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Biocompatible polymeric materials that can degrade in response to external irradiation with high spatial and temporal control show enormous potential in the field of biomedical applications. Herein, two six-membered cyclic carbonate monomers with a light-cleavable bromocoumarin functional pendent moiety attached via a carbamate linkage were prepared from 2-amino-1,3-propanediol (serinol) and 2-(aminomethyl)-2-methylpropane-1,3-diol, respectively. A series of light-degradable polycarbonates were synthesized by organo-catalyzed ring opening polymerization (ROP) of both monomers, and meanwhile their polymerization kinetics were investigated. Upon light-induced deprotection, both types of polycarbonates degraded rapidly into low molecular-weight compounds. The results of size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy and ultraviolet/visible (UV/VIS) spectroscopy confirmed the polymer structures and the light-induced degradation behavior. The photo-cleavage rates of bromocoumarin pendent groups and the degradation rates of the polymers were strongly dependent on polymer structures and used solvents.

Discovering renewable energy resources is receiving increased attention both in industrial and academic research. Vegetable oils are a promising route to renewable chemicals and polymers due to their ready availability, inherent biodegradability, and low toxicity. Also, bio-renewable fuels have been prepared from vegetable oils. Here, the soy oil monoglyceride has been obtained from the soybean oil by alcoholysis, and its structure was confirmed by the spectral analyses. To increase the yield of the monoglyceride formation and to prevent the ester interchange reversible reaction, we found that rapid cooling of the mixture with high-speed stirring allowed the best yield of soy oil monoglyceride. Then, three new polyester resins have been synthesized by the reaction of the monoglyceride with phthalic and/or maleic anhydrides with different ratios. The synthesized resins have been characterized by spectral analyses, and their morphological and physico-chemical properties such as acid value, iodine value, volatile matter content, and viscosity have been studied. The three polyester resins were soluble in common organic solvents. The effect of phthalic and maleic anhydrides ratio on the physical and chemical properties of the resin was also studied. The incorporation of maleic anhydride decreases the iodine value of the resins compared to phthalic anhydride-based resin.

In this work, poly(dimethylacrylamide)-b-poly(trimethylene carbonate) (PDMAAm-b-PTMC) block copolymers containing a pH-sensitive imine linkage were successfully synthesized by combination of ring-opening polymerization (ROP) and reversible addition–fragmentation chain transfer (RAFT) polymerization. A variety of vanillin terminated PTMC block copolymers were prepared by ROP of trimethylene carbonate (TMC) initiated by modified vanillin in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an organo-catalyst. The analysis of the resultant homopolymers by 1H NMR spectroscopy, size exclusion chromatography (SEC) and ESI-ToF masspectrometry (ESI-ToF-MS) revealed the excellent control of molar masses (Mn up to 14 000 g mol−1), dispersities (ĐM < 1.15) and end groups. The PTMC homopolymer was subsequently end-capped with an amino functionalized RAFT-agent leading to a macroinitiator containing imine group. Using this macroinitiator, PDMAAm-b-PTMC block copolymers with various molar masses were successfully prepared. In aqueous solution at pH 7.4, micelles could be formed by self-assembly of the amphiphilic block copolymer using a dialysis method. The hydrodynamic diameter (Dh) of the micelles was 76.3 ± 2.4 nm with a polydispersity index (PDI) of 0.179 ± 0.002. Under weak acidic conditions (pH 6.0), the hydrophilic PDMAAm block could be cleaved from micelles by hydrolysis of the imine linkage, while PTMC nanoparticles formed in situ with an average size of 149.8 ± 4.5 nm (PDI = 0.287 ± 0.007). Based on our strategy, these pH-cleavable PTMC-based amphiphilic block copolymers will expand the range of biodegradable synthetic polymers available for potential biomedical applications, such as controlled drug and gene delivery.

In this work, a variety of hyperbranched polymers (HBPs), such as hyperbranched polycarbonates, polyesters, polyurethanes and polyacetals, was successfully synthesized from castor oil and soybean oil based monomers via a A2 + B3 polycondensation. First, B3 monomer triols (TriOL), trialdehydes (TriAD), and tricarboxylic acids (TriAC) were obtained by ozonolysis of castor oil and soybean oil with following reductive or oxidative treatment. Their structures were characterized by 1H NMR and ATR-FTIR spectroscopy as well as electrospray ionization-Time of Flight-mass spectrometry. These trifunctional B3 monomers were applied in the preparation of HBPs. The resulting HBPs had number averaged molar mass (Mn) up to 9400 g/mol and weight averaged molar mass (Mw) up to 40,000 g/mol. Through adjusting the initial molar ratio of A2 to B3 monomers, hydroxyl terminated (from TriOL monomers) or carboxylic acid (from TriAC monomers) terminated HBPs could be obtained. All the HBPs were characterized by 1H NMR, size exclusion chromatography, and DSC. These HBPs are potential candidates for the synthesis of cross-linked polymeric materials or in biomedical applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2104–2114

A new eco-friendly strategy for the preparation of linear and hyperbranched polycarbonates was developed. Our work referred to a one-pot condensation polymerization of various alcohols (diols and triols) with equivalent amounts of eco-friendly dimethyl carbonate (DMC) at 120 °C, atmospheric pressure and in 1,4-dioxane solution using 4-dimethylaminopyridine (DMAP) or lithium acetylacetonate (LiAcac) as a catalyst. Polymer chains were built by pure transesterification of hydroxyl and methyl carbonate chain ends, and the single byproduct (methanol) was removed using a pressure-equalized addition funnel filled with 4 A molecular sieves as the crucial equipment in this work. Using this strategy, hyperbranched polycarbonates with high molar masses (Mn up to 10 000 g mol−1 and Mw up to 64 000 g mol−1) and high hydroxyl end group contents (up to 94%) were successfully prepared using dimethyl carbonate instead of toxic phosgene or phosgene-based monomers for the first time. In addition, linear aliphatic polycarbonates of various diols were also synthesized with Mn up to 16 000 g mol−1 and low molar mass distributions (ĐM < 1.70). Another eco-friendly aspect of this work was the use of equimolar amounts of DMC to avoid waste and the disposal of excess DMC; in a classic 2-step polycondensation for polycarbonate synthesis excess DMC is a prerequisite in order to obtain high molar masses.

Aliphatic polycarbonates have attracted significant attention for biomedical application over the last few years due to their biodegradability, low toxicity and good biocompatibility. However, in most cases, the use of metal-based catalysts is required for the preparation of aliphatic polycarbonates by the polycondensation method, which is difficult to remove completely from the final polymer. For this reason, our work is focused on the synthesis of high-molecular-weight aliphatic polycarbonates using organo-catalysts via a two-step polycondensation of dimethyl carbonate and a linear alkane diol as monomers. A variety of organo-catalysts have been surveyed for the synthesis of aliphatic polycarbonates. The influence of thiourea with mono- or bi-electron acceptor groups as cocatalysts, which were found to activate the carbonyl groups of lactide and trimethylene carbonate in the ring opening polymerization successfully, was investigated in the polycondensation. In summary, high-molecular-weight aliphatic polycarbonates, such as poly(1,4-butylene carbonate) (PBC), poly(1,5-pentamethylene carbonate) (PPC) and poly(1,6-hexamethylene carbonate) (PHC), were successfully prepared with number averaged molar masses (Mn) up to 23 000 g mol−1, dispersities below 1.8 and high yield of >80% under relatively mild operating conditions (T < 130 °C) using 4-dimethylaminopyridine (DMAP) as the catalyst. At 170 °C the poly(1,4-butylene carbonate) with Mn of 52 000 g mol−1 was synthesized. Additionally, hydroxyl group terminated poly(1,4-butylene carbonate) with Mn up to 17 000 g mol−1 was obtained and characterized by 1H NMR spectroscopy and ESI-TOF-mass spectrometry. The ratio of end groups (–OH/–OC(O)O–CH3) could be adjusted by using different feed ratios or catalysts.

In the present work, a new and facile strategy for the synthesis of light-responsive polyurethanes (LrPUs) based on serinol with o-nitrobenzyl pendent groups is developed. Stable monodisperse nanoparticles from these LrPUs can be formulated reproducibly in a simple manner, which is shown by dynamic light scattering (DLS) measurements. Upon irradiation with UV light, both polymers and nanoparticles undergo rapid degradation, which is investigated by DLS, scanning electron microscopy, size exclusion chromatography, and UV-vis spectroscopy. The nanoparticles are also employed for the encapsulation of the model drug Nile Red, and by exposure to UV light, a burst release of the payload is detected via fluorescence spectroscopy. This strategy can be easily applied to the straightforward synthesis of various new serinol-based monomers with different stimuli-responsive properties and therefore expand the family of biodegradable polymers.