Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents

Zhen-Zhen Sun; Yan-Ning Zhang; Hao-Yu Qiu; Xue-Ting Lu; Liang-Xuan Ren; Le-Fei Shen; Wen Li; Afang Zhang

doi:10.1007/s10118-023-2991-6

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Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents

RESEARCH ARTICLE | Updated：2023-09-21

- Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents
- Chinese Journal of Polymer Science Vol. 41, Issue 10, Pages: 1543-1554(2023)
- Affiliations：
  
  International Joint Laboratory of Biomimetic and Smart Polymers, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
- Author bio：
  
  wli@shu.edu.cn (W.L.)
  azhang@shu.edu.cn (A.Z.)
- Funds：
- DOI：10.1007/s10118-023-2991-6
  CLC：
- Received：01 April 2023，
  
  Revised：2023-4-15，
  
  Accepted：17 April 2023，
  
  Online First：12 June 2023，
  
  Published：01 October 2023
- Accepted：
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Sun, Z. Z.; Zhang, Y. N.; Qiu, H. Y.; Lu, X. T.; Ren, L. X.; Shen, L. F.; Li, W.; Zhang, A. Synthesis of helical poly(phenylacetylene)s carrying dendritic pendants with varied branching densities through polymerization in different solvents. Chinese J. Polym. Sci. 2023, 41, 1543–1554

Zhen-Zhen Sun, Yan-Ning Zhang, Hao-Yu Qiu, et al. Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents[J]. Chinese Journal of Polymer Science, 2023, 41(10): 1543-1554.
Sun, Z. Z.; Zhang, Y. N.; Qiu, H. Y.; Lu, X. T.; Ren, L. X.; Shen, L. F.; Li, W.; Zhang, A. Synthesis of helical poly(phenylacetylene)s carrying dendritic pendants with varied branching densities through polymerization in different solvents. Chinese J. Polym. Sci. 2023, 41, 1543–1554 DOI： 10.1007/s10118-023-2991-6.

Zhen-Zhen Sun, Yan-Ning Zhang, Hao-Yu Qiu, et al. Synthesis of Helical Poly(phenylacetylene)s Carrying Dendritic Pendants with Varied Branching Densities Through Polymerization in Different Solvents[J]. Chinese Journal of Polymer Science, 2023, 41(10): 1543-1554. DOI： 10.1007/s10118-023-2991-6.

摘要

A homologous series of dendronized helical poly(phenylacetylene)s (PPAs) carrying dendritic oligoethylene glycols (OEGs) with different branching density were synthesized. These dendronized PPAs exhibit different thermoresponsiveness according to branching density of the OEGs

and their helicities are relevant to polymerization solvents due to varied shielding effect from the dendritic OEGs.

Abstract

Helical poly(phenylacetylene)s (PPAs) have received extensive attention because of their features in dynamic chirality and promising applications. Therefore

understanding relationship among the polymer molecular structures

polymerization conditions and tunability of their chirality is of key scientific value. Recently

we developed a novel class of dendronized PPAs carrying 3-fold dendritic oligo(ethylene glycols) (OEGs)

via

alanine linkage

and found that these bulky polymers exhibited tunable helical conformations through thermally-mediated dehydration and aggregation. Herein

we report on synthesis of a homologous series of dendronized PPAs that carry 2-fold

3-fold or 6-fold dendritic OEG pendants

and focus on effects of molecular topological structures

peripheral units and polymerization solvents on the thermoresponsiveness and their conformation switching behaviors. Effects of branching density and peripheral units (ethoxyl or methoxyl) of the dendritic OEG pendants were examined

and found to play a decisive role on the helical conformation and thermoresponsiveness of these dendronized PPAs due to their different bulkiness and overall hydrophilicity. In addition

different polymerization solvents were checked for their possible influence on the polymerization

thermoresponsive behavior and the chirality of the resulting polymers. For polymerization in selective solvents like water or methanol

the obtained dendronized PPAs exhibited weak thermal transitions

while polymerization in non-selective solvent like THF furnished PPAs with characteristic thermoresponsive behavior

indicating that solvents were involved in the process of polymerization of the dendronized macromonomers. More interestingly

different chiralities of the PPAs through polymerization in various solvents were retained

irrelevant to the purification process and solvents treatments. This work suggests that the topological structures together with polymerization solvents can modulate the thermoresponsive behavior and helical conformation of the dendronized PPAs.

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