p-Methoxystyrene (MOS), butyl vinyl ether (BVE), and N-vinylcarbazole (VCZ) were polymerized in high yield by azoinitiators such as 2, 2'-azodiisobutyronitrile (AIBN) in the presence of electron acceptors such as Ph2I+PF6−. An electron paramagnetic resonance (ESR) study of the model radicals of the propagating radical showed the transformation of the radical to the corresponding cation in the presence of the electron acceptors. In the case of BVE, the polymer formation was caused by cationic species produced by the transformation of the initiating radical. The polymerizations of MOS and VCZ were ascribed to the transformation of the growing radical to the corresponding cation during the propagation step which was classified as the radical/cation transformation polymerization. Block copolymers of MOS/cyclohexene oxide (1, 2-epoxycyclohexane) (CHO) and VCZ/CHO were effectively prepared by the radical/cation transformation polymerization of the appropriate monomers in the presence of AIBN, electron acceptor and CHO. The formation of block copolymers was characterized by turbidimetry, thin-layer chromatography, and solubility tests. 相似文献
Abstract ESR study on the primary radicals obtained by decomposition of azo-compounds showed that primary radicals with electron donating substituents were transformed to the corresponding cations in the presence of electron acceptors such as ph2I+PF?6. Accordingly, propagating radicals are transformed to the corresponding cations in the polymerization of p-methoxy-styrene (MOS), n-butyl vinyl ether (BVE), and N-vinylcarbazole (VCZ) with azoinitiators such as AIBN in the presence of electron acceptors such as Ph2I+PF?6. In the case of BVE, the polymer formation was caused by cationic species produced by the transformation of the initiating radical. The polymerizations of MOS and VCZ were ascribed to the transformation of the growing radical to the corresponding cation during the propagation step which was classified as the radical/cation transformation polymerization. Block copolymers of MOS/cyclohexene oxide (CHO) and VCZ/CHO were effectively prepared by the radical/cation transformation polymerization of the appropriate monomers in the presence of AIBN, electron acceptor and CHO. The formation of block copolymers was characterized by turbidimetry, thin-layer chromatography, and solubility tests. 相似文献
Polymerizations of methyl acrylate (MA) and (DL)-α-methyl-benzyl methacrylate (MBMA) with binary initiator system of cobaltocene [Co(C5H5)2] and bis(ethyl acetoacetato)copper(II) [Cu(eacac)2] were studied in acetonitrile at 25°C. The molecular weight of the polymers obtained by MA was found to increase with time in the early stage of polymerization. Although MBMA was also polymerized by this system, asymmetric selective polymerization was not induced in the presence of (-)-sparteine. The synthesis of the block copolymer of MA and MBMA was attempted by using this initiator system. The block copolymer was obtained in 90% yield in the polymerization of MBMA with a polymer radical which prepared from MA with this system for 1 day. The yield of the block copolymer depended on the prepolymeriza-tion time of MA by this system. The resulting block copolymer was characterized by IR, 1H-NMR, and gel-permeation chromatography. 相似文献
The electron spin resonance (ESR) spectra of polymer radicals found to be trapped in polytetrafluoroethylene (PTFE) polymerized with radical initiators were comparatively examined under various conditions and assigned. They are identified as the primary (propagating) radicals RCF2CF2·, which are transformed to primary peroxy radicals RCF2CF2OO· in the atmosphere. Studies of the rates of polymerization and postpolymerization and ESR measurements indicate that the radical content steadily increases during polymerization. The results are discussed in connection with the mechanism of polymerization of tetrafluoroethylene (TFE) and the unusual thermal stability of these radicals in PTFE prepared with initiator. 相似文献
Vinyl monomers having electron acceptor groups such as nitroethylene, acrylonitrile, and acrolein were polymerized by KO2–charge transfer agent initiator systems in dimethylsulfoxide (DMSO) at 25°C. The new initiator systems were found to be stable for almost 1 month under nitrogen atmosphere. The initial rate of polymerization was so fast that both conversion and molecular weight of the polymers obtained were high. Especially their molecular weight distribution was observed to be very narrow by means of gel permeation chromatography (GPC). The anion radicals generated by one electron transfer from potassium superoxide (KO2) to charge transfer agents such as naphthalene, benzoquinone, azobenzene, etc., were suitable as initiator for the anionic polymerization of electron acceptor monomers. Study on block copolymerization of nitroethylene with acrylonitrile or acrolein was also attempted. 相似文献
A functionalized compound, 4‐(2‐bromoisobutyryl)‐2,2,6,6‐tetra‐methylpiperidine‐1‐oxyl (Br‐TEMPO), was synthesized and used to synthesize block copolymers through tandem nitroxide‐mediated radical polymerization (NMRP) and atom transfer radical polymerization (ATRP). First, Br‐TEMPO was used to mediate the polymerization of styrene. The kinetics of polymerization proved a typical “living” nature of the reaction and the effectiveness in the mediation of polymerization of Br‐TEMPO. Then the PS‐Br macroinitiator was used to initiate atom transfer radical polymerization (ATRP). A series of acrylates were initiated by PS‐Br macroinitiators in typical ATRP processes at various conditions. The controlled polymerization of ATRP was also confirmed by molecular weight and kinetic analysis. Several cleavable block copolymers of PS‐b‐P(t‐BA), PS‐b‐P(n‐BA), and PS‐b‐PMA, with different molecular weights, were synthesized via this strategy. Relatively low polydispersities (<1.5) were observed and the molecular weights were in agreement with the theoretical ones. Hydrolysis of PS‐b‐P(t‐BA) was carried out, giving amphiphilic block copolymer PS‐b‐PAA without the cleavage of C‐ON bond or ester bond. All the block copolymers have two Tgs as demonstrated by DSC. A typical cleavable block copolymer of PS‐b‐PMA was cleaved by adding phenylhydrazine at 120°C to produce homopolymers in situ. 相似文献
Curcumin (Cur), a natural colorant found in the roots of the Turmeric plant, has been reported for the first time as photoinitiator for the copolymerization of styrene (Sty) and methylmethacrylate (MMA). The kinetic data, inhibiting effect of benzoquinone and ESR studies indicate that the polymerization proceeds via a free radical mechanism. The system follows ideal kinetics (Rp α[Cur]0.5[Sty]0.97[MMA]1). The reactivity ratios calculated by using the Finemann–Ross and Kelen‐Tudos models were r1(MMA)=0.46 and r2(Sty)=0.52. IR and NMR analysis confirmed the structure of the copolymer. NMR spectrum showing methoxy protons as three distinct groups of resonance between 2.2–3.75 δ and phenyl protons of styrene at 6.8–7.1 δ confirmed the random nature of the copolymer. The mechanism for formation of radicals and random copolymer of styrene and MMA [Sty‐co‐MMA] is also discussed. 相似文献
Very thick slurry of sodium sulfohexyl methacrylate (SSHMA) with little amount of water was plasma-initiated and polymerized. The mechanism and kinetics of plasma-initiated polymerization of SSHMA were preliminarily studied. The existence of macromolecular "living" chains were ascertained by experiments. Thus, SSHMA-acrylic acid block copolymers were obtained by adding acrylic acid to livingSSHMA segments. The ESR results suggest that propagating radicals CH2C(CH3)CO-O(CH2)6SO3Na might be present in the SSHMA system initiated by plasma. It was found that no"living"chains were present in the SSHMA system initiated by either UV light or radical initiators under the same conditions. 相似文献
Novel fullerene‐grafted poly(3‐hexylthiophene) (P3HT)‐based rod‐coil block copolymers have been synthesized. The regioregular P3HT rod block has been synthesized by a modified Grignard metathesis reaction (GRIM). An original in situ end‐capping reaction has been developed in order to convert the P3HT block into an efficient macro‐initiator for the nitroxide‐mediated radical polymerization (NMRP) of the coil block. Controlled radical polymerization of the second poly(butylacrylate‐stat‐chloromethylstyrene) [P(BA‐stat‐CMS)] block has been done through various conditions leading to different coil block lengths. The final electron donor‐acceptor block copolymer has been obtained after C60 grafting in soft conditions. Copolymers have been characterized by 1H NMR and size exclusion chromatography. Optical characterizations, before and after C60 grafting, are reported.
An unsymmetrical triphenylethane, ethane-1,1,2-triyltribenzene (ETB), was successfully prepared from phenyl lithium, trans-1,2-diphenylethylene, and methanol. Characterization of the compound was performed by 1H and 13C nuclear magnetic resonance spectroscopy (NMR). The polymerization of methyl methacrylate (MMA) was performed in the presence of ETB at 85 °C or higher. The free radicals obtained were characterized by ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC/Q-TOF MS). Gel permeation chromatography (GPC) traces of the average molecular weight of poly(MMA) (PMMA) showed a series of translations with increasing time. The average molecular weight of PMMA indicated narrow polydispersity, and a linear relationship was found between ln([M]0/[M]) and polymerization time. These results indicated the “living” nature of the polymerization of MMA in the presence of ETB. The structure of ETB was also introduced to the end of polystyrene (PS), polyisoprene (PI), and polyisoprene-b-polystyrene (PIS) chains which were obtained by living anionic polymerization. Hence, they initiated radical polymerization of MMA as ETB-end-macroinitiators to obtain block copolymers. Thus, living anionic polymerization and this radical polymerization method were combined together to prepare block copolymers without the intermediate transformation step. 相似文献
Degradation processes of N-methylmorpholine-N-oxide monohydrate (NMMO), cellulose and cellulose/NMMO solutions were studied by high performance liquid chromatography (HPLC)
and electron spin resonance (ESR) spectroscopy. Kinetics of radical accumulation processes under UV (λ = 248 nm) excimer laser
flash photolysis was investigated by ESR at 77 K. Beside radical products of cellulose generated and stabilized at low temperature,
radicals in NMMO and cellulose/NMMO solutions were studied for the first time in those systems and attributed to nitroxide
type radicals ∼CH2–NO•–CH2∼ and/or ∼CH2–NO•–CH3∼ at the first and methyl •CH3 and formyl •CHO radicals at the second step of the photo-induced reaction. Kinetic study of radicals revealed that formation and recombination
rates of radical reaction depend on cellulose concentration in cellulose/NMMO solutions and additional ingredients, e.g.,
Fe(II) and propyl gallate. HPLC measurements showed that the concentrations of ring degradation products, e.g., aminoethanol
and acetaldehyde, are determined by the composition of the cellulose/NMMO solution. Results based on HPLC are mainly maintained
by ESR that supports the assumption concerning a radical initiated ring-opening of NMMO. 相似文献