SalenCo<sup>(Ⅲ)</sup>CN的合成及其催化二氧化碳和环氧化物共聚研究

李佳佳; 周宇杰; 程瑞华; 刘柏平

doi:10.11777/j.issn1000-3304.2017.17049

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SalenCo^(Ⅲ)CN的合成及其催化二氧化碳和环氧化物共聚研究

研究论文 | 更新时间：2021-01-26

- SalenCo^(Ⅲ)CN的合成及其催化二氧化碳和环氧化物共聚研究
- Synthesis of SalenCo^(Ⅲ) CN Catalyst for Copolymerization and Terpolymerization of Epoxides and Carbon Dioxide
- 高分子学报 2017年第12期页码：1915-1921
- 作者机构：
  
  华东理工大学化学工程联合国家重点实验室上海 200237
- 作者简介：
  
  程瑞华, E-mail: rhcheng@ecust.edu.cn Rui-hua Cheng, E-mail: rhcheng@ecust.edu.cn
- 基金信息：
  
  上海市浦江人才计划(16PJD016)
- DOI：10.11777/j.issn1000-3304.2017.17049
  中图分类号：
- 纸质出版日期：2017-12-20，
  
  收稿日期：2017-3-15，
  
  修回日期：2017-4-11，
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李佳佳, 周宇杰, 程瑞华, 刘柏平. SalenCo^(Ⅲ)CN的合成及其催化二氧化碳和环氧化物共聚研究[J]. 高分子学报, 2017,(12):1915-1921.

Jia-jia Li, Yu-jie Zhou, Rui-hua Cheng, Bo-ping Liu. Synthesis of SalenCo^(Ⅲ) CN Catalyst for Copolymerization and Terpolymerization of Epoxides and Carbon Dioxide[J]. Acta Polymerica Sinica, 2017,(12):1915-1921.
李佳佳, 周宇杰, 程瑞华, 刘柏平. SalenCo^(Ⅲ)CN的合成及其催化二氧化碳和环氧化物共聚研究[J]. 高分子学报, 2017,(12):1915-1921. DOI： 10.11777/j.issn1000-3304.2017.17049.

Jia-jia Li, Yu-jie Zhou, Rui-hua Cheng, Bo-ping Liu. Synthesis of SalenCo^(Ⅲ) CN Catalyst for Copolymerization and Terpolymerization of Epoxides and Carbon Dioxide[J]. Acta Polymerica Sinica, 2017,(12):1915-1921. DOI： 10.11777/j.issn1000-3304.2017.17049.

摘要

采用具有新型轴向配体的SalenCo

（Ⅲ）

CN催化剂在25~100℃的聚合温度下催化二氧化碳和环氧丙烷（PO）共聚制备聚碳酸酯（PPC）.CN具有吸电子能力，在50℃下SalenCo

（Ⅲ）

CN/PPNCl体系催化二氧化碳和环氧丙烷聚合的活性为TOF=379 h

-1

，产物的区域选择性

95%，碳酸酯单元含量

99%，且分子量分布极窄.在该催化体系中分别加入二环戊二烯环氧化物（EP1）、1，3，5-三缩水甘油-

-三嗪三酮（EP2）与二氧化碳和环氧丙烷三元调聚合.在相同条件下，EP1使催化活性显著升高至624 h

-1

，但对产物分子量和玻璃化转变温度（

）影响不明显；EP2的加入对活性的影响不明显，但可使聚碳酸酯的分子量增大至

=1.97×10

，PDI=5.07，产物的

升至45℃.

Abstract

A new type of the SalenCo

(Ⅲ)

with CN as the co-ligand is developed to catalyze the copolymerization of CO

with propylene oxide (PO) to afford poly(propylene carbonate) (PPC). The co-ligand (X) is the initiating group during the reaction and becomes the site at which the growing polymer chain is proposed to propagate. The copolymerization rate

selectivity of the polymer to the cyclic carbonate

stereoselectivity

and regioselectivity of the polycarbonate exhibit a pronounced dependence on the nature of the axial ligand. Compared with the SalenCo

(Ⅲ)

Cl and SalenCo

(Ⅲ)

Br catalysts

the PPC obtained by SalenCo

(Ⅲ)

CN catalyst at 25℃ presented 98% head-to-tail (HT) connectivity

and without head-to-head linkage. Further increasing the reaction temperature from 25℃ to 75℃

the polymerization activity over SalenCo

(Ⅲ)

CN catalysts increased

and the product still maintained a high selectivity for carbonate linkages. The PPC achieved using the SalenCo

(Ⅲ)

CN/PPNCl (PPNCl=bis(triphenylphosphino)iminium chloride) catalyst systems at 50℃ within 2 h with TOF=379 mol PO·mol

-1

Co·h

-1

was highly regioregular (HT up to 95%) and had carbonate linkages of up to 99% with a narrow molecular weight distribution (MWD). The SalenCo

(Ⅲ)

CN catalyst showed good stability and polymer chain control ability even at 75℃. This novel catalyst efficiently terpolymerized CO

and two other kinds of epoxide monomers. When the quantity of the third epoxide was added gradually

the MWD of the generated polymers was broader

indicating the epoxide was incorporated into the PPC chain successfully. The third epoxide monomer not only acted as an interlinkage in the terpolymerization of CO

and PO

which increased the MW of the resultant terpolymer to a value that increased the glass transition temperature (

)

but also strongly influenced the productivity of PPC and the selectivity. Introducing the dicyclopentadiene dioxide (EP1) could greatly increase the activity of the catalyst system to TOF=624 h

-1

with a slight effect on

. For the case of 1

5-triglycidyl isocyanurate (EP2)

it increased MW of the resultant copolymer and the

up to 45℃.

关键词

二氧化碳聚碳酸酯Salen催化剂聚合温度分子量

Keywords

Carbon dioxidePolycarbonateSalenCo(Ⅲ)CNPolymerization temperatureMolecular weight

references

S Inoue , H Koinuma , T Tsuruta . Die Makromol Chem , 1969 . 130 ( 1 ): 210 - 220 . DOI:10.1002/macp.1969.021300112http://doi.org/10.1002/macp.1969.021300112.

Z Qin , C M Thomas , S Lee , G W Coates . Angew Chem Int Ed , 2003 . 42 ( 44 ): 5484 - 5487 . DOI:10.1002/(ISSN)1521-3773http://doi.org/10.1002/(ISSN)1521-3773.

M Tokunaga , J F Larrow , F Kakiuchi , E N Jacobsen . Science , 1997 . 277 ( 5328 ): 936 - 938 . DOI:10.1126/science.277.5328.936http://doi.org/10.1126/science.277.5328.936.

Y Tao , X Wang , X Chen , X Zhao , F Wang . J Polym Sci, Part A:Polym Chem , 2008 . 46 ( 13 ): 4451 - 4458 . DOI:10.1002/(ISSN)1099-0518http://doi.org/10.1002/(ISSN)1099-0518.

H Li , Y Niu . React Funct Polym , 2011 . 71 ( 2 ): 121 - 125 . DOI:10.1016/j.reactfunctpolym.2010.11.026http://doi.org/10.1016/j.reactfunctpolym.2010.11.026.

H C Li , Y S Niu . Polym Adv Technol , 2016 . 27 ( 9 ): 1191 - 1194 . DOI:10.1002/pat.v27.9http://doi.org/10.1002/pat.v27.9.

D J Darensbourg , J L Rodgers , R M Mackiewicz , A L Phelps . Catal Today , 2004 . 98 ( 4 ): 485 - 492 . DOI:10.1016/j.cattod.2004.09.017http://doi.org/10.1016/j.cattod.2004.09.017.

D J Darensbourg , J C Yarbrough , Ortiz A Cesar , C C Fang . J Am Chem Soc , 2003 . 125 ( 25 ): 7586 - 7591 . DOI:10.1021/ja034863ehttp://doi.org/10.1021/ja034863e.

R Eberhardt , M Allmendinger , B Rieger . Macromol Rapid Commun , 2003 . 24 ( 2 ): 194 - 196 . DOI:10.1002/(ISSN)1521-3927http://doi.org/10.1002/(ISSN)1521-3927.

S D Allen , D R Moore , E B L And , G W Coates . J Am Chem Soc , 2002 . 124 ( 48 ): 14284 - 14285 . DOI:10.1021/ja028071ghttp://doi.org/10.1021/ja028071g.

X B Lu , B Liang , Y J Zhang , Y Z Tian , Y M Wang , C X Bai , H Wang , R Zhang . J Am Chem Soc , 2004 . 126 ( 12 ): 3732 - 3733 . DOI:10.1021/ja049734shttp://doi.org/10.1021/ja049734s.

C T Cohen , Chu A Tony , G W Coates . J Am Chem Soc , 2005 . 127 ( 31 ): 10869 - 10878 . DOI:10.1021/ja051744lhttp://doi.org/10.1021/ja051744l.

Jian Zhou , Youhua Tao , Xianhong Wang , Xiaojiang Zhao , Fosong Wang . Acta Polymerica Sinica , 2007 . ( 10 ): 913 - 917 . DOI:10.3321/j.issn:1000-3304.2007.10.004http://doi.org/10.3321/j.issn:1000-3304.2007.10.004http://www.gfzxb.org/CN/abstract/abstract11095.shtml.

周坚 , 陶友华 , 王献红 , 赵晓江 , 王佛松 . 高分子学报 , 2007 . ( 10 ): 913 - 917 . DOI:10.3321/j.issn:1000-3304.2007.10.004http://doi.org/10.3321/j.issn:1000-3304.2007.10.004http://www.gfzxb.org/CN/abstract/abstract11095.shtml.

Yaming Zhang , Fengxiang Gao , Qinghai Zhou , Yusheng Qin , Xianhong Wang , Fosong Wang . Acta Polymerica Sinica , 2015 . ( 1 ): 106 - 112 . http://www.gfzxb.org/CN/abstract/abstract14232.shtml.

张亚明 , 高凤翔 , 周庆海 , 秦玉升 , 王献红 , 王佛松 . 高分子学报 , 2015 . ( 1 ): 106 - 112 . http://www.gfzxb.org/CN/abstract/abstract14232.shtml.

D J Darensbourg , G P Wu . Angew Chem Ind Ed , 2013 . 52 ( 40 ): 10602 - 10606 . DOI:10.1002/anie.201304778http://doi.org/10.1002/anie.201304778.

X Li , R L Duan , X Pang , B Gao , X H Wang , X S Chen . Appl Catal B , 2016 . 182 580 - 586 . DOI:10.1016/j.apcatb.2015.10.019http://doi.org/10.1016/j.apcatb.2015.10.019.

X B Lu , L Shi , Y M Wang , R Zhang , Y J Zhang , X J Peng , Z C Zhang , B Li . J Am Chem Soc , 2015 . 128 ( 128 ): 1664 - 1674 . http://www.ncbi.nlm.nih.gov/pubmed/16448140.

G P Wu , S H Wei , W M Ren , X B Lu , T Q Xu , D J Darensbourg . J Am Chem Soc , 2011 . 133 ( 38 ): 15191 - 15199 . DOI:10.1021/ja206425jhttp://doi.org/10.1021/ja206425j.

G P Wu , S H Wei , X B Lu , W M Ren , D J Darensbourg . Macromolecules , 2010 . 43 ( 21 ): 9202 - 9204 . DOI:10.1021/ma1021456http://doi.org/10.1021/ma1021456.

X B Lu , W M Ren , G P Wu . Acc Chem Res , 2012 . 45 ( 10 ): 1721 - 1735 . DOI:10.1021/ar300035zhttp://doi.org/10.1021/ar300035z.

S E Schaus , B D Brandes , J F Larrow , M Tokunaga , K B Hansen , A E Gould , M E Furrow , E N Jacobsen . J Am Chem Soc , 2002 . 124 ( 7 ): 1307 - 1315 . DOI:10.1021/ja016737lhttp://doi.org/10.1021/ja016737l.

I K Lee , Y H Ju , C Cao , D W Park , C S Ha , I Kim . Catal Today , 2009 . 148 ( 3 ): 389 - 397.

X B Lu , Y Wang . Angew Chem Int Ed , 2004 . 43 ( 27 ): 3574 - 3577 . DOI:10.1002/(ISSN)1521-3773http://doi.org/10.1002/(ISSN)1521-3773.

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

DOI：10.11777/j.issn1000-3304.2017.17049

摘要

Abstract

关键词

Keywords

references

SalenCo^(Ⅲ)CN的合成及其催化二氧化碳和环氧化物共聚研究

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