Due to the concern on residue toxic metal in biodegradable poly(propylene carbonate) (PPC), soil tolerant and heavy metal free aluminum complexes, that is, bifunctional aluminum porphyrin catalysts bearing quaternary ammonium salts on the ligand framework were prepared. Variation of the quaternary ammonium anion and the axial ligand had dramatic effects on the catalytic activity of resultant complex, among which complex 3b yielded perfectly alternative PPC with high molecular weight and relatively narrow polydispersity, and its TOF reached 3,407 h⁻¹ at [PO]/[cat.] ratio of 20,000 at 110 °C, although the PPC selectivity was 71%. By introducing specific substituent on the ligand framework, the electronic environment at the active center can be changed, among which complex 5b bearing tertiary butyl-functionalized aryl substituents exhibited a TOF of 449 h⁻¹ at [PO]/[cat.] ratio of 5,000 at 70 °C, with PPC selectivity of 92% and number average molecular weight of 36 kg mol⁻¹. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2346–2355

Common CO₂-based biodegradable polycarbonates like poly(propylene carbonate) or poly(cyclohexene carbonate) are generally hydrophobic, leading to slow biodegradation rate and poor cell adhesion, which limit their applications in the biomedical field. Here hydrophilic polycarbonates were prepared by one-pot terpolymerization of CO₂, propylene oxide (PO), and 2-((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl)oxirane (ME₃MO) using binary Salen Co(III)-Cl/PPNCl catalyst system. The resultant terpolymers showed one glass transition temperature (T_g), which decreased with the increase of ME₃MO units in the terpolymers (F_ME3MO). Water contact angles of the resultant terpolymers with F_ME3MO of 4.2−23.6% were 68−25°, while that of poly(propylene carbonate) was 90°, indicating that the terpolymers became hydrophlilic. Furthermore, the terpolymers with F_ME3MO more than 25.8% exhibited reversible and rapid thermo-responsive property in water, and the lower critical solution temperature (LCST) was highly sensitive to F_ME3MO. In particular, aqueous solution of the terpolymer with F_ME3MO of 72.6% showed a LCST around 35.2 °C, close to body temperature, which was promising for biomedical applications, especially for in vivo applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2834–2840.

Novel biodegradable poly(carbonate-ether)s (PCEs) with lower critical solution temperature (LCST) at body temperature were synthesized by copolymerization of CO₂ and ethylene oxide (EO) under double metal cyanide (DMC) catalyst. The PCEs showed carbonate unit (CU) content of 1.0–42.4 mol % and molecular weight of 2.7–247 kg/mol, which exhibited reversible thermoresponsive feature in deionized water with LCST in a broad window from 21.5 to 84.1 °C. The LCST was highly sensitive to the CU content and the molecular weight of PCEs, and it showed a linear relation with CU content for PCEs with similar molecular weight. In particular, aqueous solution of PCE with a 26.0 mol % of CU showed an LCST around 36.1 °C, which was very close to the body temperature. Interestingly, it was found that the phase transition behavior changed with PCE concentration. For PCE with M_n of 2.7 kg/mol and CU content of 30.0 mol %, the LCST increased from 21.5 to 36.7 °C when the PCE concentration changed from 10 to 1 g/L. Dynamic light scattering indicated that the phase transition was possibly due to a coil-to-globule transition. The thermoresponsive biodegradable PCE with LCST at body temperature is promising for biomedical applications, especially for in vivo applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

A convenient one-pot terpolymerization of CO₂, propylene oxide (PO), and L-lactide (L-LA) in short polymerization time (10 h or shorter) to afford poly(propylene carbonate-lactide) with excellent mechanical property and thermal stability using Y(CCl₃COO)₃-ZnEt₂-glycerin rare-earth ternary catalyst is reported. The yield of the copolymerization was between 69.7 and 111.7 g/(g Zn), corresponding to L-LA/PO molar feed ratio varying from 0 to 0.1, and the number average molecular weight was between 5.5×10⁴ and 11.9×10⁴. The L-LA content in the terpolymer increased from 1.1% to 34.7% when L-LA/PO molar feed ratio changed from 0.01 to 0.1. Introducing L-LA as the third comonomer could significantly improve the mechanical strength and thermal stability of PPC. For the terpolymer obtained from L-LA/PO molar feed ratio of 1:50, the elongation at break reached 40.5%, which is 3 times of that of pure PPC, and the thermal decomposition temperature increased by 32°C compared with pure PPC.

Low-molecular weight oligo(carbonate-ether) diols are important raw materials for polyurethane formation, which with tunable carbonate unit content (CU) may endow new thermal and mechanical performances to polyurethane. Herein, facile synthesis of oligo(carbonate-ether) diols with number average molecular weight (M_n) below 2000 g mol⁻¹ and CU tunable between 40% and 75% are realized in high activity by immortal copolymerization of CO₂/propylene oxide (PO) using zinc-cobalt double metal cyanide complex (Zn-Co-DMCC) in the presence of sebacic acid (SA). M_n of the oligomer is in good linear relationship to the mole ratio of PO and SA (PO/SA) and hence can be precisely controlled by adjusting PO/SA. Besides, the molecular weight distribution is quite narrow due to the rapid reversible chain transfer in the immortal copolymerization. High pressure and low temperature are favorable for raising CU. In all the reactions, the weight fraction of propylene carbonate (W_PC) can even be controlled as low as 2.0 wt %, and the catalytic activity of Zn-Co-DMCC is above 1.0 kgg⁻¹ cat. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Poly(ether carbonate)s (PPCs) with carbonate unit (CU) content ranging from 57.8 to 97.1% and number average molecular weight (M_n) around 100 kg/mol were conveniently prepared via copolymerization of CO₂ and propylene oxide under combinatorial catalyst of rare earth ternary (RET) complex and double metal cyanide (DMC) complex. Enhancement of catalytic activity and reduction of propylene carbonate byproduct were realized due to synergetic effect of the two metal catalysts, where DMC can be activated in the presence of RET. Solubility fractionation confirmed that the obtained PPCs were copolymers, not physical blends of each polymer. Thermal performances of the PPCs were closely related to their CU content, their glass transition temperatures (T_g) were tunable in the range of 6.7–36.3 °C, which decreased with decreasing CU content, while their thermal stabilities were enhanced significantly, an increase of 50.5 °C in 50% weight loss temperature was observed when CU content decreased from 97.1 to 57.8%. Both shear storage modulus and complex viscosity increased with increasing CU content, which became more obvious at lower frequency, featuring well with the CU content in the PPCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Poly(propylene carbonate) (PPC) is a biodegradable alternative copolymer of propylene oxide and carbon dioxide. As an amorphous polymer with lower glass transition temperature around 35 °C, PPC shows poor mechanical performance in that it becomes brittle below 20 °C and its dimensional stability deteriorates above 40 °C; thus toughening of PPC is urgently needed. Here we describe a biodegradable hyperbranched poly(ester-amide) (HBP) that is suitable for this purpose. Compared with pure PPC, the PPC/HBP blend with 2.5 wt% HBP loading showed a 51 °C increase in thermal decomposition temperature and a 100% increase in elongation at break, whilst the corresponding tensile strength remained as high as 45 MPa and tensile modulus showed no obvious decrease. Crazing as well as cavitation was observed in the scanning electron microscopy images of the blends, which provided good evidence for the toughening mechanism of PPC. The intermolecular hydrogen bonding interaction confirmed by Fourier transform infrared spectral analysis proved to be the reason for the toughening phenomenon. Copyright © 2011 Society of Chemical Industry

Aliphatic poly(urethane-amine) (PUA) was synthesized from copolymerization of CO₂ and 2-methylaziridine (MAZ) using Y(CCl₃COO)₃-ZnEt₂-glycerine coordination catalyst, the urethane content of PUA was over 80%, and its yield could reach 90%. PUA with molecular weight as high as 31.0 kg/mol was obtained when the copolymerization reaction was carried out in N,N-dimethylacetamide (DMAc), mainly due to the good solubility of PUA in DMAc. PUA exhibited reversible thermo-responsive property in deionized water, and the lower critical solution temperature (LCST) was highly sensitive to its urethane content and molecular weight, which was observed in a broad window from 37 to 90 °C. Furthermore, the phase transition behavior could also be controlled by change of pH value. When the pH value of the PUA aqueous solution changed from 9.2 to 13, the LCST value of the solution decreased from 48.4 °C to 30 °C. Therefore, the PUA showed thermo- and pH- dual responsive performance in water. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

2-Furyloxirane (FO), a monomer usually obtained from a nonpetroleum route, was prepared from the epoxidation reaction of furfural and trimethylsulfonium chloride. About 200–300 g FO can be obtained in each preparation process. Although anionic polymerization of FO generally gives low- molecular-weight polymers even after long periods of polymerization, the reaction was greatly improved when macrocyclic ether was used as a cocatalyst to potassium tert-butoxide. When 18-crown-6 was used as a cocatalyst, poly(2-furyloxirane) (PFO) with a number-average molecular weight (M_n) of 41.5 kg/mol and a polydispersity index of 1.3 was obtained at 94% yield after polymerization at 40 °C for 72 h. The PFO obtained contained a 61.7% head-to-tail (H-T) structure in the absence of the macrocyclic ether, and it reached 70.6% when cryptand[2,2,2] was used as a cocatalyst. PFO with higher regioregular structures showed improved thermal properties. For PFO with M_n of around 20.0 kg/mol, its glass transition temperature (T_g) increased from −3 to 6 °C when the H-T content was increased from 61.7 to 70.6%. Raising the M_n of PFO also raised T_g. For PFO with 68.9% H-T structure, its T_g could reach 7 °C when M_n was increased to 40 kg/mol. This study shows two effective ways to improve the thermal and mechanical performances of the polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Recently, rare earth ternary coordination catalyst represented as Y(CCl₃OO)₃-Glycerin-ZnEt₂ has been used for producing poly(propylene carbonate) (PPC, an alternating copolymer of carbon dioxide and propylene oxide) in industry scale, but its catalytic activity needs further improvement. One reason for the relatively low catalytic activity lied in that only 11.7% of active center was efficient due to possible embedding of active center in the heterogeneous catalyst. In this report, supporting strategy was developed, where Y(CCl₃OO)₃-Glycerin-ZnEt₂ was supported on various inorganic oxides. Two supporting methods were carried out. One way was to mix Y(CCl₃OO)₃-Glycerin with inorganic oxide first and then ZnEt₂ was dropped to form the supported catalyst, and the other was to make Y(CCl₃OO)₃-Glycerin-ZnEt₂ at first and then mixing with inorganic oxides. The former showed decreasing catalytic activity compared with corresponding unsupported rare earth ternary catalyst, while an improvement of 16–36% in catalytic activity was realized in the latter. PPC with an average number molecular weight (M_n) of over 100 kg/mol and carbonate unit (CU) content of higher than 96% was prepared by both supported catalysts. The catalytic activity of the supported catalyst depended significantly on the supports, which increased in the following order: α-Al₂O₃ < MgO < ZnO ≈ SiO₂ <γ-Al₂O₃. γ-Al₂O₃ was the best support for rare earth ternary catalyst, which showed a remarkable 36% increase in catalytic activity, corresponding to the utilization of 17% of active center. Although MgO supported catalyst gave only an 8% increase in catalytic activity, the M_n and CU content of PPC were raised to about 143 kg/mol and 99%, whereas the PPC from common rare earth ternary catalyst was about 108 kg/mol and 97%, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Cobalt porphyrin complex (TPPCo^IIIX) (TPP = 5, 10, 15, 20-Tetraphenyl- porphyrin; X = halide) in combination with ionic organic ammonium salt was used for the regio-specific copolymerization of propylene oxide and carbon dioxide. A turnover frequency of 188 h⁻¹ was achieved after 5 h, and the byproduct propylene carbonate was successfully controlled to below 1%, where the obtained poly(propylene carbonate) (PPC) showed number average molecular weight (M_n) of 48 kg/mol, head-to-tail content of 93%, and carbonate linkage of over 99%. When the polymerization time was prolonged to 24 h, PPC with M_n over 115 kg/mol and head-to-tail linkage maintaining 90% was prepared, whose glass transition temperature reached 44.5 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5959–5967, 2008

Lewis base modification strategy on rare earth ternary catalyst was disclosed to enhance nucleophilic ability of active center during copolymerization of carbon dioxide and propylene oxide (PO), poly(propylene carbonate) (PPC) with H-T linkages over 83%, and number–average molecular weight (M_n) up to 100 kg/mol was synthesized at room temperature using Y(CCl₃OO)₃-ZnEt₂-glycerine catalyst and 1,10-phenanthroline (PHEN) cocatalyst. Coordination of PHEN with active Zinc center enhanced the nucleophilic ability of the metal carbonate, which became more regio-specific in attacking carbon in PO, leading to PPC with improved H-T linkages. Moreover, the binding of PHEN to active Zinc center also raised the carbonate content of PPC to over 99%, whereas the PPC from common rare earth ternary catalyst was about 96%. Unlike the highly regio-regular structure PPC but with relatively low molecular weight recently reported in the literature, our high molecular weight regio-regular PPC did show significant improvement in thermal and mechanical performances. PPC with H-T linkages up to 83.2% showed glass transition temperature (T_g) of 43.3 °C, while T_g of PPC with H-T linkages of 69.7% was only 36.1 °C. When H-T connectivity was raised from 69.7 to 83.2%, the modulus of PPC showed a 78% increase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4451–4458, 2008