Loose Semirigid Aromatic Polyester Bottle Brushes at Poly(2-isopropyl-2-oxazoline) Side Chains of Various Lengths: Behavior in Solutions and Thermoresponsiveness

Overview

Journal Polymers (Basel)

Publisher MDPI

Date 2022 Dec 23

PMID 36559721

Authors

Elena Tarabukina

Anna Krasova

Mikhail Kurlykin

Andrey Tenkovtsev

Alexander Filippov

Affiliations

Soon will be listed here.

Abstract

A polycondensation aromatic polyester with an oxygen spacer was synthesized and used as a macroinitiator for the grafting of linear poly(2-isopropyl-2-oxazoline) (PiPrOx) by the cationic polymerization method. The length of the thermosensitive side chains was varied by the initiator:monomer ratio. Using methods of molecular hydrodynamics, light scattering and turbidimetry, the copolymers were studied in organic solvents and in water. The molecular characteristics of the main chain and graft copolymers, the polymerization degree of side chains and their grafting density have been determined. The equilibrium rigidity of the macroinitiator and the conformations of grafted macromolecules were evaluated. In selective solvents, they take on a star-like conformation or aggregate depending on the degree of shielding of the main chain by side chains. The thermoresponsiveness of graft copolymers in aqueous solutions was studied, and their LCST were estimated. The results are compared with data for graft copolymers composed of PiPrOx side chains and flexible or rigid chain backbones of aromatic polyester type.

References

Buhler J, Muth S, Fischer K, Schmidt M . Collapse of cylindrical brushes with 2-isopropyloxazoline side chains close to the phase boundary. Macromol Rapid Commun. 2013; 34(7):588-94. DOI: 10.1002/marc.201200784. View

Dutta S, Wade M, Walsh D, Guironnet D, Rogers S, Sing C . Dilute solution structure of bottlebrush polymers. Soft Matter. 2019; 15(14):2928-2941. DOI: 10.1039/c9sm00033j. View

Tarabukina E, Fatullaev E, Krasova A, Kurlykin M, Tenkovtsev A, Sheiko S . Synthesis, Structure, Hydrodynamics and Thermoresponsiveness of Graft Copolymer with Aromatic Polyester Backbone at Poly(2-isopropyl-2-oxazoline) Side Chains. Polymers (Basel). 2020; 12(11). PMC: 7698206. DOI: 10.3390/polym12112643. View

Hoogenboom R, Thijs H, Jochems M, van Lankvelt B, Fijten M, Schubert U . Tuning the LCST of poly(2-oxazoline)s by varying composition and molecular weight: alternatives to poly(N-isopropylacrylamide)?. Chem Commun (Camb). 2008; (44):5758-60. DOI: 10.1039/b813140f. View

Li X, ShamsiJazeyi H, L Pesek S, Agrawal A, Hammouda B, Verduzco R . Thermoresponsive PNIPAAM bottlebrush polymers with tailored side-chain length and end-group structure. Soft Matter. 2014; 10(12):2008-15. DOI: 10.1039/c3sm52614c. View

De La Rosa V . Poly(2-oxazoline)s as materials for biomedical applications. J Mater Sci Mater Med. 2013; 25(5):1211-25. DOI: 10.1007/s10856-013-5034-y. View

Liu X, Claesson P . Bioinspired Bottlebrush Polymers for Aqueous Boundary Lubrication. Polymers (Basel). 2022; 14(13). PMC: 9269121. DOI: 10.3390/polym14132724. View

Kato H, Nakamura A, Kinugasa S . Effects of Angular Dependency of Particulate Light Scattering Intensity on Determination of Samples with Bimodal Size Distributions Using Dynamic Light Scattering Methods. Nanomaterials (Basel). 2018; 8(9). PMC: 6163781. DOI: 10.3390/nano8090708. View

Schlaad H, Diehl C, Gress A, Meyer M, Demirel A, Nur Y . Poly(2-oxazoline)s as Smart Bioinspired Polymers. Macromol Rapid Commun. 2011; 31(6):511-25. DOI: 10.1002/marc.200900683. View

10.

Tarabukina E, Fatullaev E, Krasova A, Sokolova M, Kurlykin M, Neelov I . Thermoresponsive Molecular Brushes with a Rigid-Chain Aromatic Polyester Backbone and Poly-2-alkyl-2-oxazoline Side Chains. Int J Mol Sci. 2021; 22(22). PMC: 8622345. DOI: 10.3390/ijms222212265. View

11.

Rzayev J . Molecular Bottlebrushes: New Opportunities in Nanomaterials Fabrication. ACS Macro Lett. 2022; 1(9):1146-1149. DOI: 10.1021/mz300402x. View

12.

Gil Alvaradejo G, Nguyen H, Harvey P, Gallagher N, Le D, Ottaviani M . Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents. ACS Macro Lett. 2019; 8(4):473-478. PMC: 6615754. DOI: 10.1021/acsmacrolett.9b00016. View

13.

Sui K, Zhao X, Wu Z, Xia Y, Liang H, Li Y . Synthesis, rapid responsive thickening, and self-assembly of brush copolymer poly(ethylene oxide)-graft-poly(N,N-dimethylaminoethyl methacrylate) in aqueous solutions. Langmuir. 2011; 28(1):153-60. DOI: 10.1021/la2031472. View

14.

Sauer M, Haefele T, Graff A, Nardin C, Meier W . Ion-carrier controlled precipitation of calcium phosphate in giant ABA triblock copolymer vesicles. Chem Commun (Camb). 2002; (23):2452-3. DOI: 10.1039/b107833j. View

15.

Wessels M, Jayaraman A . Molecular dynamics simulation study of linear, bottlebrush, and star-like amphiphilic block polymer assembly in solution. Soft Matter. 2019; 15(19):3987-3998. DOI: 10.1039/c9sm00375d. View

16.

Yuan J, Xu Y, Walther A, Bolisetty S, Schumacher M, Schmalz H . Water-soluble organo-silica hybrid nanowires. Nat Mater. 2008; 7(9):718-22. DOI: 10.1038/nmat2232. View

17.

Dalsin S, Rions-Maehren T, Beam M, Bates F, Hillmyer M, Matsen M . Bottlebrush Block Polymers: Quantitative Theory and Experiments. ACS Nano. 2015; 9(12):12233-45. DOI: 10.1021/acsnano.5b05473. View

18.

Hsiue G, Chiang H, Wang C, Juang T . Nonviral gene carriers based on diblock copolymers of poly(2-ethyl-2-oxazoline) and linear polyethylenimine. Bioconjug Chem. 2006; 17(3):781-6. DOI: 10.1021/bc050317u. View

19.

Nakamura Y . Stiffness parameter of brush-like polymers with rod-like side chains. J Chem Phys. 2016; 145(1):014903. DOI: 10.1063/1.4954920. View

20.

Hadjichristidis N, Pitsikalis M, Pispas S, Iatrou H . Polymers with complex architecture by living anionic polymerization. Chem Rev. 2001; 101(12):3747-92. DOI: 10.1021/cr9901337. View