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Study of Preparation and Properties of Stereoregular Poly(cyclohexenylene carbonate).

ABSTRACT: Fixing carbon dioxide as a polymer material is an effective and environmentally beneficial approach for reducing the harm of CO₂ greenhouse gas. In this paper, carbon dioxide and cyclohexene oxide were used as co-monomers, and a chiral binuclear cobalt complex with a biphenyl linker was employed as the catalyst to successfully prepare a poly(cyclohexenylene carbonate) with high stereoregularity. The influence of catalyst structure, CO₂ pressure, and operating temperature on the copolymerization rate and polymer structure were systematically investigated. Optimal catalyst structure and operating conditions were determined, resulting in an excellent poly(cyclohexenylene carbonate) with a stereoregularity as high as 93.5%. Performance testing revealed that the polyester had a molecular weight of approximately 20 kg/mol, a glass transition temperature of 129.7 °C, an onset decomposition temperature of 290 °C, and a tensile strength of 42.8 MPa. These results demonstrate high thermal stability and mechanical strength, indicating the potential for expanding the applications of aliphatic polycarbonate materials.

SUBMITTER: Zhang M

PROVIDER: S-EPMC10343680 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature

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Study of Preparation and Properties of Stereoregular Poly(cyclohexenylene carbonate).

Zhang Ming M Zhang Chengqian C Zhang Pengyuan P Liang Zhengyong Z

Molecules (Basel, Switzerland) 20230705 13

Fixing carbon dioxide as a polymer material is an effective and environmentally beneficial approach for reducing the harm of CO<sub>2</sub> greenhouse gas. In this paper, carbon dioxide and cyclohexene oxide were used as co-monomers, and a chiral binuclear cobalt complex with a biphenyl linker was employed as the catalyst to successfully prepare a poly(cyclohexenylene carbonate) with high stereoregularity. The influence of catalyst structure, CO<sub>2</sub> pressure, and operating temperature on ...[more]

PMID: 37446895

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Project description:Carbon dioxide/epoxide copolymerization is an efficient way to add value to waste CO2 and to reduce pollution in polymer manufacturing. Using this process to make low molar mass polycarbonate polyols is a commercially relevant route to new thermosets and polyurethanes. In contrast, high molar mass polycarbonates, produced from CO2, generally under-deliver in terms of properties, and one of the most widely investigated, poly(cyclohexene carbonate), is limited by its low elongation at break and high brittleness. Here, a new catalytic polymerization process is reported that selectively and efficiently yields degradable ABA-block polymers, incorporating 6-23 wt % CO2. The polymers are synthesized using a new, highly active organometallic heterodinuclear Zn(II)/Mg(II) catalyst applied in a one-pot procedure together with biobased ε-decalactone, cyclohexene oxide, and carbon dioxide to make a series of poly(cyclohexene carbonate-b-decalactone-b-cyclohexene carbonate) [PCHC-PDL-PCHC]. The process is highly selective (CO2 selectivity >99% of theoretical value), allows for high monomer conversions (>90%), and yields polymers with predictable compositions, molar mass (from 38-71 kg mol-1), and forms dihydroxyl telechelic chains. These new materials improve upon the properties of poly(cyclohexene carbonate) and, specifically, they show good thermal stability (Td,5 ∼ 280 °C), high toughness (112 MJ m-3), and very high elongation at break (>900%). Materials properties are improved by precisely controlling both the quantity and location of carbon dioxide in the polymer chain. Preliminary studies show that polymers are stable in aqueous environments at room temperature over months, but they are rapidly degraded upon gentle heating in an acidic environment (60 °C, toluene, p-toluene sulfonic acid). The process is likely generally applicable to many other lactones, lactides, anhydrides, epoxides, and heterocumulenes and sets the scene for a host of new applications for CO2-derived polymers.

Project description:A pH-responsive nanoparticle platform, based on PEG-b-poly (carbonate) block copolymers have been proposed that can respond to low pH as found in many cancer micro- and intracellular environment, including that in pancreatic cancer. The hydrophobic domain, i.e., the poly (carbonate) segment has been substituted with tertiary amine side chains, such as N, N'-dibutylethylenediamine (pKa = 4.0, DB) and 2-pyrrolidin-1-yl-ethyl-amine (pka = 5.4, Py) to generate two different sets of block copolymers namely PEG-DB and PEG-PY systems. These side-chain appended amines promote disassembly of nanoparticles and activation of drug release in response to pH conditions mimicking extra- (pH 6.9-6.5) and intracellular compartments (5.5-4.5, from early endosome to lysosome) of cancer tissues respectively. A frontline chemotherapy used for pancreatic cancer, i.e., gemcitabine (GEM) and a Hedgehog inhibitor (GDC 0449) has been used as the model combination to evaluate the encapsulation and pH-dependent release efficiency of these block copolymers. We found that, depending on the tertiary amine side chains appended to the polycarbonate segment, these block copolymers self-assemble to form nanoparticles with the size range of 100-150 nm (with a critical association concentration value in the order of 10-6 M). We also demonstrated an approach where GEM and GDC 0449-encapsulated PEG-DB and PEG-PY nanoparticles, responsive to two different pH conditions, when mixed at a 1:1 vol ratio, yielded a pH-dependent co-release of the encapsulated contents. We envision that such release behaviour can be exploited to gain spatiotemporal control over drug accumulation in pathological compartments with different pH status. The mixture of pH-responsive nanoparticles was found to suppress pancreatic cancer cell proliferation when loaded with anticancer agents in vitro. Cell-proliferation assay showed that both variants of PEG-b-polycarbonate block copolymers were inherently non-toxic. We have also immobilized iRGD peptide on intracellularly activable PEG-DB systems to augment cellular uptake. These targeted nanoparticles were found to promote selective internalization of particles in pancreatic cancer cells and tumor tissue.

Dataset Information

Study of Preparation and Properties of Stereoregular Poly(cyclohexenylene carbonate).

Publications

Study of Preparation and Properties of Stereoregular Poly(cyclohexenylene carbonate).

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