Search results for "Polymerization"
showing 10 items of 1689 documents
Mechanism of anionic polymerization of methyl methacrylate in the presence of aluminium alkyls
1995
Methyl methacrylate was polymerized with tert-butyl lithium in the presence of triethylaluminium or triisobutylaluminium at 78°C in toluene. As indicated by GPC and MALDI-TOF mass spectrometry, the polymerization is accompanied by side reactions. The lower oligomers were fractionated by distillation and characterised by NMR, FT-IR, UV and electron impact (EI) mass spectrometry. All these data show that part of the polymer chains are carrying exactly one tert-butyl isoprenyl ketone unit. In order to avoid the formation of tert-butyl isoprenyl ketone a molar ratio of Al/Li>2 is necessary.
An Easy Way Towardɛ-Caprolactone Macromonomers by Microwave Irradiation Using Early Lanthanide Halides as Catalysts
2002
Poly(e-caprolactone) macromonomers were synthesized under microwave irradiation from commercial caprolactone, using commercial hydrated lanthanide halides as catalysts. The molecular weight of the polymers was in the range 3 000–5 000. Higher molecular weights (5 000–20 000) and lower polydispersity indices were obtained with THF adducts of the lanthanide halides as catalysts and also by applying longer reaction times or using diethylene glycol as a coupling reagent.
The first structurally characterized cationic lanthanide–alkyl complexesElectronic supplementary information (ESI) available: experimental and spectr…
2002
Reaction of rare earth metal–alkyl complexes [Ln(CH2SiMe3)3(THF)2] (Ln = Y, Lu) with B(C6X5)3 (X = H, F) in the presence of crown ethers gives crystallographically characterized ion pairs [Ln(CH2SiMe3)2(CE)(THF)n]+[B(CH2SiMe3)(C6X5)3]– (CE = [12]-crown-4, n = 1; CE = [15]-crown-5 and [18]-crown-6, n = 0).
Rare Earth Half-Sandwich Catalysts for the Homo- and Copolymerization of Ethylene and Styrene
2001
The synthesis of rare earth metal half-sandwich hydrido complexes [Ln(η5:η1-C5Me4SiMe2NCMe3)(THF)(μ-H)]2(Ln = Y, Lu, Yb, Er, Tb) through σ-bond metathesis of the alkyl complexes [Ln(η5:η1- C5Me4SiMe2NCMe3)(CH2SiMe3)(THF)], easily accessible by the reaction of the amino-cyclopentadiene with [Ln(CH2SiMe3)3(THF)2], was developed. The dimeric lanthanide hydrido complexes are highly fluxional involving THF dissociation and cis-trans isomerization of the linked amidocyclopentadienyl ligand. The presence of a monomer-dimer equilibrium is suggested by cross-over experiments. They were tested as single-site, single-component catalysts for the polymerization of ethylene, α-olefin, and styrene, as wel…
NHC-Stabilized Gold(I) Complexes: Suitable Catalysts for 6-exo-dig Heterocyclization of 1-(o-Ethynylaryl)ureas
2010
3-Substituted 1-(o-ethynylaryl)ureas 1 selectively undergo either 6-exo-dig or 5-endo-dig cyclization (to give 4-methylene-3,4-quinazolin-2-ones 2 or indoles 3, respectively) depending on the choice of the metal, ligand, and reaction conditions. The best results (up to 96% yield) in the preparation of the hydroamination products 2 are achieved with the highly bulky NHC-stabilized cationic gold(I) complex [Au(IPr)](+). Conversely, ureas bearing an internal alkyne lead to the 5-endo-dig cyclization mode regardless of the gold(I) complex employed. Whereas the nature of the substituent at N-3 does not have any influence on the regiochemistry observed, it does, in some cases, affect the efficien…
Chemical recycling of polyenaminones by transamination reaction via amino–enaminone polymerisation/depolymerisation
2019
Abstract Novel oligo- and polyenaminones with Mw ∼ 3000 Da were prepared in excellent yields by amino–enaminone ‘click’ polymerisation of 1,3- and 1,4-bis[3-(dimethylamino)acryloyl]arenes with 1,3- and 1,4-phenylenediamine. The obtained oligomers and polymers were depolymerised quantitatively to the starting bis-enaminones and diamines by treatment with excess dimethylamine in ethanol at 50 °C. This simple polymerisation/depolymerisation method allows for a closed-loop recycling of polyenaminone-based materials. UV light absorbance at wavelengths below 470 nm indicates promising optical properties of these polymers.
Lauroyl peroxide as thermal initiator of lauryl methacrylate monolithic columns for CEC
2008
The preparation of lauryl methacrylate (LMA)-based monolithic columns for CEC using lauroyl peroxide (LPO) as thermal initiator of polymerization has been investigated. The influence of initiator amount and composition of porogenic solvent on the physical and electrochromatographic properties of the resulting LMA-based monoliths was evaluated. A comparison with LMA-based columns thermally polymerized with AIBN was performed. At a given porogenic solvent composition, LMA stationary phases initiated with LPO showed higher permeabilities and better efficiency values than those prepared using AIBN as initiator. The optimum polymerization mixture found for LPO initiator provided a minimum plate …
Polymeric monolayers and liposomes as models for biomembranes. How to bridge the gap between polymer science and membrane biology?
1984
This contribution deals with the stabilization of membrane model systems, especially vesicles. The desired further biological functionalization of these stabilized polymeric membranes is possible via the incorporation of proteins. Addition of natural lipids to polymerizable membranes and degradation of the unpolymerized component after polymerization allows selective opening of otherwise stable compartments. Finally, first attempts are made to combine biological properties of natural cells and the durability of polymerized membranes via fusion of synthetic vesicles with natural cells.
A Deeper Insight into the Postpolymerization Modification of Polypenta Fluorophenyl Methacrylates to Poly(N -(2-Hydroxypropyl) Methacrylamide)
2014
This work provides a detailed insight into the synthesis of N-(2-hydroxypropyl)methacrylamide (HPMA) polymers employing the activated ester approach. In this approach, polypenta fluorophenyl methacrylate (PFPMA)-activated ester polymers are synthesized by the reversible addition-fragmentation chain transfer (RAFT) polymerization and transferred into HPMA-based systems by the use of 2-hydroxypropylamine. To prove quantitative conversion in the absence of side reactions, special attention is devoted to investigate different reaction conditions by different analytical methods ((1) H, (19) F, inverse-gated (13) C NMR, and zeta potential measurements). Furthermore the influence of common solvent…
Degradable cationic nanohydrogel particles for stimuli-responsive release of siRNA.
2014
Well-defined nanogels have become quite attractive as safe and stable carriers for siRNA delivery. However, to avoid nanoparticle accumulation, they need to provide a stimuli-responsive degradation mechanism that can be activated at the payload's site of action. In this work, the synthetic concept for generating well-defined nanohydrogel particles is extended to incorporate disulfide cross-linkers into a cationic nanonetwork for redox-triggered release of oligonucleotide payload as well as nanoparticle degradation under reductive conditions of the cytoplasm. Therefore, a novel disulfide-modified spermine cross-linker is designed that both allows disassembly of the nanogel as well as removal…