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Synthesis and characterization of isotactic poly(p-hydroxystyrene)- block-1,4-trans-polybutadiene by sequential monomer addition using titanium complex with an [OSSO]-type Bis(phenolate) ligand

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Abstract

Herein, we demonstrated the synthesis and characterization of a well-defined diblock copolymer consisting of isotactic poly(p-hydroxystyrene) (iP(p-HOS)) and 1,4-trans-polybutadiene (1,4-trans-PBD), iP(p-HOS)-b-1, 4-trans-PBD, by the combination of sequential monomer addition and deprotection. Isospecific living polymerization of p-tert- butyldimethylsilyloxystyrene and living trans-1,4-polymerization of 1,3-butadiene were catalyzed by 1, 4-dithiabutandiyl-2, 2ʹ-bis(6-cumenyl-4-methylphenoxy) titanium dichloride (complex 1) activated by methylaluminoxane (MAO) at room temperature to provide highly stereospecific isotactic poly(p-tert-butyldimethylsilyloxystyrene) (iP(p-TBDMSOS)) and 1,4-trans-polybutadiene (1,4-trans-PBD) with narrow molecular weight distribution. Furthermore, the iP(p-TBDMSOS)-b-1, 4-trans-PBD was prepared via sequential monomer addition in the presence of complex 1 and MAO. The deprotection of the iP(p-TBDMSOS) block was promoted by concentrated hydrochloric acid to produce iP(p-HOS)-b-1, 4-trans-PBD. In addition, the resultant diblock copolymer and intermediate polymers were characterized by gel permeation chromatography, nuclear magnetic resonance and differential scanning calorimeter.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (21174167, 51573212) and the NSF of Guangdong Province (S2013030013474, 2014A030313178).

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Authors and Affiliations

  1. GDHPPC Lab, School of Chemistry, Sun Yat-sen University, Guangzhou, 510275, China

    HuaQing Liang, Sihan Li, Dong Liu, Yijun Liu, YongJiang Long, GuoDong Liang & FangMing Zhu

  2. Key Lab for Polymer Composite and Functional Materials of Ministry of Education, School of Chemistry, Sun Yat-sen University, Guangzhou, 510275, China

    GuoDong Liang & FangMing Zhu

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  1. HuaQing Liang
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  2. Sihan Li
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  3. Dong Liu
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  7. FangMing Zhu
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Correspondence to FangMing Zhu.

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Liang, H., Li, S., Liu, D. et al. Synthesis and characterization of isotactic poly(p-hydroxystyrene)- block-1,4-trans-polybutadiene by sequential monomer addition using titanium complex with an [OSSO]-type Bis(phenolate) ligand. J Polym Res 26, 15 (2019). https://doi.org/10.1007/s10965-018-1675-3

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