Search results for "Reversible addition−fragmentation chain-transfer polymerization"

What Limits the Molecular Weight and Controlled Synthesis of Poly(3-alkyltellurophene)s?

2016

Polytellurophenes are an emerging class of conjugated polymers; however, their controlled polymerization leading to high molecular weight materials has been a major challenge. Here we present a systematic investigation of the synthesis of poly(3-alkyltellurophene)s using the catalyst transfer polycondensation methodology. Learning that previous syntheses were limited by both polymerization reaction kinetics and polymer solubility, we design new tellurophene monomers to overcome these limitations. Controlled polymerization behavior up to Mn = 25 kDa, chain extension, block copolymerization, external initiation, and well-defined end groups are demonstrated for poly(3-alkyltellurophene)s with …

Branched and Functionalized Polybutadienes by a Facile Two-Step Synthesis

2008

Anionic polymerization was used to prepare silane-endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9 000 to 34000 g .mol- 1 . These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB 2 + A type "pseudocopolymerization" method. All branched polymers were analyzed by SEC, SEC-MALLS, SEC-viscosimetry…

Primary radical termination and chain transfer in vinyl polymerization

1974

Cyclodextrins in polymer synthesis: free radical polymerization of cyclodextrin host-guest complexes of methyl methacrylate or styrene from homogenou…

2000

The polymerization of methylated β-cyclodextrin (m-β-CD) 1 : 1 host-guest compounds of methyl methacrylate (MMA) (1) or styrene (2) is described. The polymerization of complexes 1 a and 2 a was carried out in water with potassium peroxodisulfate (K2S2O8)/sodium hydrogensulfite (NaHSO3) as radical redox initiator at 60°C. Unthreading of m-β-CD during the polymerization led to water-insoluble poly(methyl methacrylate) (PMMA) (3) and polystyrene (4). By comparison, analogously prepared polymers from uncomplexed monomers 1 and 2 in ethanol as organic solvent with 2,2′-azoisobutyronitrile (AIBN) as radical initiator showed significantly lower molecular weights and were obtained in lower yields i…

Highly Ordered Nanoporous Thin Films from Photocleavable Block Copolymers

2011

Poly(styrene-block-ethylene oxide) with an o-nitrobenzyl ester photocleavable junction (PS-hν-PEO) was synthesized by a combined RAFT polymerization and “click chemistry“ approach and represents the first report utilizing this method for the synthesis of photocleavable block copolymers. After solvent annealing, highly ordered thin films were prepared from PS-hν-PEO. Following a very mild UV exposure and successive washing with water, PS-hν-PEO thin films were transformed into highly ordered nanoporous thin PS films with pore diameters of 15–20 nm and long range ordering (over 2 μm × 2 μm). Afterwards the pores were filled with PDMS by spin-coating in combination with capillary forces. After…

Macromonomers on the basis of 2-phenyl-2-oxazoline

1988

By initiation of the ring-opening polymerization of 2-phenyl-2-oxazoline (1) with p-iodomethylstyrene a macromonomer with a styrene end-group (2) is obtained. The degree of polymerization was varied between 10 and 16. The radical copolymerization of 2 with styrene is described. 1 forms with methyl triflate a very stable oxazolinium salt which is a good initiator for the bulk polymerization of 1 at temperatures of 50–70°C. It was conclusively proved that under these conditions the polymerization proceeds by a living mechanism. By termination with N, N-dimethylaminopropylmeth-acrylamide a macromonomer (5) was obtained. 5 can be radically homopolymerized. This comb-like polymer 6 has the typic…

Reductive Decationizable Block Copolymers for Stimuli-Responsive mRNA Delivery

2016

Messenger ribonucleic acids (mRNAs) are considered as promising alternatives for transient gene therapy, but to overcome their poor pharmacokinetic properties, smart carriers are required for cellular uptake and stimuli-responsive release. In this work, a synthetic concept toward reductive decationizable cationic block copolymers for mRNA complexation is introduced. By combination of RAFT block copolymerization with postpolymerization modification, cationic block copolymers are generated with disulfide-linked primary amines. They allow effective polyplex formation with negatively charged mRNA and subsequent release under reductive conditions of the cytoplasm. In first in vitro experiments w…

RAFT Polymerization of Pentafluorophenyl Methacrylate: Preparation of Reactive Linear Diblock Copolymers

2005

Reversible addition fragmentation chain transfer (RAFT) polymerization of pentafluorophenyl methacrylate (PFMA) was carried out in the presence of cumyldithiobenzoate and 4-cyano-4-((thiobenzoyl)sulfanyl)pentanoic acid, respectively. These chain transfer agents with 2,2'-azoisobutyronitrile (AIBN) as initiator yielded the active ester polymer poly(PFMA) with M n up to 17000 g . mol -1 and low polydispersity index (M w /M n <1.2). Kinetic analysis using 19 F NMR spectroscopy and gel permeation chromatography (GPC) measurements showed controlled polymerization behavior for both chain transfer agents. Successful preparation of linear diblock copolymers consisting of an active ester block and m…

PAA-PAMPS Copolymers as an Efficient Tool to Control CaCO3 Scale Formation

2013

Scale formation, the deposition of certain minerals such as CaCO3, MgCO3, and CaSO4 center dot 2H(2)O in industrial facilities and household devices, leads to reduced efficiency or severe damage. Therefore, incrustation is a major problem in everyday life. In recent years, double hydrophilic block copolymers (DHBCs) have been the focus of interest in academia with regard to their antiscaling potential. In this work, we synthesized well-defined blocklike PAA-PAMPS copolymers consisting of acrylic acid (AA) and 2-acrylamido-2-methyl-propane sulfonate (AMPS) units in a one-step reaction by RAFT polymerization. The derived copolymers had dispersities of 1.3 and below. The copolymers have then b…

Targeting cells of the immune system: mannosylated HPMA–LMA block-copolymer micelles for targeting of dendritic cells

2016

Background: Successful tumor immunotherapy depends on the induction of strong and sustained tumor antigen-specific immune responses by activated antigen-presenting cells (APCs) such as dendritic cells (DCs). Since nanoparticles have the potential to codeliver tumor-specific antigen and DC-stimulating adjuvant in a DC-targeting manner, we wanted to assess the suitability of mannosylated HPMA-LMA block polymers for immunotherapy. Materials &amp; methods: Fluorescence-labeled block copolymer micelles derived from P(HPMA)-block-P(LMA) copolymers and according statistical copolymers were synthesized via RAFT polymerization, and loaded with the APC activator L18-MDP. Both types of copolymers wer…