Search results for "PLASTICS"
showing 10 items of 2724 documents
Biphasic ethylene polymerisation using 1-n-alkyl-3-methylimidazolium tetrachloroaluminate ionic liquid as a medium of the Cp2TiCl2 titanocene catalyst
2008
Abstract A systematic analysis was performed on a series of 1- n -alkyl-3-methylimidazolium tetrachloroaluminates (where alkyl = ethyl, butyl, hexyl, and octyl), applied as a medium of the Cp 2 TiCl 2 titanocene catalyst, to evaluate the influence of the physical properties of the ionic liquids on the polymerisation reaction carried out in the biphasic ionic liquid/hexane mode. Two alkylaluminium compounds, AlEtCl 2 and AlEt 2 Cl, were used as activators. The influence of the activator/catalyst molar ratio on the performance of the ethylene polymerisation was determined for each ionic liquid studied. The best results were obtained using 1- n -octyl-3-methylimidazolium tetrachloroaluminate. …
One-step synthesis of multi-alkyne functional hyperbranched polyglycerols by copolymerization of glycidyl propargyl ether and glycidol
2013
By copolymerization of glycidol with the alkyne-containing oxirane monomer glycidyl propargyl ether (GPE), hyperbranched polyglycerol (hbPG) with a defined number of alkyne functionalities (up to 38%) can be obtained in a one-step procedure. The number of alkynes can be adjusted by the glycidol/GPE ratio to provide multi-alkyne functional hbPGs, maintaining the highly branched polyether structure. Interestingly, the acidic proton of the alkyne moiety does not interfere with the proton exchange mechanism during the polymerization of glycidol. By specific modification of the synthesis procedure, crosslinking reactions can be suppressed. The polymers exhibit molecular weights ranging from 1800…
Linear-Hyperbranched Graft-Copolymers via Grafting-to Strategy Based on Hyperbranched Dendron Analogues and Reactive Ester Polymers
2012
The synthesis of hyperbranched polyglycerol dendron analogues with precisely one focal amino functionality (H2N-hbPG) and their use for the synthesis of linear-hyperbranched graft-copolymers in a grafting-to approach is reported. By use of N,N-dibenzyl tris(hydroxylmethyl) aminomethane as a novel initiator for the ring-opening multibranching polymerization of glycidol, dendron analogues with one focal amino functionality of molecular weights ranging from 500 to 15000 g mol–1 and narrow to moderate polydispersities (Mw/Mn = 1.2–1.9) were synthesized, as confirmed by NMR and SEC. After removal of the benzyl protective groups, the accessibility and selective transformation of the focal amino g…
Molecular parameters of hyperbranched polymers made by self-condensing vinyl polymerization of macroinimers
2000
The molecular weight averages and the degree of branching, DB, of a hyperbranched polymer obtained by self-condensing vinyl polymerization (SCVP) of a macroinimer A-(m)γ-B* is calculated by modifying the existing equations for SCVP. The polydispersity is lowered by a factor (γ + 1), where γ is the degree of polymerization of the macroinimer. DB decreases with γ, however, at full conversion the DB of the polymacroinimer is approximately 60% higher than expected from the “dilution” of an AB* inimer with linear m units. This is the result of the existence of a new kind of branched units. The structure of polymacroinimers is similar to the pattern of a highly branched copolymer obtained by self…
Metal-free anionic polymerization of methyl methacrylate in tetrahydrofuran using bis(triphenylphosphoranilydene)ammonium (PNP+) as counterion
2000
Bis(triphenylphosphoranilydene)ammonium (PNP + ) triphenylmethanide (Ph 3 C - ) is a new metal-free initiator for the living polymerization of methyl methacrylate (MMA). The kinetics of the polymerization strongly depend on the metal counterion the initiator precursor. When the initiator is made from the metathesis reaction of Ph 3 CK and PNPCl, the polymerization follows first-order kinetics up to 0°C with half-lives below 0.1 s. The propagation rate constants are much higher than those obtained with tetraphenylphosphonium (TPP + ) cations, indicating a smaller fraction of dormant ylides. When the initiator is synthesized from Ph 3 CLi, polymerization proceeds much slower and molecular wei…
Kinetics of Complex Formation between DNA and Cationically Charged Cylindrical Brush Polymers Observed by Stopped Flow Light Scattering
2009
The complex formation of pUC19 DNA and a cylindrical brush polymer with quaternized poly(vinyl pyridinium) side chains is investigated by stopped flow light scattering (LS). In highly dilute solutions up to two kinetic processes are observable, depending on the mole fraction of anionic charges, x(anion) . For x(anion) 0.4-0.5 only one kinetic process was identified leading to the largest complexes at x(anion) = 0.4 well below charge stoichiometry. For 0.2 < x(anion) < 0.4 two kinetic growth processes were identified: The initially formed complexes on the time scale of a few hundred milliseconds keep growing by an unusual fractal growth process until after several minutes they become stab…
Pencil Lead as a Matrix for MALDI-ToF Mass Spectrometry of Sensitive Functional Polymers
2007
With the increase in complexity of functional polymers in recent years, MALDI-ToF has become an important tool for gaining precise information on polymer functionality, end groups, and, in special cases, molecular weights. Here we describe how pencil lead, deposited by simply drawing with a regular pencil onto conventional MALDI-ToF targets, can be used as a very attractive matrix for MALDI-ToF mass spectrometry of synthetic polymers. Highly sensitive polymers such as silyl hydride functional poly(styrene), poly(butadiene), and poly(isoprene) have been investigated using conventional MALDI-ToF matrices as well as pencil lead. In all cases, the use of pencil lead prevented oxidation of the h…
Monomer Sequence Distribution Monitoring in Living Carbanionic Copolymerization by Real-Time 1H NMR Spectroscopy
2013
Detailed understanding of the monomer sequence distribution in carbanionic copolymerization was achieved by direct online monitoring of copolymerizations in an NMR tube. Obtaining detailed knowledge of the changing monomer concentration in stock during the reaction, this technique permits to determine the incorporation probability for each monomer at every position of the polymer chain. An in situ kinetic study of two different carbanionic copolymerizations has been carried out. On the one hand, the copolymerization of the structurally similar, protected hydroxystyrene derivatives, p-(1-ethoxy ethoxy)styrene (pEES) and 4-tert-butoxystyrene (tBuOS), and on the other hand the copolymerization…
Hetero-Telechelic Dye-Labeled Polymer for Nanoparticle Decoration
2009
The synthesis of poly(methyl methacrylate) (PMMA) exhibiting one fluorescent dye (Texas Red) and one methyl disulfide end group is described. It is shown that the latter end group enabled the exchange of both oleic amine on gold nanoparticles (AuNP) and of oleic acid on CdSe/ZnS quantum dots (QD), allowing for a phase transfer of both types of nanoparticles (NP) from hexane into dimethylformamide due to the solubility provided by the PMMA chains. For AuNP, a fluorescence quenching of the dye was found due to fluorescence resonance energy transfer (FRET) from the dye to the AuNP, while QDs caused a fluorescence enhancement by FRET from the QD to the attached dyes. Due to the hetero-telecheli…
Synthesis and characterization of poly(phenylacetylenes) featuring activated ester side groups
2010
Four monomers based on 4-ethynylbenzoic acid have been synthesized, one of those featuring an activated ester. With the metathesis catalytic system WCI 6 /Ph 4 Sn, these acetylenic monomers could successfully be polymerized yielding conjugated polymers with molecular weights of around 10,000 to 15,000 g/mol and molecular weight distributions M w / M n < 2.1. Also the copolymerization of phenylacetylene or methyl 4-ethynylbenzoate with pentafluorophenyl 4-ethynyl-benzoate as reactive unit was conducted. Polymer analogous reactions of the reactive polymers and copolymers with amines have been investigated and it was found that poly(pentafluorophenyl 4-ethynylbenzoate) featured a significant r…