a.Research Center for Polymer Materials, School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, China
b.Key Laboratory of Rubber-Plastics, Ministry of Education/Shandong Provincial Key Laboratory of Rubber-Plastics, Qingdao University of Science & Technology, Qingdao 266061, China
c.Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, Japan
shenxiande@cust.edu.cn (X.D.S.)
hengliu@qust.edu.cn (H.L.)
kakuchi@eng.hokudai.ac.jp (T.K.)
收稿:2022-06-01,
修回:2022-8-7,
录用:2022-8-24,
网络首发:2022-10-10,
纸质出版:2023-03-01
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Fang, L.; Zhang, C. Y.; Zhang, X. Q.; Shen, X. D.; Liu, H.; Kakuchi, T. Ni(acac)2 mediated vinyl polymerization of norbornene in the presence of bulky salicylaldiminate ligands: an effective strategy to access soluble polynorbornenes. Chinese J. Polym. Sci. 2023, 41, 356–364 DOI: 10.1007/s10118-022-2855-5.
Liang Fang, Chun-Yu Zhang, Xue-Quan Zhang, et al. Ni(acac)2 Mediated Vinyl Polymerization of Norbornene in the Presence of Bulky Salicylaldiminate Ligands: An Effective Strategy to Access Soluble Polynorbornenes[J]. Chinese Journal of Polymer Science, 2023, 41(3): 356-364. DOI: 10.1007/s10118-022-2855-5.
Fang, L.; Zhang, C. Y.; Zhang, X. Q.; Shen, X. D.; Liu, H.; Kakuchi, T. Ni(acac)2 mediated vinyl polymerization of norbornene in the presence of bulky salicylaldiminate ligands: an effective strategy to access soluble polynorbornenes. Chinese J. Polym. Sci. 2023, 41, 356–364 DOI: 10.1007/s10118-022-2855-5. DOI:
Liang Fang, Chun-Yu Zhang, Xue-Quan Zhang, et al. Ni(acac)2 Mediated Vinyl Polymerization of Norbornene in the Presence of Bulky Salicylaldiminate Ligands: An Effective Strategy to Access Soluble Polynorbornenes[J]. Chinese Journal of Polymer Science, 2023, 41(3): 356-364. DOI: 10.1007/s10118-022-2855-5. DOI:
The present research sheds light on future ligand designing for late-transition metal promoted NB polymerizations if soluble PNB products. The linear mainchain structure as well as the decreased stereoselectivities of PNB
due to the incorporation of salicylaldiminate ligands to the active species
contributed most to the well-improved solubilities.
Late transition metals have long served as workhorses for vinyl polymerization of norbornene derivatives. Nevertheless
for such catalytic systems
insoluble polynorbornene (PNB) products are often produced which hampers their further detailed characterizations
such as molecular weights
polydispersities
stereoregularities
etc
. In this work
we surprisingly found that for a traditional Ni(acac)
2
/MAO system that was previously reported to give insoluble PNBs
incorporation of highly bulk salicylaldiminate ligands could significantly improve the solubility of the PNBs in common organic solvents
which allowed for subsequent thorough detailed analysis of the polymer products. Moreover
it was also observed that high-temperature polymerization was beneficial for further improving the PNB’s solubilities due to the decreased molecular weights and stereoregularities. Different ligand skeletons and ligand equivalents were also investigated to give a comprehensive view of their influences on the polymers’ solubilities
and based on these results
a plausible mechanism that caused such a big difference was tentatively proposed.
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