Novel polymers based on atom transfer radical polymerization of 2-methoxyethyl acrylate (original) (raw)
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European Polymer Journal, 2003
The synthesis of tert-butyl acrylate by atom transfer radical polymerization (ATRP) is reported. This polymer was prepared using FeCl 2 AE 4H 2 O(PPh 3 ) 2 catalyst system in conjunction with methyl 2-bromopropionate as initiator, in bulk and in solution using acetone as a solvent. The addition of solvent was necessary in order to decrease the polymerization rate and to afford low polydispersity polymers. The number-average molecular weights of the resulting polymers increased in direct proportion to the monomer conversion, and the polydispersities (M w =M n ) were as low as 1.2. In addition, the preparation of an AB diblock copolymer of poly (n-butyl methacrylate)-block-poly (tert-butyl acrylate) by ATRP is reported. The resulting polymers and copolymers were characterized by means of size exclusion chromatography and 1 H-NMR Spectroscopy.
European Polymer Journal, 2003
Homopolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) by atom transfer radical polymerization (ATRP) were carried out at 90°C using methyl-2-bromopropionate (MBP) as initiator, copper halide (CuX, X ¼ Cl, Br) as catalyst, 2,2 0-bipyridine (bpy) or N,N,N 0 ,N 0 ,N 00-pentamethyldiethylenetriamine (PMDETA) as ligand in 1-butanol (less polar and containing OH) and acetonitrile (more polar) solvents. It was found that with CuCl/bpy catalyst ATRP of MA and MMA in 1-butanol proceeded faster than that in acetonitrile. The rate of ATRP of MA and MMA in acetonitrile and 1-butanol was comparable when CuCl/PMDETA used as catalyst system. The numberaverage molecular weights ðM n Þ increased with conversion and polydispersities were low ðM w =M n < 1:5Þ. The ATRP of MA and MMA with vinyl acetate telomer having trichloromethyl end group (PVAc-CCl 3) were also used to synthesize new block copolymers. The structures and molecular weight of synthesized PVAc-b-PMA and PVAc-b-PMMA were characterized by 1 H NMR, FTIR spectroscopy and gel permeation chromatography (GPC) and shown that the block copolymers were novel.
Journal of Polymer Science Part A: Polymer Chemistry, 2005
The syntheses of triblock copolymers by the atom transfer radical polymerization of tert-butyl and iso-butyl acrylates as inner blocks with cyclohexyl methacrylate as outer blocks are reported. The living behavior and blocking efficiency of these polymerizations were investigated in each case. The use of difunctional macroinitiators led to ABA triblock copolymers with narrow polydispersities and controlled number-average molecular weights. These copolymers were prepared from bromo-terminated macroinitiators of poly(tert-butyl acrylate) and poly(iso-butyl acrylate), with copper chloride/N,N,N 0 ,N@,N@-pentamethyldiethylenetriamine as the catalytic system, at 40 8C in 50% (v/v) toluene solutions. The block copolymers were characterized with size exclusion chromatography and 1 H NMR spectroscopy. Differential scanning calorimetry measurements were performed to reveal the phase segregation. The glass transition of the inner block was not clearly detected, with the exception of the copolymer synthesized with the longest poly(iso-butyl acrylate) macroinitiator length.
Polymer, 2001
The synthesis of diblock copolymers using atom transfer radical polymerization (ATRP), of methyl methacrylate (MMA), and butyl acrylate (BA), is reported. These copolymers were prepared from bromo-terminated macroinitiators of poly(MMA) and poly(BA), using copper chloride, CuCl,/N,N,N H ,N HH ,N HH -pentamethyldiethylenetriamine (PMDETA), as catalyst system, at 1008C in bulk and in benzonitrile solution. The block copolymers were characterized by means of size exclusion chromatography (SEC), and 1 H-NMR spectroscopy. The SEC analysis of the synthesized diblock copolymers con®rmed the importance of solvent on the molecular weight control. In addition, differential scanning calorimetry (DSC), measurements were performed, showing for all the copolymers a phase separation. q
Synthesis of poly(isobornyl acrylate) containing copolymers by atom transfer radical polymerization
Journal of Polymer Science Part A: Polymer Chemistry, 2008
For the first time, a detailed study of the atom transfer radical polymerization of isobornyl acrylate (iBA) is reported. On the basis of these results, well-defined PiBA-containing block copolymers were synthesized, focussing on the preparation of amphiphilic poly(acrylic acid) (PAA) containing block copolymers. The precursor monomers 1-ethoxyethyl acrylate (EEA) as well as tert-butyl acrylate have been used to synthesize the PAA-segments of the PiBA-b-PAA block copolymers. Finally, the synthesis of ''block-like'' copolymers of PiBA and PEEA via a one-pot procedure was investigated. By optimizing the copper and ligand concentration, and choosing the appropriate solvent, a controlled polymerization behaviour was obtained in all cases, as evidenced by a detailed kinetic analysis, GPC, NMR, and MALDI-TOF data. Thermogravimetric analysis confirmed the quantitative transformation of the precursor polymer PEEA to the corresponding PAA-containing copolymers. V
Journal of Polymer Science Part A-polymer Chemistry, 2000
The synthesis of di-and triblock copolymers using atom transfer radical polymerization (ATRP) of n-butyl acrylate (BA) and methyl methacrylate (MMA) is reported. In particular, synthetic procedures that allow for an easy and convenient synthesis of such block copolymers were developed by using CuBr and CuCl salts complexed with linear amines. Polymerizations were successfully conducted where the monomers were added to the reactor in a sequential manner. Poor cross-propagation between poly(n-butyl acrylate) (PBA) macroinitiators and MMA was minimized, and therefore control of molecular weights and distributions was realized, by using halogen exchange-a technique involving the addition of CuCl to the MMA during the chain extension of the PBA macroinitiator. High molecular weight (M n ϳ 90,000) and low polydispersity (M w /M n Ͻ 1.35) ABA triblock copolymers were also prepared and their structure and properties in bulk have been preliminary characterized indicating the potential of ATRP for the production of all-acrylic thermoplastic elastomers.
Atom-Transfer Radical Polymerization of a Reactive Monomer: 3-(Trimethoxysilyl)propyl Methacrylate
Macromolecules, 2004
Atom-transfer radical polymerizations (ATRPs) of a reactive monomer, 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), mediated by CuBr/N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PM-DETA) in anisole have been studied using ethyl 2-bromoisobutyrate (2-EBiB) and poly(ethylene oxide) methyl ether 2-bromoisobutyrate (PEO-Br) as initiators. In general, the polymerizations of TMSPMA exhibited first-order kinetics, and molecular weights increased linearly with monomer conversion. Molecular weight distributions remained low throughout the polymerizations (M w/Mn ) 1.20-1.40). The overall rate of polymerization with PEO-Br as the initiator was enhanced compared to that with 2-EBiB as the initiator. A series of reactive diblock copolymers, poly(ethylene oxide)-b-poly[3-(trimethoxysilyl)propyl methacrylate] (PEO-b-PTMSPMA), were thus synthesized. By random copolymerization with methyl methacrylate (MMA), PEO-b-P(TMSPMA-r-MMA) copolymer was prepared at the same time. Organic/inorganic hybrid nanospheres were produced by the self-assembly of PEO-b-P(TMSPMA-r-MMA) in a selective solvent and further gelation of the trimethoxylsilyl groups within each individual sphere. Preparation of organic/inorganic nanocomposites was also explored preliminarily on the basis of the solgel process of PEO-b-PTMSPMA diblock copolymers and the tetraethyl orthosilicate.
Macromolecular Rapid Communications, 1999
Poly(oxyethylene)s terminated at both ends with 2-bromopropionate end-groups were prepared and characterized by means of MALDI TOF mass spectrometry. It was shown, that atom transfer radical polymerization (ATRP) of methyl methacrylate with a poly(oxyethylene) macroinitiator in bulk proceeds with low initiation efficiency while polymerization of tert-butyl acrylate proceeds with practically quantitative initiation, leading to ABA block copolymers. Originally formed tert-butyl acrylate blocks contain terminal bromine, as expected for the ATRP mechanism. MALDI TOF analysis indicates, however, that in the later stages of polymerization side reactions lead to elimination of terminal bromine.