Limited Fraction of Crystallized Side Chains in Bottlebrush Poly(<italic style="font-style: italic">n</italic>-alkyl methacrylate)s

Ming-Yue Xiang; Dong Lyu; Ling-Zhi Liu; Yong-Feng Men

doi:10.1007/s10118-021-2579-y

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Limited Fraction of Crystallized Side Chains in Bottlebrush Poly(n-alkyl methacrylate)s

ARTICLE | Updated：2021-06-04

- Limited Fraction of Crystallized Side Chains in Bottlebrush Poly(n-alkyl methacrylate)s
- Chinese Journal of Polymer Science Vol. 39, Issue 9, Pages: 1211-1216(2021)
- Affiliations：
  
  a.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
- Author bio：
  
  liulz@ciac.ac.cn (L.Z.L.)
  men@ciac.ac.cn (Y.F.M.)
- Funds：
- DOI：10.1007/s10118-021-2579-y
  CLC：
- Received：19 January 2021，
  
  Revised：2021-2-28，
  
  Accepted：11 March 2021，
  
  Online First：04 June 2021，
  
  Published：18 July 2021
- Accepted：
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Xiang, M. Y.; Lyu, D.; Liu, L. Z.; Men, Y. F. Limited fraction of crystallized side chains in bottlebrush poly(n-alkyl methacrylate)s. Chinese J. Polym. Sci. 2021, 39, 1211–1216

Ming-Yue Xiang, Dong Lyu, Ling-Zhi Liu, et al. Limited Fraction of Crystallized Side Chains in Bottlebrush Poly(n-alkyl methacrylate)s[J]. Chinese Journal of Polymer Science, 2021, 39(9): 1211-1216. DOI: 10.1007/s10118-021-2579-y.
Xiang, M. Y.; Lyu, D.; Liu, L. Z.; Men, Y. F. Limited fraction of crystallized side chains in bottlebrush poly(n-alkyl methacrylate)s. Chinese J. Polym. Sci. 2021, 39, 1211–1216 DOI： 10.1007/s10118-021-2579-y.

Ming-Yue Xiang, Dong Lyu, Ling-Zhi Liu, et al. Limited Fraction of Crystallized Side Chains in Bottlebrush Poly(n-alkyl methacrylate)s[J]. Chinese Journal of Polymer Science, 2021, 39(9): 1211-1216. DOI: 10.1007/s10118-021-2579-y. DOI：

摘要

Abstract

Crystallinity of bottlebrush polymers due to side chain crystallization has been considered to be related to the length of the side chains only under the assumption of complete participation of crystallization by all side chains. Recent experimental results revealed that in poly(

-alkyl methacrylate)s a fraction of side chains could not crystallize due to constraints imposed by the trapped main chain entanglements and required expansion of main chain-main chain distance. This result renders the original simplified consideration of the origin of crystallinity in bottlebrush polymers questionable. In this work

we introduce a new parameter

the fraction of crystallizable side chains

to better describe the crystallinity of bottlebrush polymers. A linear relationship between the melting enthalpy and the number of alkyl groups in side chains for bottlebrush polymers reported repeatedly indicates that

remains essentially unchanged when bottlebrush polymers had the same main chain structure and grafting degree but different side chain lengths. The slope of the above-mentioned linear relationship is thus Δ

$$H_{{\rm{CH}}_2} $$

http://notExist.jpg

where Δ

$$H_{{\rm{CH}}_2} $$

http://notExist.jpg

stands for the melting enthalpy of one mole alkyl group packed into the crystal. With a known value of

it is possible to estimate the value of Δ

$$H_{{\rm{CH}}_2} $$

http://notExist.jpg

. In case of poly(

-alkyl methacrylate)s

we estimated Δ

$$H_{{\rm{CH}}_2} $$

http://notExist.jpg

of hexagonal crystal being at most 5.74 kJ/mol with the knowledge of possibly smallest

of 0.67 obtained from small angle X-ray scattering data. Therefore

the crystallinity of bottlebrush polymer would be calculated based on the equation

$${X_{\rm{c}}} = {f_{\rm{c}}} \times \dfrac{{{N_{\rm{c}}}}}{N}$$

http://notExist.jpg

with

and

being the number of alkyl groups in a side chain and those packed in the crystalline structure

respectively. Both chemical structure and grafting degree of bottlebrush polymers affect

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Limited Fraction of Crystallized Side Chains in Bottlebrush Poly(n-alkyl methacrylate)s

DOI：10.1007/s10118-021-2579-y

摘要

Abstract

关键词

Keywords

references