Summary: A novel aliphatic polycarbonate based on ketal protected dihydroxyacetone was synthesized by ring‐opening polymerization of cyclic carbonate monomer, 2,2‐ethylenedioxypropane‐1,3‐diol carbonate (EOPDC), in bulk. Effects of polymerization conditions such as catalysts, catalyst concentration, reaction temperature and reaction time on the polymerization were investigated. The polycarbonate obtained was characterized by GPC, FTIR, 1H NMR, 13C NMR and DSC. The study on in vitro degradation of PEOPDC shows that the degradation mainly results from surface erosion.
Synthesis of an aliphatic polycarbonate with a high molecular weight by ring‐opening polymerization of cyclic carbonate monomer EOPDC. 相似文献
The six-membered cyclic carbonate monomer, 2,2-dimethoxy-1,3-propanediol carbonate based on dihydroxyacetone with methanol ketal protected carbonyl group, was prepared by a two-step reaction including protection and ring-closing, starting from dihydroxyacetone. The ring-opening polymerization of 2,2-dimethoxy-1,3-propanediol carbonate was carried out in bulk at 110–140°C initiated by stannous octanoate to give polycarbonate, poly(2,2-dimethoxypropane-1,3-diol carbonate). The effects of different reaction conditions including different catalyst, reaction temperature, molar ratio of monomer to initiator and polymerization time on the polymerization were investigated. Polycarbonate was obtained with the yield of 58.9–91.0%. The number average molecular weight of polycarbonate was in the range of 1.43 × 104 to 13.82 × 104 with polydispersity indexes from 1.31 to 1.91. The protecting ketal group was partly removed by hydrolysis using 50% trifluroacetic acid as a catalyst to give a functional polycarbonate containing 70% ketone carbonyl group, which improved the hydrophilicity of initial polycarbonate. The in vitro degradation tests were carried out in a phosphate buffer solution with pH 7.4 at 37°C, which showed that the modified polycarbonate degraded completely after 5 days. 相似文献
Main-chain biodegradable liquid crystal (LC) based on cholesteryl end-capped polycarbonate copolymers was investigated. The novel LC was synthesised through ring-opening copolymerisation of trimethylene carbonate with ε-caprolactone (CL) initiated by cholesterol, without adding any catalyst. The chemical structure of the resulting polymers was confirmed by 1H NMR. The liquid crystalline properties were validated by X-ray diffraction, differential scanning calorimetry and polarising optical microscopy. The results showed that the synthesised polycarbonate copolymers Chol-(TMCL)x + y exhibited liquid crystallinity in particular temperature ranges because of the incorporation of the cholesterol moieties. Furthermore, the effect of CL content on the mesomorphism properties of Chol-(TMCL)x+y was also investigated; the higher the CL content, the lower the mesomorphism properties. It might be attributed to the hindered orientation of LC caused by the crystallinity of the poly(ε-caprolactone) (PCL) segments in the polymer chain. 相似文献
We here report the organocatalytic and temperature-controlled depolymerization of biobased poly(limonene carbonate) providing access to its trans-configured cyclic carbonate as the major product. The base TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) offers a unique opportunity to break down polycarbonates via end-group activation or main chain scission pathways as supported by various controls and computational analysis. These energetically competitive processes represent an unprecedented divergent approach to polycarbonate recycling. The trans limonene carbonate can be converted back to its polycarbonate via ring-opening polymerization using the same organocatalyst in the presence of an alcohol initiator, offering thus a potential circular and practical route for polycarbonate recycling. 相似文献
Poly(5-benzyloxy-trimethylene carbonate) (PBTMC), a new functional polycarbonate was synthesized by enzymatic ring-opening polymerization in bulk at 150°C using Porcine pancreas lipase (PPL) or Candida rugosa lipase (CL) as catalyst. Influences of different polymerization conditions such as the source of enzyme, enzyme concentration and polymerization time on the molecular weight and yield were studied. The results showed that PPL exhibited higher activity than CL. Both higher molecular weight(Mn, 18953) and yield(98%) could be obtained by the use of PPL as catalyst. 1H NMR spectrum showed no decarboxylation occurrence during the ring-opening polymerization. 相似文献
The air-stable, chiral (salen)Cr(III)Cl complex (3), where H(2)salen = N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexene diamine, has been shown to be an effective catalyst for the coupling of cyclohexene oxide and carbon dioxide to afford poly(cyclohexenylene carbonate), along with a small quantity of its trans-cyclic carbonate. The thus produced polycarbonate contained >99% carbonate linkages and had a M(n) value of 8900 g/mol with a polydispersity index of 1.2 as determined by gel permeation chromatography. The turnover number (TON) and turnover frequency (TOF) values of 683 g of polym/g of Cr and 28.5 g of polym/g of Cr/h, respectively for reactions carried out at 80 degrees C and 58.5 bar pressure increased by over 3-fold upon addition of 5 equiv of the Lewis base cocatalyst, N-methyl imidazole. Although this chiral catalyst is well documented for the asymmetric ring-opening (ARO) of epoxides, in this instance the copolymer produced was completely atactic as illustrated by (13)C NMR spectroscopy. Whereas the mechanism for the (salen)Cr(III)-catalyzed ARO of epoxides displays a squared dependence on [catalyst], which presumably is true for the initiation step of the copolymerization reaction, the rate of carbonate chain growth leading to copolymer or cyclic carbonate formation is linearly dependent on [catalyst]. This was demonstrated herein by way of in situ measurements at 80 degrees C and 58.5 bar pressure. Hence, an alternative mechanism for copolymer production is operative, which is suggested to involve a concerted attack of epoxide at the axial site of the chromium(III) complex where the growing polymer chain for epoxide ring-opening resides. Preliminary investigations of this (salen)Cr(III)-catalyzed system for the coupling of propylene oxide and carbon dioxide reveal that although cyclic carbonate is the main product provided at elevated temperatures, at ambient temperature polycarbonate formation is dominant. A common reaction pathway for alicyclic (cyclohexene oxide) and aliphatic (propylene oxide) carbon dioxide coupling is thought to be in effect, where in the latter instance cyclic carbonate production has a greater temperature dependence compared to copolymer formation. 相似文献
Silica nanoparticles were first used as the carrier for the porcine pancreas lipase (PPL) immobilization. The result of transmission electron microscopy (TEM) showed that the immobilized lipase was still in nanosize after enzyme immobilization. The ring-opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC) catalyzed by this immobilized PPL (IMPPL) was explored. 1H NMR spectra suggested no evidence of decarboxylation during propagation. Influences of IMPPL concentration and reaction temperature on the molecular weight and yield of poly(DTC) were studied. The recovery and reuse of IMPPL for the ring-opening polymerization of DTC was also investigated. The recycling IMPPL showed even higher catalytic activity and a higher molecular weight of polycarbonate could be achieved. 相似文献
The polycarbonate copolymer poly(trimethylene carbonate-co-5,5-dimethyl trimethylene carbonate) (P(TMC-co-DTC)) was synthesized by the polymerization of trimethylene carbonate (TMC) and 5,5-dimethyl trimethylene carbonate (DTC) using tin (II) 2-ethylhexanoate [Sn(Oct)(2)] as a catalyst. In vitro degradation tests indicated this polycarbonate copolymer degraded slowly in phosphate buffer saline solution (PBS, 0.1 mol/L, at 37°C). Magnetic polymer microspheres (MMC-PC-M) generated from the P(TMC-co-DTC) copolymer and containing Fe(3)O(4) magnetic ultrafine powders and an anticancer drug, mitomycin C (MMC) were prepared by a solvent evaporation technique. These anticancer magnetic polycarbonate microspheres showed strong magnetic responsiveness and high MMC loading capacity. In vitro drug release studies indicated that these microspheres sustained steady release rates of MMC in PBS. In vitro cytotoxicity assays demonstrated the microspheres were strongly inhibitory to human hepatic carcinoma (Bel-7204) cells. In vivo site-specific therapy in nude mice with human hepatic carcinoma indicated that the microspheres possessed markedly high antitumor activity against human hepatic carcinoma (Bel-7204). 相似文献
New polydithiocarbonates and polythiocarbonates were obtained by interfacial polymerization of bis(4-mercaptophenyl)methane, bis(4-mercaptophenyl)ether and bis(4-mercaptophenyl)sulfide with phosgene, bisphenol A bischloroformate and bisphenol A polycarbonate oligomers (-OH/-O-CO-Cl terminated). Polymerization process was carried out under interfacial conditions using a phase-transfer catalyst, as earlier described for the synthesis of polydithiocarbonates and polythiocarbonates from 2,2-bis(4-mercaptophenyl)propane. The structures of the polymers were examined by IR and NMR spectroscopies; their thermal properties were investigated by thermogravimetric analysis and differential scanning calorimetry. In particular, the effect of the substitution of one or both the ethereal oxygen atoms of the carbonate group by sulfur has been analyzed by comparing the Tg values and the ability to crystallize of the sulfur containing polymers with those of the corresponding polycarbonates. 相似文献