10.1021/acs.macromol.5b01759

Luo Jing(罗婧), Sun Xingyu(孙星宇), Wang Xiadi(王霞弟), Zhou Hui(周辉), Lu Xiaobing(吕小兵). Chinese Science Bulletin(科学通报), 2020, 65(31): 3418-3428. doi:10.1360/tb-2020-0320http://dx.doi.org/10.1360/tb-2020-0320

Liu Y, Wang M, Ren W M, Xu Y C, Lu X B. Angew Chem Int Ed, 2015, 54(24): 7042-7046. doi:10.1002/anie.201501417http://dx.doi.org/10.1002/anie.201501417

Diallo A K, Kirillov E, Slawinski M, Brusson, J M, Guillaume S M, Carpentier J F. Polym Chem, 2015, 6: 1961-1971. doi:10.1039/c4py01713ghttp://dx.doi.org/10.1039/c4py01713g

更多指标>

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Synthesis, Structure and Properties of Isobutylene Oxide-CO₂ Copolymer

Synthesis of SalenCo^(Ⅲ) CN Catalyst for Copolymerization and Terpolymerization of Epoxides and Carbon Dioxide

SYNTHESIS, CHARACTERIZATION AND THERMAL DEGRADATION KINETICS OF CARBON DIOXIDE-PROPYLENE OXIDE-D,L-LACTIDE TERPOLYMER

Related Author

No data

Related Institution

State Key Laboratory of Motor Vehicle Biofuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering

China Center of Chemistry for Frontier Technologies, Zhejiang University

Shandong Shida Shenghua Chemical Group Co. Ltd.

State Key Laboratory of Chemical Engineering, East China University of Science and Technology

China Center of Chemistry for Frontier Technologies, Zhejiang University

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰