Control of thermoresponsivity of biocompatible poly(trimethylene carbonate) with direct introduction of oligo(ethylene glycol) under various circumstances

Abstract

Poly(trimethylene carbonate) (PTMC) is a well‐known biodegradable polymer with good biocompatible properties which make it suitable for biomedical applications. Poly(5‐[2‐{2‐(2‐methoxyethoxy)ethyoxy}‐ethoxymethyl]‐5‐methyl‐1,3‐dioxa‐2‐one) (PTMC‐MOE3OM) and copolymers, bearing oligo ethylene glycol (OEG) at the side chain of PTMC backbone, were selected to investigate the cloud point behavior by solvents such as PBS, water, 10% ethanol solution and various ionic strengths. A pH‐responsive copolymer, poly(TMCM‐MOE3OM‐co‐(5‐methyl‐5‐carboxylic‐1,3‐dioxane‐2‐one)) as carboxylic acid carbonate showed a decreased critical temperature at pH 2. Photo‐responsive copolymer, poly(TMCM‐MOE3OM‐co‐coumarin derivatives) bearing 1% and 10% of photo‐induced molecules (7‐[(5‐(5‐methyl‐1,3‐dioxa‐2‐one)methoxy)]‐methoxy coumarin (TMCM‐coumarin)) exhibited a low cloud point because of the hydrophobic moieties. Meanwhile, alternative coumarin polymer including 2% of 4‐methyl‐7‐[(5‐(5‐methyl‐1,3‐dioxa‐2‐one)methoxy)butoxy)]‐methoxy coumarin (TMCM‐4‐methyl‐coumarin) has been successfully synthesized and copolymerized as a novel molecule. The various combinations of monomers were studied and the significant properties were determined via external triggers after copolymerization. This study showed basically synthetic progress toward designs and trivial rationalization of thermoresponsive copolymers close to body temperature. At present, various pendant groups as side part affect to the lower critical solution temperature (LCST) and biodegradable polymer in order to utilize the actual external stimuli application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3466–3474

Synthesis of amphiphilic block copolymer using trimethylene carbonate bearing oligo(ethylene glycol) and investigation of thin film including cilostazol

“…[ 17 ] The synthesis of poly(TMCM‐MOE3OM) was carried out with reference to the literature. [ 24 ] Poly(TMCM‐MOE3OM) was synthesized via anionic polymerization. TMCM‐MOE3OM 3.90 g (13.3 mmol) was dissolved in anhydrous CH 2 Cl 2 and made anhydrous solution using MS4A was added to two‐neck round‐bottom flask under N 2 atmosphere.…”

“…In addition, due to the mobility of OEG, decomposition behavior that differed from conventional PTMC was achieved. [ 23 ] Development of a photo‐crosslinked polymer for improvement of mechanical strength [ 24 ] and nanoparticles for drug delivery [ 25 ] were also achieved with block copolymers. By grafting OEG to the polymer backbone, intermolecular interaction is inhibited and it becomes a flexible polymer.…”

Insights into the polymerization kinetics of thermoresponsive polytrimethylene carbonate bearing a methoxyethoxy side group

“…An aliphatic polycarbonate that exhibits thermogelling behavior that may be suitable for these applications is poly(trimethylene carbonate) (PTMC) bearing pendant methoxyethoxy (MOE) groups 8,11,12 . These polymers can be prepared by functionalizing a cyclic carbonate monomer followed by ring opening polymerization, 11 which provides control over the polymer arcitecture 13 .…”

Viscoelastic Evaluation of Poly(Trimethylene Carbonate)s Bearing Oligoethylene Glycol Units Which Show Thermoresponsive Properties at Body Temperature

“…These change to carboxylic acid groups after degradation and have the potential to cause inflammation. Therefore, ester‐free PTMC derivatives bearing the side chain were designed in previous research by our group …”

“…Their block copolymers were obtained as a solid although the ester group was converted to a carboxylic acid group during degradation which induce the acid condition as a side effect compared with ester‐free PTMC derivatives . Above all, the properties of PTMC bearing the ethylene glycol chain have not been widely studied although several properties were investigated such as, degradation behaviors and photo‐ and thermo‐sensitive behaviors …”