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showing 10 items of 7296 documents
Insight into the synthesis of N-methylated polypeptides
2020
The ring-opening polymerization (ROP) of N-carboxy anhydrides (NCAs) is mostly divided into two classes: NCAs of α-substituted amino acids and N-methylated NCAs of α-unsubstituted glycine derivatives (NNCAs). The use of both monomer types offers different mechanistic features and results in a multitude of functional materials. To combine these properties, the synthesis and ROP of α-substituted and N-methylated NCAs (αNNCAs) of several amino acids were investigated. The current study provides insight into the influence of polymerization conditions and the limitations caused by the enhanced steric demand of the amino acid NCA monomers and their N-methylated derivatives. Namely, the effects of…
Stable Expression of Heterologous Sulfotransferase in V79 Cells: Activation of Primary and Secondary Benzylic Alcohols
1994
Abstract A sulfotransferase (ST) capable of activating 1-hydroxymethylpyrene (HMP) and 9-hydroxymethylanthracene (HMA) to mutagens was purified from rat liver. This enzyme appeared to be identical with hydroxysteroid STa, whose cDNA was cloned and stably expressed in Chinese hamster V79 cells. Several primary and secondary benzylic alcohols derived from polycyclic aromatic hydrocarbons induced gene mutations, sister chromatid exchanges (SCE) and/or cytotoxicity in these cells.
Surfactant Assisted Polymerization of Tetrafluoroethylene in Supercritical Carbon Dioxide with a Pilot Scale Batch Reactor.
2008
Chain-free radical polymerization of tetrafluoroethylene (TFE) was carried out in supercritical carbon dioxide (scCO2), at 50 °C and 121–133 bar, with tertiary-amyl-per-pivalate as a free radical initiator, using a 5-L pilot scale batch reactor. Experiments were carried out both in the absence and in the presence of perfluoropolyether (PFPE) carboxylate surfactants. Stabilizers were employed under the free acid form and as sodium and calcium salts. An expanded fibrillated poly(TFE) was obtained in all experiments. In the case of surfactant-free polymerizations, the product was mainly constituted by irregular shape macroparticles having size in the range 200–500 μm. Quite interestingly, when…
Monte Carlo methods for polymer chains in two - dimensional geometries (polymers at surfaces and interfaces)
1993
Coarse-grained models of polymers at interfaces can be defined such that their treatment by Monte Carlo simulation is most convenient and efficient for the problem at hand. This simulation strategy is briefly illustrated with three examples: (1) The orientational ordering of rigid rod-like polymers grafted to a surface, where “table methods” can be used, applying a fine discretization of the angles describing rod orientation. (2) Surface enrichment of one species in a polymer blend is treated by a semi-grand-canonical technique. (3) The number of configurations and structure of a star polymer attached with its center to a wall is studied by a “growth technique” generalizing simple sampling …
Sustainable nanocomposites based on halloysite nanotubes and pectin/polyethylene glycol blend
2013
Abstract This study was focused on the preparation and characterization of biofilms based on pectin/polyethylene glycol 20000 (PEG) blend and halloysite nanotubes (HNTs). The obtained blends loaded with a natural nanoclay are proposed as sustainable alternative to the polymers produced from non-renewable resources such as fossil fuels. Properties of technological interest have been monitored and they were correlated to the structural features of the nanocomposites. It turned out that the wettability of the films can be tuned by changing the composition and the distribution of HNTs into the material as well as the surface roughness. The tensile properties of the blend are enhanced by the pre…
Hetero-Multifunctional Poly(ethylene glycol) Copolymers with Multiple Hydroxyl Groups and a Single Terminal Functionality
2009
Hetero-multifunctional poly(ethylene glycol-co-glycerol) random copolymers with multiple hydroxyl functionalities and a single terminal functionality have been prepared by copolymerization of ethylene oxide (EO) and ethoxy ethyl glycidyl ether (EEGE) with the use of a suitable initiator, introducing a protected amino group or a double bond, respectively. Acidic deprotection was used for removal of the acetal protecting groups in the chain, and the terminal amino group was regenerated by catalytic hydrogenation. A series of copolymers with narrow polydispersity was obtained, varying comonomer fractions from 3 to 67% and molecular weights in the range of 5 000-32 000 g · mol(-1) (1.05 < $\ove…
Networks of Partially Hydrogenatedcis-1,4-Polybutadiene and ‘Rigid Rods’
1996
Networks of 'flexible' and 'rigid' chains were synthesized. As 'flexible' component we have used different partially hydrogenated cis-1,4-polybutadiene. The 'rigid' component was synthesized from bis(1,2,4-triazoline-3,5-dione)s and biscyclohexadienes via repetitive Diels-Alder reaction. A slight excess of bis(1,2, 4-triazoline-3,5-dione)s leads to polymers with 1,2,4-triazoline-3,5-dione end groups, which can easily react with the partially hydrogenated cis-1,4-polybutadiene. The influence of the extent of hydrogenation and the amount of crosslinker on the mechanical and thermal behaviour is described.
Synthesis of new polymers via Diels–Alder reaction. III. Biscyclohexadienephthalimides as dienes
1993
Difunctional cyclohexadienes with dihydrophthalimide central unitsand phenyl side groups to increase solubility are used as bisdienes in repetitive Diels-Alder polyadditions with bis(4-(1,2,4,-triazoline-3,5-dione-4-yl)phenyl)methane as a difunctional dienophile. The polymers show good solubility in CH 2 Cl 2 and CHCl 3 . Non-stoichiometric Diels-Alder polyaddition with slight excess of the bistriazolinedione provides the possibility of synthesizing telechelics with highly reactive triazolinedione end groups
Heterotelechelic Ring-Opening Metathesis Polymers
2009
By combining sacrificial synthesis with the vinyl lactone termination technique, heterotelechelic polymers were synthesized. The nonterminating nature of sacrificial synthesis was utilized to introduce a hydroxyl group at the start of the polymer chain. Lactone termination was used to functionalize the chain ends with aldehydes or carboxylic acids. The synthesis of well-defined heterotelechelic polymers was thus accomplished employing the Grubbs’ first generation catalyst as the initiator. The living nature of this polymerization allowed for precise control over the molecular weight and guaranteed full functionalization of both polymer chain ends. The presence of the functional groups is sh…
Synthesis of Heterotelechelic α,ω Dye-Functionalized Polymer by the RAFT Process and Energy Transfer between the End Groups
2009
The synthesis of a vinyl polymer with two different fluorescent dye end groups using reversible addition-fragmentation chain transfer (RAFT) polymerization is described. Use of a pentafluorophenyl (PFP) activated ester chain transfer agent (CTA) provided a polymer with an R end group that was reactive toward amines and a dithioester ω end group. The R PFP ester was amidated with Oregon Green Cadaverin. This did not harm the ω dithioester, which was subsequently aminolyzed with an excess of n-propylamine in the presence of Texas Red-2-sulfonamidoethyl methanethiosulfonate, resulting in a disulfide bond connecting the second dye to the polymer chain. Excess dyes and side products were removed…