Search results for "Reversible"
showing 10 items of 140 documents
Synthesis of well-defined polymeric activated esters
2008
Monomers bearing an activated ester group can be polymerized under various controlled polymerization techniques, such as ATRP, NMP, RAFT polymerization, or ROMP. Combining the functionalization of polymers via polymeric activated esters with these controlled polymerization techniques generate possibilities to realize highly functionalized polymer architectures. Within this highlight two different research areas of activated esters in polymer science will be discussed: (i) the preparation of defined reactive polymer architectures by controlled polymerization techniques and (ii) the preparation of defined reactive thin films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6…
Synthesis of Functional Inorganic−Organic Hybrid Polymers Based on Poly(silsesquioxanes) and Their Thin Film Properties
2008
New stable and adherent coating materials have been synthesized on the basis of inorganic/organic hybrid polymers. As the inorganic part, different poly(silsesquioxanes) (PSSQ) have been functionalized to act as polymeric chain transfer agents (CTAs) for a reversible addition fragmentation chain transfer polymerization, thereby determining the starting point of a controlled radical polymerization of vinyl-type monomers. Using two different CTAs acrylates, we have successfully polymerized methacrylates and styrene under RAFT polymerization conditions. Different monomers were copolymerized in such an organic block to incorporate multiple functionalities. The variation of the block ratios and …
Well-defined carbohydrate-based polymers in calcium carbonate crystallization: Influence of stereochemistry in the polymer side chain on polymorphism…
2015
Abstract In this work we demonstrate the remarkable phase control on the crystallization of calcium carbonate by the stereochemistry of carbohydrate-based polymers. The polymers (poly(2-(2,3,4,6-tetra-O-acetyl-β- d -glucosyloxy)ethyl methacrylate) and poly(2-(2,3,4,6-tetra-O-acetyl-β- d -galactosyloxy)ethyl methacrylate)) have been synthesized from the respective glucose or galactose containing monomers (3 step synthesis) by RAFT polymerization leading to well-defined carbohydrate-based polymers with number averages of the molecular weights (Mw) of 10,000–18,000 g/mol and a dispersities (Đ) from 1.1 to 1.2. For the deprotected polymers we found differences in the phase selection of calcium …
Synthesis, Characterization and Preliminary Biological Evaluation of P(HPMA)-b-P(LLA) Copolymers: A New Type of Functional Biocompatible Block Copoly…
2010
We describe a synthetic pathway to functional P(HPMA)-b-P(LLA) block copolymers. The synthesis relies on a combination of ring-opening polymerization of L-lactide, conversion into a chain transfer agent (CTA) for the RAFT polymerization of pentafluorophenyl methacrylate. A series of block copolymers was prepared that exhibited molecular weights $\overline M _{\rm n}$ ranging from 7 600 to 34 300 g · mol(-1) , with moderate PDI between 1.3 and 1.45. These reactive precursor polymers have been transformed into biocompatible P(HPMA)-b-P(LLA) copolymers and their fluorescently labeled derivatives by facile replacement of the pentafluorophenyl groups. The fluorescence label attached to this new …
Nonlinear Macromolecules by Ring-Opening Polymerization
2012
Ring-opening polymerization (ROP) is a well-established method for the controlled synthesis of linear polymers, which can be found in various everyday applications. However, during the past decades, there has been an increasing interest in the generation of nonlinear highly branched polymers, profiting from the fascination created by the structurally perfect dendrimers. The applicability of various heterocyclic monomers renders the ring-opening multibranching polymerization (ROMBP), a versatile tool for the generation of multifunctional hyperbranched polymers. First, the historical key steps leading to the development of ROMBP are described, which is the basis for the controlled synthesis o…
The uptake of N-(2-hydroxypropyl)-methacrylamide based homo, random and block copolymers by human multi-drug resistant breast adenocarcinoma cells
2009
A series of well-defined, fluorescently labelled homopolymers, random and block copolymers based on N-(2-hydroxypropyl)-methacrylamide were prepared by reversible addition–fragmentation chain transfer polymerization (RAFT polymerization). The polydispersity indexes for all polymers were in the range of 1.2–1.3 and the number average of the molar mass (Mn) for each polymer was set to be in the range of 15–30 kDa. The cellular uptake of these polymers was investigated in the human multi-drug resistant breast adenocarcinoma cell line MCF7/ADR. The uptake greatly depended on the polymer molecular mass and structure. Specifically, smaller polymers (approx. 15 kDa) were taken up by the cells at m…
Poly-l-Lysine-Poly[HPMA] Block Copolymers Obtained by RAFT Polymerization as Polyplex-Transfection Reagents with Minimal Toxicity
2015
Herein we describe the synthesis of poly-L-lysine-b-poly[N-(2-hydroxypropyl)-metha-crylamide)] (poly[HPMA]) block copolymers by combination of solid phase peptide synthesis or polymerization of α-amino acid-N-carboxy-anhydrides (NCA-polymerization) with the reversible addition-fragmentation chain transfer polymerization (RAFT). In the presence of p-DNA, these polymers form polyplex micelles with a size of 100-200 nm in diameter (monitored by SDS-PAGE and FCS). Primary in vitro studies with HEK-293T cells reveal their cellular uptake (FACS studies and CLSM) and proof successful transfection with efficiencies depending on the length of polylysine. Moreover, these polyplexes display minimal to…
Comparison of living polymerization systems
1994
Recent developments in the field of living polymerization are surveyed. Comparison of the available mechanistic and kinetic information is made for living anionic, cationic, free radical, group transfer, ring-opening metathesis, Ziegler-Natta and immortal polymerizations. This evaluation indicates that the majority of living polymerizations involve quasiliving equilibrium between active (propagating) and dormant (nonpropagating) polymer chains. On the basis of the kinetics of a general model for quasiliving and ideal living polymerizations it is concluded that ideal living polymerization is a special subclass of quasiliving polymerizations. Classification of living polymerization systems is…
RAFT-polymerized poly(hexafluoroisopropyl methacrylate)s as precursors for functional water-soluble polymers
2014
Post-polymerization modification of well-defined precursor polymers is a versatile tool to obtain multifunctional water-soluble polymers that cannot be synthesized by common polymerization techniques. For the first time, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA) based homo and block copolymers were synthesized via RAFT polymerization to provide precise precursors for the post-polymerization modification of the 1,1,1,3,3,3-hexafluoroisopropyl ester side chains with water-soluble amines (methoxy tri(ethylene glycol) amine, 2-hydroxypropyl amine and 3-(dimethylamino)-1-propylamine). Sequential aminolysis using Oregon Green cadaverine first followed by 2-hydroxypropyl amine enables …
RAFT polymerization of activated 4-vinylbenzoates
2009
The reversible addition fragmentation chain transfer (RAFT) polymerization of five active ester monomers based on 4-vinylbenzoic acid had been investigated. Pentafluorophenyl 4-vinylbenzoate could be polymerized under RAFT conditions yielding polymers with very good control over molecular weight and narrow molecular weight distributions. Following the synthesis of diblock copolymers consisting of polystyrene, polypentafluorostyrene, poly(4-octylstyrene), or poly(4-acetoxystyrene) as an inert block and poly(pentafluorophenyl 4-vinylbenzoate) as a reactive block was successfully performed. The diblock copolymer poly(pentafluoro styrene)-block-poly(pentafluorophenyl 4-vinylbenzoate) had been a…