Comparative study of the radiation-induced grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) and polypropylene substrates. I: Kinetics and structural investigation

A comparative study has been made of the radiation grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) and polypropylene (PP) substrates, using the simultaneous irradiation method. Effects of grafting conditions such as monomer concentrations, type of solvent, dose rate and irradiation dose on the grafting yield were investigated. Under the same grafting conditions it was found that a higher degree of grafting of styrene was obtained using a mixture of dichloromethane/methanol solvents for PFA and methanol for PP and the degree of grafting was higher in PP than in PFA at all doses. However, the micro-Raman spectroscopy analysis of the graft revealed that, for the same degree of grafting, the penetration depth of the grafted polystyrene into the substrate was higher in PFA than in PP substrates. In both polymers the crystallinity was hardly affected by the grafting process and the degree of crystallinity decreased slightly with grafting dose. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be 0.6 and 1.4 order for PFA and 0.15 and 2.2 for PP, respectively. The degree of grafting increased with increasing radiation dose in both polymers. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield for PFA and PP was accompanied by a proportional increase in the penetration depth of the graft into the substrates. (C) 2003 Society of Chemical Industry.

Copolymers obtained by the radiation-induced grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) substrates. 1. Preparation and structural investigation

A study has been made to investigate the radiation grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) (PFA) substrates, using the simultaneous irradiation method. Two PFA polymers of different comonomer perfluoropropyl vinyl ether (PPVE) content and degree of crystallinity were used. Effects of grafting conditions such as monomer concentrations, type of solvent, dose rate, and irradiation dose on the grafting yield were investigated. Of the six different solvents used, the most efficient in terms of increasing grafting yield were dichloromethane, benzene, and methanol. The degree of grafting increased with increasing radiation dose up to 500 kGy, stabilizing above this dose. However, the grafting yield decreased with an increase in the dose rate. The grafting of styrene onto the PFA substrates was confirmed by FTIR-ATR and micro-Raman spectroscopy, The increase in the overall grafting yield was accompanied by a proportional increase in the penetration depth of the grafts into the substrate.

Spectroscopic study of the penetration depth of grafted polystyrene onto poly (tetrafluoroethylene-co-perfluoropropylvinylether) substrates. 1. Effect of grafting conditions

This study concerns the radiation grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinylether) (PFA) substrates and the penetration depth of the graft. Grafting was obtained by the simultaneous irradiation method, and the spectroscopic analysis was made with the micro-Raman technique. Effects of grafting conditions such as the type of solvent, dose rate, and irradiation dose on the grafting yield were investigated. Of the different solvents used, the most efficient in terms of increasing grafting yield were dichloromethane, benzene, and methanol, respectively. A mixture of methanol and dichloromethane used as a solvent for styrene achieved a higher degree of grafting and concentration of grafted polystyrene onto the surface of PFA substrates than solutions of the monomer in the separate solvents. The degree of grafting increased with increasing radiation dose up to 500 kGy, stabilizing above this dose. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield was accompanied by a proportional increase in the penetration depth of the grafts into the substrate. (C) 2002 Wiley Periodicals, Inc.

Characterisation of grafted supports used for solid-phase synthesis

A series of 'pellicular' type supports were fabricated by direct gamma-radiation-mediated graft polymerisation of styrene onto polypropylene, followed by aminomethylation. Raman spectroscopy was used for measuring the level of penetration of polystyrene graft into polypropylene, and other structural features such as density of graft and depth of functionalisation. The kinetics of the coupling of fluorenylmethylcarbamate (Fmoc)-labelled amino acids, to the aminomethylated polystyrene grafts have been measured by UV absorption followed cleavage of the Fmoc chromophore. The Raman spectroscopy results showed that for this series of experiments the calculated rate coefficient for coupling of Fmoc-labelled amino acids was primarily dependent on graft thickness, but was also influenced by the proportion of polystyrene graft to polypropylene. In general, it was also shown that with increasing loading capacity of support the calculated rate coefficient for amino-acid coupling decreased correspondingly. In addition, a support that had both a high rate coefficient and a high loading capacity was prepared from polypropylene base material with a co-continuous porous structure (high surface area). (C) 2003 Society of Chemical Industry.

Polyethylene-layered silicate nanocomposites for rotational moulding

A series of polyethylene-layered silicate nanocomposites has been studied as possible new candidates for rotational moulding. Two organically treated layered silicates were melt-compounded into a maleated linear low-density polyethylene host polymer at loadings of 6 and 9%, by weight. The morphology and properties of the nanocomposites were assessed by using dynamic mechanical thermal analysis, parallel-plate rheometry, wide-angle X-ray diffraction and transmission electron microscopy. The sintering behaviour of the nanocomposites was qualitatively assessed via hot-stage microscopy, indicating that the choice of nanofiller will play an important role in terms of producing nanocomposite materials with acceptable processability for rotational moulding. (C) 2003 Society of Chemical Industry.

Flow patterns in granulating systems

Particle flow patterns were investigated for wet granulation and dry powder mixing in ploughshare mixers using Positron Emission Particle Tracking (PEPT). In a 4-1 mixer, calcium carbonate with mean size 45 mum was granulated using a 50 wt.% solution of glycerol and water as binding fluid, and particle movement was followed using a 600-mum calcium hydroxy-phosphate tracer particle. In a 20-1 mixer, dry powder flow was studied using a 600-mum resin bead tracer particle to simulate the bulk polypropylene powder with mean size 600 mum. Important differences were seen between particle flow patterns for wet and dry systems. Particle speed relative to blade speed was lower in the wet system than in the dry system, with the ratios of average particle speed to blade tip speed for all experiments in the range 0.01-015. In the axial plane, the same particle motion was observed around each blade; this provides a significant advance for modelling flow in ploughshare mixers. For the future, a detailed understanding of the local velocity, acceleration and density variations around a plough blade will reveal the effects of flow patterns in granulating systems on the resultant distribution of granular product attributes such as size, density and strength. (C) 2002 Elsevier Science B.V All rights reserved.

Dog peritoneal and pleural cavities as bioreactors to grow autologous vascular grafts

Objective: The purpose of this study was to grow artificial blood vessels for autologous transplantation as arterial interposition grafts in a large animal model (dog). Method and results: Tubing up to 250 mm long, either bare or wrapped in biodegradable polyglycolic acid (Dexon) or nonbiodegradable polypropylene (Prolene) mesh, was inserted in the peritoneal or pleural cavity of dogs, using minimally invasive techniques, and tethered at one end to the wall with a loose suture. After 3 weeks the tubes and their tissue capsules were harvested, and the inert tubing was discarded. The wall of living tissue was uniformly 1-1.5 mm thick throughout its length, and consisted of multiple layers of myofibroblasts and matrix overlaid with a single layer of mesothelium. The myofibroblasts stained for a-smooth muscle actin, vimentin, and desmin. The bursting strength of tissue tubes with no biodegradable mesh scaffolds was in excess of 2500 mm Hg, and the suture holding strength was 11.5 N, both similar to that in dog carotid and femoral arteries. Eleven tissue tubes were transplanted as interposition grafts into the femoral artery of the same dog in which they were grown, and were harvested after 3 to 6.5 months. Eight remained patent during this time. At harvest, their lumens were lined with endothelium-like cells, and wall cells stained for alpha-actin, smooth muscle myosin, desmin and smoothelin; there was also a thick adventitia containing vasa vasorum. Conclusion: Peritoneal and pleural cavities of large animals can function as bioreactors to grow myofibroblast tubes for use as autologous vascular grafts.

Novel cuticular hydrocarbons from the cane beetle Antitrogus parvulus - 4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes - Unprecedented anti-anti-anti-stereochemistry in the 4,6,8,10-methyltetrad

[GRAPHICS] The major cuticular hydrocarbons from the cane beetle species Antitrogus parvulus are 4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes, I and 2, respectively. Stereoisomers of 2,4,6,8-tetramethylundecanal of established relative stereochemistry were derived from 2,4,6-trimethylphenol and were then coupled with appropriate methyl-substituted phosphoranes 62 and 25 to furnish alkenes, which on reduction provided diastereomers of I and 2, respectively. Capillary gas chromatography, mass spectrometry, and high resolution C-13 NMR spectroscopy confirmed 1 as either 84a or 84b and 2 as either 15a or 15b. The novelty of these structures and their relative stereochemistry is briefly related to polyketide assembly.

An ESR study of the radiolysis of semi-crystalline ethylene-propylene copolymers containing DOP mobilizer

The radiolysis of a poly(ethylene-co-propylene), Elpro, marketed by Thai Polypropylene Co. Ltd for the manufacture of medical goods has been investigated at 77 K. Calcium stearate was blended with the Elpro as a processing aid; and dioctyl phthalate, DOP, was added in various amounts as a radiation stabilizer. The ESR spectra of Elpro and Elpro+Ca were very similar and characterized principally by the presence of PP a-carbon radicals. The spectra of the samples containing DOP were similar to those for Elpro but with an additional narrow singlet arising from DOP radicals. On annealing the irradiated polymers to higher temperatures, the singlet was lost between 250 and 270 K, and at room temperature the principal radicals remaining were allyl radicals. The G-values for radical formation at 77 K for Elpro and Elpro+Ca at 77 K were 3.0 and 3.2, respectively, but incorporation of DOP resulted in lower G-values, ranging from 1.6 to 1.4 for 0.5 and 2.5 phr DOP, respectively.(c) 2005 Wiley Periodicals, Inc.

Biocompatible properties of surgical mesh using an animal model

To study the biocompatibility of surgical meshes for use in pelvic reconstructive surgery using an animal model. Eight different types of mesh: Atrium, Dexon, Gynemesh, IVS tape, Prolene, SPARC tape, TVT tape and Vypro II, were implanted into the abdominal walls of rats for 3 months' duration. Explanted meshes were assessed, using light microscopy, for parameters of rejection and incorporation. Type 1 (Atrium, Gynemesh, Prolene, SPARC and TVT) and type 3 (Vypro II, Dexon and IVS) meshes demonstrated different biocompatible properties. Inflammatory cellular response and fibrosis at the interface of mesh and host tissue was most marked with Vypro II and IVS. All type 1 meshes displayed similar cellular responses despite markedly different mesh architecture. The inflammatory response and fibrous reaction in the non-absorbable type 3 meshes tested (IVS and Vypro II) was more marked than the type 1 meshes. The increased inflammatory and fibrotic response may be because of the multifilamentous polypropylene components of these meshes. Material and filament composition of mesh is the main factor in determining cellular response.

A rheology study of high-energy radiolysis of a semicrystalline ethylene-propylene copolymer containing DOP mobilizer

The ractiolysis of a poly(ethylene-co-propylene), Elpro grade P 750 J, marketed by Thai Polypropylene Co. Ltd. for the manufacture of medical goods, was investigated at ambient temperature and melt rheology measured. The roles of calcium stearate, blended with the Elpro as a processing aid, and dioctyl phthalate (DOP), added in various amounts as a radical scavenger, were assessed. Following radiolysis, G' and the viscosity of the polymer melts at 453 K both decreased with increasing radiation dose, even when the mobilizer was present. The results indicated that although the DOP did scavenge radicals, it did not protect the polymer from net chain scission in a low-dose regimen. The value of (G(S) - 4G(X)) was approximately 0.6-0.7. (c) 2006 Wiley Periodicals, Inc.