Interest in thermoresponsive polymers has steadily grown over many decades, and a great deal of work has been dedicated to developing temperature sensitive macromolecules that can be crafted into new smart materials. However, the overwhelming majority of previously reported temperature-responsive polymers are based on poly(N-isopropylacrylamide) (PNIPAM), despite the fact that a wide range of other thermoresponsive polymers have demonstrated similar promise for the preparation of adaptive materials. Herein, we aim to highlight recent results that involve thermoresponsive systems that have not yet been as fully considered. Many of these (co)polymers represent clear opportunities for advancements in emerging biomedical and materials fields due to their increased biocompatibility and tuneable response. By highlighting recent examples of newly developed thermoresponsive polymer systems, we hope to promote the development of new generations of smart materials.

New directions in thermoresponsive polymers.

Beyond Poly(ethylene glycol): Linear Polyglycerol as a Multifunctional Polyether for Biomedical and Pharmaceutical Applications

Current academic and industrial research sustains large efforts to synthesize and develop environmentally responsive smart materials. The temperature-responsive materials with a trigger temperature in the physiological range attract much attention due to their potential biomedical applications. We describe their chemistry and the way to synthesize them, focusing on applications for smart clothing fabrication. Copyright © 2007 Society of Chemical Industry

Temperature-responsive polymers with LCST in the physiological range and their applications in textiles

Chain transfer reactions limit the molecular weight of polyglycidol prepared via alkali metal based initiating systems

Linear and star shaped polyglycidols (synonym with polyglycerols) are prepared in a controlled ring opening polymerization of protected glycidols. Beside the molar mass and the polydispersity, the architecture of the polyglycidols is controlled by using mono- and multifunctional mono- and polydispers initiators. Copolymers of dissimilarly protected glycidols as well as copolymers with nonfunctional oxiranes were prepared by means of anionic polymerization while copolymers of protected glycidol with tetrahydrofuran were prepared by means of cationic polymerization. Polyethers with functional groups in the side chains (functional polyethers) with special emphasis on polyglycidols (containing hydroxymethyl groups in the side chains) were used to prepare multifunctional polymers and (hetero)grafted polymer brushes via chemical and enzyme catalyzed reaction. The potential of poly(glycidol-graft-e-caprolactone)-co-glycidol) prepared via enzyme catalyzed grafting of polyglycidols using e-caprolactone as a monomer and Lipase B from Candida antarctica as a catalyst is presented. Finally, comparative degradation studies of densely and loosely grafted polyglycidols are presented and discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3209–3231, 2009

https://onlinelibrary.wiley.com/doi/pdf/10.1002/pola.23359

Synthesis and degradation of biomedical materials based on linear and star shaped polyglycidols

Polymers of glycidol (2,3-epoxypropanol-1) of different molar masses (between 2˙104 and 2˙105) and chain topology (linear and comb-like) were synthesised and used to obtain a series of temperature responsive water-soluble poly(glycidol-co-glycidol acetate)s. The degree of the substitution of the hydroxyl groups with the acetate groups influences the solution behaviour of the obtained copolymers, the cloud point may be controlled between +4°C and +lOO°C.

Hydrophobically modified polyglycidol – the control of lower critical solution temperature

A new class of thermosensitive polymers based on polyethers is discussed. Using living anionic polymerisation techniques a series of homo- and block copolymers of 2,3-epoxypropanol-1 (the glycidol), ethoxy ethyl glycidol ether, its hydrophobic derivative, and ethylene oxide of different molar masses and topology (linear and comb-like) was obtained. By simple chemical modification of hydroxyl groups in polyglycidol segments hydrophobic elements were introduced into polymer chains, which allowed to control the transition point related to the lower critical solution temperature between 0 to 100°C. The relation between the transition temperature and the structure of obtained polymers is discussed.

Alicja Utrata

Papers

Hydrophobically modified polyglycidol – the control of lower critical solution temperature

Novel reactive thermosensitive polyethers – control of transition point