Caprolactone Monomer Research Articles

Thermoforming starch‐graft‐polycaprolactone biocomposites via one‐pot microwave assisted ring opening polymerization

AbstractA thermoformable starch‐graft‐polycaprolactone biocomposite was prepared by initiating ring‐open polymerization of caprolactone monomer onto starch under microwave irradiation. In this case, the thermoplastic and hydrophobic modification of starch could be realized by one‐pot grafting PCL, where the grafted PCL chains acted as the “plasticizing” tails of thermoforming and as the hydrophobic species of water‐resistance. The resultant biocomposites were injection‐molded as the sheets and their structure and properties were investigated by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, differential scanning calorimetry, dynamic mechanical analysis, contact angle measurement, and tensile testing. In this case, the grafted PCL chains entangled each other, and hence contributed to the strength and elongation of biocomposites. This work provided a simple strategy of one‐pot thermoplastic and hydrophobic modification of starch, and may be applied in a continuous process of modification, compounding, and molding. Meanwhile, the resultant biocomposites containing starch are believed to have a great potential application as an environment‐friendly and/or biomedical material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Structure and properties of new thermoforming bionanocomposites based on chitin whisker‐graft‐polycaprolactone

AbstractThermoformable bionanocomposites of chitin whisker‐graft‐polycaprolactone (CHW‐g‐PCL) were synthesized by initiating the ring‐opening polymerization of caprolactone monomer onto the CHW surface under microwave radiation. In this case, the “graft from” strategy contributed to long and dense “plasticizing” PCL tails onto the CHW surface as the key of thermoforming, and, therefore, such bionanocomposites were injection‐molded as the sheets with a structure of cocontinuous phase mediated with the entanglement of grafted PCL chains. The structure and properties of the molded CHW‐g‐PCL sheets were investigated by FTIR, XRD, SEM, DSC, DMTA, contact angle measurement, and tensile test. With an increase of the PCL content in CHW‐g‐PCL, the strength and elongation as well as the hydrophobicity of the nanocomposites increased at one time. This is the first report on the thermoformable polymer‐grafted nanocrystal derived from natural polysaccharide. Moreover, such new bionanocomposites with good mechanical performances could have great potential applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Degradable star polymers with high “click” functionality

AbstractDegradable polyester‐based star polymers with a high level of functionality in the arms were synthesized via the “arms first” approach using an acetylene‐functional block copolymer macroinitiator. This was achieved by using 2‐hydroxyethyl 2′‐methyl‐2′‐bromopropionate to initiate the ring‐opening polymerization (ROP) of caprolactone monomer followed by an atom transfer radical polymerization (ATRP) of a protected acetylene monomer, (trimethylsilyl)propargyl methacrylate. The hydroxyl end‐group of the resulting block copolymer macroinitiator was subsequently crosslinked under ROP conditions using a bislactone monomer, 4,4′‐bioxepanyl‐7,7′‐dione, to generate a degradable core crosslinked star (CCS) polymer with protected acetylene groups in the corona. The trimethylsilyl‐protecting groups were removed to generate a CCS polymer with an average of 1850 pendent acetylene groups located in the outer block segment of the arms. The increased functionality of this CCS polymer was demonstrated by attaching azide‐functionalized linear polystyrene via a copper (I)‐catalyzed cycloaddition reaction between the azide and acetylene groups. This resulted in a CCS polymer with “brush‐like” arm structures, the grafted segment of which could be liberated via hydrolysis of the polyester star structure to generate molecular brushes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1485–1498, 2009

Self‐Catalysis of Phthaloylchitosan for Graft Copolymerization of ε‐Caprolactone with Chitosan

AbstractSummary: A protection‐graft‐deprotection method was developed to prepare chitosan‐g‐polycaprolactone graft copolymers, during which the ring‐opening copolymerization of ε‐caprolactone onto phthaloylchitosan (PHCS) happened without any additional catalysis. The intermediate PHCS was introduced primarily to protect the active amino group of chitosan. After controlled experiments, the phthalimido compound was proposed to be a novel kind of organic catalyst for the ring‐opening polymerization of caprolactone monomers, while the hydroxyl group acted as an initiator. Hence, in this graft system, PHCS was endowed with both self‐catalysis and self‐initiation at the same time, and the PCL side chains grew from the hydroxyl groups of the chitosan backbone. magnified image

In-Situ Copolymerization of Cyclic Poly(butylene terephthalate) Oligomers and ε-Caprolactone

Copolyesters were synthesized by using ring-opening polymerization of cyclic poly(butylene terephthalate) oligomers (c-PBT) and -caprolactone monomer (CL) in the presence of stannoxane catalyst at an elevated temperature. The in-situ copolymerization was conducted with various c-PBT/CL feed ratios. The copolyesters were characterized by GPC, NMR, and FT-IR techniques. Phase separation and the relaxation behavior of the resultant copolyesters were investigated by DSC, DMTA, and dielectric spectroscopy measurements. Mechanical properties (stress-strain behavior) are also reported and can be adjusted by varying the -caprolactone content of the copolymer.

Stereospecific synthesis of chiral caprolactone monomers from d-glucose

The synthesis and characterisation of a novel chiral bicyclic oxacaprolactone is reported. The choice of diisopropylidene- d-glucose as a starting material allowed selective introduction of the synthetic equivalent necessary for the formation of the seven-membered ring of the lactone, i.e., one carbon atom and the carbonyl of the ester which was to become the carbonyl group of the lactone. In order to complete the formation of the seven-membered ring, via intramolecular lactonisation, it was necessary to excise carbon six and to establish a primary alcohol group at C-5. The lactone was fully characterised and available for ring-opening polymerisation.

Poly(η-caprolactone) layered silicate nanocomposites: effect of clay surface modifiers on the melt intercalation process

AbstractNanocomposites based on biodegradable poly(e-caprolactone) (PCL) and layered silicates (montmorillonite) modified by various alkylammonium cations were prepared by melt intercalation. Depending on whether the ammonium cations contain non-functional alkyl chains or chains terminated by carboxylic acid or hydroxyl functions, microcomposites or nanocomposites were recovered as shown by X-ray diffraction and transmission electron microscopy. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. The layered silicate PCL nanocomposites exhibited some improvement of the mechanical properties (higher Young’s modulus) and increased thermal stability as well as enhanced flame retardant characteristics as result of a charring effect. This communication aims at reporting that the formation of PCL-based nanocomposites strictly depends on the nature of the ammonium cation and its functionality, but also on the selected synthetic route, i.e. melt intercalation vs. in situ intercalative polymerization. Typically, protonated w-aminododecanoic acid exchanged montmorillonite allowed to intercalate ε -caprolactone monomer and yielded nanocomposites upon in situ polymerization, whereas they exclusively formed microcomposites when blended with preformed PCL chains. In other words, it is shown that the formation of polymer layered silicate nanocomposites is not straightforward and cannot be predicted since it strongly depends on parameters such as ammonium cation type and functionality together with the production procedure, i.e., melt intercalation, solvent evaporation or in situ polymerization.

Polymerisation and stabilisation of polycaprolactone using a borontrifluoride–glycerol catalyst system

This paper describes a new synthetic route to poly-ε-caprolactone. A new cationic polymerisation has been developed which uses a borontrifluoride catalyst to open the caprolactone monomer, and glycerol to increase the molecular weights of the products. A post-treatment method has also been developed to reduce the amount of residual catalyst in the final product. This reduces the extent of borontrifluoride catalysed hydrolysis and therefore allows variation of the degradation rate of the material.

Physical and biocompatibility properties of poly- ε-caprolactone produced using in situ polymerisation: a novel manufacturing technique for long-fibre composite materials

Preliminary investigations into a novel process for the production of poly- ε-caprolactone (PCL) to be used as a matrix material in a bioabsorbable composite material are detailed. This material is primarily being developed as a bone substitute for use in maxillofacial reconstructive surgery, however, the technique described could be adapted to other areas where bioabsorbable composite materials may be used. The development of a totally bioabsorbable long-fibre composite material would allow a two-stage degradation to occur with the matrix material degrading first leaving a scaffold structure of degradable fibres which would be absorbed at a later stage. Caprolactone monomer was polymerised in situ within a tool cavity to produce a net shape moulding. Inclusion of a fibre preform within the tool cavity which was impregnated by the liquid monomer produces a long-fibre composite material. PCL with a range of molecular weights has been produced using this liquid moulding technique to assess the physical and biocompatibility properties compared to commercially available PCL. Osteoblast-like cells derived from human craniofacial bone (CFC) have been used to assess the in vitro biocompatibility of the PCL. The results show that high-quality PCL with a narrow molecular weight distribution and properties similar to commercially available PCL can be produced using this technique. Polymerisation of the monomer around a woven fibre preform made of a poly(lactic acid) (PLA)/poly(glycolic acid) (PGA) copolymer (vicryl mesh) produced a bioabsorbable long-fibre composite material. Further work is ongoing to develop this system towards a method for improving craniofacial bone reconstruction.