Search results for "Addition polymer"
showing 10 items of 114 documents
Graft Copolymers with Complex Polyether Structures: Poly(ethylene oxide)-graft-Poly(isobutyl vinyl ether) by Combination of Living Anionic and Photoi…
2014
Polyether Core-Shell Cylinder-Polymerization of Polyglycidol Macromonomers
2005
The synthesis and polymerization of macromonomers containing a polymerizable styrene head group and a tail of ethylene oxide derivatives of different character were investigated. The synthesis of macromonomers was based on living anionic polymerization of oxiranes. Two monomers were used: 1-ethoxyethyl glycidyl ether (glycidol acetal), which after hydrolysis forms hydrophilic glycidol blocks and glycidyl phenyl ether forming hydrophobic blocks. Polymerizable double bonds were introduced by terminating the living chain with p-(chloromethyl)styrene. The radical polymerization of the macromonomers was carried out in water with addition of a non-polar solvent (benzene) and AIBN as initiator. Co…
Group transfer and anionic polymerization: A critical comparison
1990
The mechanism of group transfer polymerization (GTP) of methacrylates in THF is investigated by using data on kinetics of homo- and copolymerization, polymer microstructure and molecular weight distribution. By comparison with corresponding data on anionic polymerization it is concluded that the mechanisms of monomer addition to the active chain end is very similar for both anionic and group transfer polymerization and that GTP is ionic in character. On the other hand, GTP uniquely is characterized by the existence of a catalyst exchange equilibrium. The position of this equilibrium determines the rates of polymerization, and the dynamics determine the molecular weight distribution.
PEG-based Multifunctional Polyethers with Highly Reactive Vinyl-Ether Side Chains for Click-Type Functionalization
2011
Introduction of highly reactive vinyl ether moieties along a poly(ethylene-glycol) (PEG) backbone has been realized by copolymerization of the novel epoxide monomer ethoxy vinyl glycidyl ether (EVGE) with ethylene oxide (EO). A series of copolymers with varying structure (block and random) as well as EVGE comonomer content (5-100%) with molecular weights in the range of 3,900-13,200 g/mol and narrow molecular weight distributions (M-w/M-n = 1.06-1.20) has been synthesized and characterized with respect to their microstructure and thermal properties. The facile transformation of the vinyl ether side chains in click type reactions was verified by two different post polymerization modification…
Amphiphilic Linear-Hyperbranched Block Copolymers with Linear Poly(ethylene oxide) and Hyperbranched Poly(carbosilane) Block
2008
The synthesis of amphiphilic linear-hyperbranched block copolymers with a linear poly(ethylene oxide) (PEO) segment and a hyperbranched poly(carbosilane)s (PCS) block in a rapid three-step strategy is described, combining oxyanionic polymerization with carbosilane chemistry. A linear precursor block copolymer was synthesized via anionic polymerization of allyl glycidyl ether onto a commercial hydroxyl-terminated PEO, using its cesium alkoxide as macro-initiator. The resulting linear AB or ABA-type di- or triblock copolymers serve as polymer cores for the subsequent hydrosilylation polyaddition of an AB2-type carbosilane monomer. Di(allyl)methylsilane or methyldi(undec-10-enylsilane) were em…
Synthesis and properties of amphiphilic “dumbbell”-shaped grafted block copolymers, 1. Anionic synthesis via a polyfunctional initiator
1994
Two poly(ethylene oxide) stars linked by a long polystyrene chain represent a novel amphiphilic architecture (dumbbell), which is available by anionic grafting of ethylene oxide from a hydroxylated polybutadiene-block-polystyrene-block-polybutadiene triblock copolymer. The short butadiene end-blocks (DPB = 36) of a BSB triblock copolymer with a long styrene middle block (DPS = 650) was first modified by hydroboration and oxidation. A multifunctional alkoxide initiator is thus prepared by titration of the hydroxyl groups of the “polybutadiene” end-block with cumylpotassium. Gelation and precipitation of the polyfunctional initiator in THF could be avoided by complexing the cation (K+) with a…
Synthesis of SBC, SC and BC block copolymers based on polystyrene (S), polybutadiene (B) and a crystallizable poly(ɛ-caprolactone) (C) block
1996
The sequential anionic polymerization of polystyrene-block-polybutadiene-block-poly(e-caprolactone) (SBC) triblock copolymers as well as polystyrene-block-poly(e-caprolactone) (SC) and polybutadiene-block-poly(e-caprolactone) (BC) diblock copolymers was achieved in benzene. To initiate the polymerization of the highly reactive e-caprolactone, the nucleophilicity of the carbanion has to be reduced. For this purpose 1,1-diphenylethylene (DPE) was used. To avoid inter- and intramolecular transesterification reactions of the growing caprolactone block, the reaction time of this monomer in the block copolymers was strictly controlled. The reaction between polybutadienyl anions and DPE is too slo…
Synthesis and Characterization of Poly(glyceryl glycerol) Block Copolymers
2008
On the anionic polymerization of dialkylaminoisoprenes, 3. A nuclear magnetic resonance study of the structure of oligo[5-(N,N-diisopropylamino)isopr…
1995
The structure of oligo[(5-N,N-diisopropylamino)isoprenyllithium] (number-average degree of polymerization Pn = 1-2) prepared by reaction of alkyllithium with 5-(N,N-diisopropylamino)-isoprene1 in nonpolar (benzene) and polar (tetrahydrofuran) solvents has been studied by 1H and 13C NMR spectroscopy. In tetrahydrofuran, as expected, the negative charge at the terminal chain unit is more delocalized than in benzene and, consequently, the carbon-lithium bond has a more ionic character. In both solvents the living chain end shows a cisoid-4, 1-structure. No cistrans isomerization could be detected. This independence of the carbanion structure of the solvent polarity is explained by the complexa…
Mechanism of anionic polymerization of (meth)acrylates in the presence of aluminium alkyls, 2. Kinetic investigations with methyl methacrylate in tol…
1995
The kinetics of the polymerization of methyl methacrylate initiated by lithium alkyls (tert-butyllithium or ethyl α-lithiobutyrate) was investigated in the presence of aluminium alkyls (triethylaluminium or triisobutylaluminium) in toluene at −78°C. The rate of polymerization decreases considerably once the living dimer is formed. This suggests that the aluminate end-group coordinates with the penultimate ester group of the polymer chain, thus decreasing reactivity. The results are at variance with an activated monomer mechanism.