Copolymerization Of Allyl Glycidyl Ether Research Articles

The Synthesis of Allyl Glycidyl Ether Copolymers and Their Thermokinetic Analysis

Abstract The copolymerization reactions of allyl glycidyl ether (AGE) by radicalic polymerization under argon atmosphere using benzoyl peroxide (BPO) as an initiator with the comonomers of allyl methacrylate (AMA) and methyl methacrylate (MMA) were studied. The synthesized copolymers were characterized by nuclear magnetic resonance ( 1 H-NMR), gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TG). FTIR and 1 H NMR spectra showed that the pendant epoxy groups in copolymers remained throughout the copolymerization of AGE. The apparent activation energies for thermal degradation of the copolymers were calculated from their TG data by using Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Coats-Redfern methods. The kinetic parameters such as pre-exponential factor, Gibbs energy, enthalpy and entropy were also calculated by Coats-Redfern method. The activation energies calculated by KAS method for Poly(AGE -co- AMA) and Poly(AGE -co- MMA) were found to be 292±10 kJ/mol and 175±27 kJ/mol for the first stage, and 252±74 kJ/mol and 232±32 kJ/mol for the second, respectively while they were 361±1 kJ/mol and 249±61 kJ/mol for Poly(AGE -co- AMA) and 136±24 kJ/mol and 278±18 kJ/mol for Poly(AGE -co- MMA) by FWO method. The most likely mechanisms of the main degradation stages were determined as F 3 model for Poly(AGE -co- AMA) and Poly(AGE -co- MMA). Thus, it is concluded that the thermal degradations of Poly(AGE -co- AMA) and Poly(AGE -co- MMA) copolymers exhibit similar behavior. Keywords: Thermal degradation, allyl glycidyl ether, allyl methacrylate, methyl methacrylate

Synthesis of thermosensitive magnetic nanocarrier for controlled sorafenib delivery

Allyl glycidyl ether/N-isopropylacrylamide-grafted magnetic nanoparticles were prepared using silica-coated magnetic nanoparticles as a substrate for radical copolymerization of allyl glycidyl ether and N-isopropylacrylamide. Chitosan was coupled with the prepared nanoparticles by opening the epoxy ring of the allyl glycidyl ether. The thermosensitive magnetic nanocarrier (TSMNC) obtained can be applied as a potent drug carrier. The TSMNC structure was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, vibrating sample magnetometer, and elemental analysis. Its morphology and size were investigated using field emission scanning electron microscopy, transmission electron microscopy and dynamic light scattering. The feasibility of employing the TSMNC for adsorption and in vitro controlled release of the chemotherapeutic agent sorafenib was tested. The effect of the adsorption parameters of pH, temperature, and loading time of sorafenib onto TSMNC was evaluated. The adsorption data was fitted to the Langmuir and Freundlich isotherms and the relevant parameters derived. The drug release profile indicated that 88% of the adsorbed drug was released within 35h at 45°C and drug release was Fickian diffusion-controlled. The results confirmed that the TSMNC has a high adsorption capacity at low temperature and good controlled release in a slow rate at a high temperature and could be developed for further application as a drug nanocarrier.

Comparative copolymerization of allyl glycidyl ether with styrene using radiation and chemical initiation methods

The 60Co-gamma rays radiation-induced and free radical-initiated copolymerizations of allyl glycidyl ether with styrene were studied comparatively. The latter was carried out at 60 °C for 1, 3, 5 and 7 days using azobis(isobutyronitrile) as a radical initiator, while in the first one the samples were irradiated at the different absorbed doses of 55, 110 and 165 kGy. Changes in chemical structure during copolymerization in both methods were analyzed by using proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform infrared spectroscopy. Thermal properties of the products were examined by means of thermogravimetry. Thermal stability values of poly(allyl glycidyl ether-co-styrene) (poly(AGE-co-St)) samples obtained by radical polymerization were quite similar to those of samples obtained by irradiation. The molecular weights (Mw and Mn) of the copolymers were determined by using gel permeation chromatography. The results showed that the polymerization method affects the polydispersity index of the copolymers. The results indicated that the radiation-induced copolymerization had a lower yield than that of radical initiator copolymerization.

The Characteristic Research of Two Kinds of Block Polymer

Dual end and single end MacroRAFT agents of polystyrene were obtained respectively by polymerizations of styrene in the presence of benzyl 1H-imidazole-1- carbodithioate (BICDT) and 4,4‘-bis(imidazole-1-carbodithioatemethyl)biphenyl (ICTMP) via the thermal initiation. Then copolymerization of allyl glycidyl ether（AGE） with methyl acrylate（MA） was performed to prepare the functional block copolymers in the presence of PSt maeorRATF agents. The results show that the process has good characteristics of living free radical polymerization. However, the top monomer conversion of triblock copolymers comparing diblock copolymers is lower under the same theory molecular weight and the content of monomer.

Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate‐free polyurethane networks

AbstractPoly(allyl glycidyl ether) and poly(allyl glycidyl ether‐co‐epichlorohydrin) were prepared by monomer‐activated anionic polymerization. Quantitative and controlled polymerization of allyl glycidyl ether (AGE) giving high molar mass polyether was achieved in a few hours at room temperature in toluene using tetraoctylammonium salt as initiator in presence of an excess of triisobutylaluminum ([i‐Bu3Al]/[NOct4Br] = 2−4). Following the same polymerization route, the copolymerization of AGE and epichlorohydrin yields in a living‐like manner gradient‐type copolymers with controlled molar masses. Chemical modification of the pendant allyl group into cyclic carbonate was then investigated and the corresponding polymers were used as precursors for the isocyanate‐free synthesis of polyurethane networks in presence of a diamine. Formation of crosslinked materials was followed and characterized by infrared and differential scanning calorimetry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Synthesis of polyester having sequentially ordered two orthogonal reactive groups by anionic alternating copolymerization of epoxide and bislactone

AbstractThis article presents a route to a novel polyester having sequentially ordered two orthogonal reactive groups. The polyester was given by the imidazole‐initiated alternating copolymerization of allyl glycidyl ether (AGE) and a bislactone 1. This copolymerization system is characterized by the following three reaction behaviors: (1) the selective participation of only one of the two lactone moieties of 1 to the copolymerization to give a linear polyester, and the consequent introduction of the second lactone into the side chain of the polyester, (2) the participation of the epoxy moiety in AGE to the copolymerization, and the consequent introduction of the carbon–carbon double bond into the side chain of the polyester, and (3) arrangement of the sequentially ordered two orthogonal reactive groups according to the alternating manner. The introduction of the two reactive groups to the side chain of the alternating copolymer allowed two routes of sequential chemoselective reactions: (A) The ring‐opening reaction of the lactone moiety with n‐propylamine and the following Pt‐catalyzed hydrosilylation of the carbon–carbon double bond with dimethylphenylsilane and (B) the sequential reactions of the reverse order. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009

Living free-radical copolymerization of allyl glycidyl ether with methyl acrylate

An investigation of the copolymerization of allyl glycidyl ether (AGE) with methyl acrylate (MA) was performed in the presence of benzyl imidazole-1-carbodithioate (BICDT) on the thermal initiation condition. Results showed that the process has good characteristics of living free radical polymerization, i.e. the molecular weight of the obtained polymer increases linearly with monomer conversion, molecular weight distribution is very narrow, and a linear relationship between ln([M]0/[M]) and polymerization time is found. The copolymer structure containing epoxy groups was demonstrated from the 1H nuclear magnetic resonance (1H NMR) spectrum. It was found that the content of AGE in the copolymer increases with the increase in monomer conversion and molar faction of the AGE in the monomer feed. However, the polymerization could slow down when the fraction of AGE increases in the monomer feed. Taking advantage of living polymerization character, functional block copolymers PSt-b-P (MA-co-AGE) were prepared in the presence of PSt RAFT agent.

Polyglycidols with Two Orthogonal Protective Groups: Preparation, Selective Deprotection, and Functionalization

Anionic ring-opening polymerization and copolymerization of allyl glycidyl ether (AGE), tert-butyl glycidyl ether (tBuGE), and ethoxyethyl glycidyl ether (EEGE) was performed using potassium 3-phenyl-1-propanol as initiator. The polymers poly(AGE), poly(tBuGE), poly(EEGE) as well as poly(AGE-co-tBuGE), poly(AGE-co-EEGE), and poly(EEGE-co-tBuGE) were obtained with controlled degree of polymerization, narrow molecular weight distribution and a predetermined ratio of repeating units. First-order kinetics with respect to the glycidyl monomers were found for homo- and copolymerization. The removal of protection groups from the homopolymers was achieved using trifluoroacetic acid for poly(tBuGE), aqueous hydrochloric acid for poly(EEGE), and a palladium catalyst for poly(AGE); in all cases a linear poly(glycidyl ether) (poly(GE), 1) was obtained. The following conversions were achieved by selective removal of only one protection group: using aqueous hydrochloric acid, poly(AGE-co-EEGE) was converted to poly(AG...

Controlled/living free-radical copolymerization of allyl glycidyl ether with methyl acrylate under 60Co γ-ray irradiation

An investigation on the copolymerization of allyl glycidyl ether (AGE), an epoxy-functional monomer, with methyl acrylate (MA) was performed in the presence of benzyl 1H-imidazole-1-carbodithioate (BICDT) under 60Co γ-ray irradiation. The polymerizations revealed good characteristics of RAFT process. The content of AGE incorporation into the copolymer increased with higher monomer conversion and higher molar fraction of the AGE in the monomer feed. However, the polymerization could slow down when the fraction of AGE increased in the monomer feed, which might be attributed to the low activity of AGE. Taking advantage of RAFT process, functional block copolymer poly(AGE/MA)- block-poly(styrene) was prepared in the presence of poly(styrene) macroRAFT agent, and the copolymer was characterized by 1H NMR spectra and GPC.

Polyfunctional Anion Exchangers Based on Copolymers of Allyl Glycidyl Ether and Polyamines

Polyfunctional anion exchangers were prepared by copolymerization of allyl glycidyl ether with polyamines in the presence of a promoter. The synthesis conditions were optimized. The composition and physicochemical features of the resins prepared were studied.

Polyethercarbonate–silica nanocomposites synthesized by copolymerization of allyl glycidyl ether with CO 2 followed by sol–gel process

The catalyst system consisting of Y(CF 3CO 2) 3, Zn(Et) 2, and pyrogallol in the solvent of 1,3-dioxolane was found to be effective for the copolymerization of allyl glycidyl ether with carbon dioxide at 60 °C and 400 psi. The IR, 1H-NMR, and 13C-NMR spectra as well as the element analysis indicated that the resulting copolymer was an alternating polyethercarbonate with the carbonate content higher than 97.5%. The resulting polyethercarbonate could react with 3-(trimethoxysilyl)propyl methacrylate via a free radical reaction to generate the alkoxysilane-containing copolymer precursors that were used in the subsequent sol–gel process to result in the polyethercarbonate–silica nanocomposite. The generated nanocomposite was characterized by 13C-NMR, 29Si-NMR, SEM, DSC, TGA, ESCA, and UV–Vis. The mechanical properties were also measured. A good compatibility between polyethercarbonate and silica and a SiO 2 network with silica particles less than 100 nm in the nanocomposite were observed. Both the thermal and mechanical properties of the resulting polyethercarbonate–silica nanocomposite were found to enhance with silica content. The optical transparency of the generated nanocomposite was comparable to that of the based polyethercarbonate.

Decay and termite resistance of boron-treated and chemically modified wood by in situ co-polymerization of allyl glycidyl ether (AGE) with methyl methacrylate (MMA)

Chemical modification was carried out on disodium octoborate tetrahydrate (DOT)-treated wood using allyl glycidyl ether (AGE) in combination with methyl methacrylate (MMA) to limit boron leaching. Co-polymerization of the monomers in DOT-treated sugi ( Cryptomeria japonica D. Don) wood was completed by catalyst heat treatment. Besides boron leachability, the dimensional stability and decay, and termite resistance of chemically modified wood were also determined. Dimensional stability in terms of anti-swelling efficiency and water absorption was found to improve in chemically modified wood specimens. Co-polymerization of AGE with MMA in DOT-treated wood resulted in less boron leaching compared with DOT-only-treated wood. Chemically modified wood containing boron proved to be more resistant to the brown-rot fungus Fomitopsis palustris (Berkeley et Curtis) Murrill (FFPRI 0507) and the white-rot fungus Trametes versicolor (L. ex Fr.) Quel. (FFPRI 1030) in laboratory decay resistance tests after severe leaching for 10 days. Termite resistance tests also showed that wood specimens treated with DOT and MMA plus AGE monomers were effective against subterranean termites Coptotermes formosanus Shiraki even after severe leaching cycles.

Synthesis and Modification of Functional Polycarbonates with Pendant Allyl Groups

Functional aliphatic polycarbonates with pendant allyl groups were synthesised by copolymerization of carbon dioxide and allyl glycidyl ether (AGE) in the presence of a catalyst system based on ZnEt2 and pyrogallol at a molar ratio 2 : 1. The functionality of some polycarbonates was reduced by replacing a part of allyl ether with saturated glycidyl ether, i.e., butyl glycidyl ether (BGE) or isopropyl glycidyl ether (IGE). Polycarbonates obtained by the copolymerization of AGE and CO2 or by the terpolymerization of AGE, IGE and CO2 were oxidized with m-chloroperbenzoic acid to their respective poly(epoxycarbonate)s. The influence of the AGE/ΣGE ratio in the polycarbonates, the polymer concentration in the reaction solution and the duration of the reaction on the conversion of allyl groups into glycidyl ones was examined. A tendency to gelation of the initial and oxidized polycarbonates during storage was observed. The initial polycarbonates and their oxidized forms were degraded in aqueous buffer of pH = 7.4 at 37°C. The course of hydrolytic degradation was monitored by the determination of mass loss.

Synthesis and Modification of Functional Polycarbonates with Pendant Allyl Groups

Functional aliphatic polycarbonates with pendant allyl groups were synthesised by copolymerization of carbon dioxide and allyl glycidyl ether (AGE) in the presence of a catalyst system based on ZnEt2 and pyrogallol at a molar ratio 2 : 1. The functionality of some polycarbonates was reduced by replacing a part of allyl ether with saturated glycidyl ether, i.e., butyl glycidyl ether (BGE) or isopropyl glycidyl ether (IGE). Polycarbonates obtained by the copolymerization of AGE and CO2 or by the terpolymerization of AGE, IGE and CO2 were oxidized with m-chloroperbenzoic acid to their respective poly(epoxycarbonate)s. The influence of the AGE/ΣGE ratio in the polycarbonates, the polymer concentration in the reaction solution and the duration of the reaction on the conversion of allyl groups into glycidyl ones was examined. A tendency to gelation of the initial and oxidized polycarbonates during storage was observed. The initial polycarbonates and their oxidized forms were degraded in aqueous buffer of pH = 7.4 at 37°C. The course of hydrolytic degradation was monitored by the determination of mass loss.

Thermal stability of the copolymers of allyl glycidyl ether with acrylonitrile and methyl methacrylate obtained via gamma irradiation

Abstract Homopolymerization of allyl glycidyl ether (AGE) initiated by gamma rays and the copolymerization of AGE with acrylonitrile (AN) and methyl methacrylate (MMA) were investigated. The thermal characterization of resulting homopolymers and copolymers were realized by Thermal Analysis Techniques and their degradation activation energies were calculated. The copolymers, P(AGE/AN), formed from AGE+AN monomers were more stable thermally than those copolymers, P(AGE/MMA), formed from AGE+MMA monomer mixtures.

Improvement of mechanical stability of beechwood by radiation-induced in situ copolymerization of allyl glycidyl ether with acrylonitrile and methyl methacrylate

Acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether (AGE), AGE + AN monomer, AGE + MMA monomer, and monomer mixtures were used to conserve and consolidate beechwood. After the impregnation of these monomer mixtures in the wood, polymerization was accomplished by gamma irradiation. The fine structures of wood + polymer(copolymer) composites were investigated by scanning electron microscopy (SEM). The copolymer obtained from AGE + MMA monomer mixtures showed the optimum compatibility with the wood. The compressive strength and Brinell hardness numbers determined for untreated and treated wood samples indicated that the mechanical strength was greater in wood + polymer(copolymer) composites than in untreated wood and was greatest in the samples containing AGE + AN and AGE + MMA copolymers. All monomer couples used in this study increased the mechanical strength of the wood and protected the samples against aging. AGE + MMA copolymers were the most effective in protecting the wood against various environmental attacks. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1515–1523, 1999

Improvement of mechanical stability of beechwood by radiation-inducedin situ copolymerization of allyl glycidyl ether with acrylonitrile and methyl methacrylate

Acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether (AGE), AGE + AN monomer, AGE + MMA monomer, and monomer mixtures were used to conserve and consolidate beechwood. After the impregnation of these monomer mixtures in the wood, polymerization was accomplished by gamma irradiation. The fine structures of wood + polymer(copolymer) composites were investigated by scanning electron microscopy (SEM). The copolymer obtained from AGE + MMA monomer mixtures showed the optimum compatibility with the wood. The compressive strength and Brinell hardness numbers determined for untreated and treated wood samples indicated that the mechanical strength was greater in wood + polymer(copolymer) composites than in untreated wood and was greatest in the samples containing AGE + AN and AGE + MMA copolymers. All monomer couples used in this study increased the mechanical strength of the wood and protected the samples against aging. AGE + MMA copolymers were the most effective in protecting the wood against various environmental attacks. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1515–1523, 1999

Comparison of the dimensional stabilities of oak and cedar wood preserved by in situ copolymerization of allyl glycidyl ether with acrylonitrile and methyl methacrylate

Oak and cedar woods were impregnated with acrylonitrile (AN), methyl methacrylate (MMA), and mixtures of allyl glycidyl ether (AGE) with AN and MMA to conserve and consolidate the wood. After impregnation, these monomer mixtures were polymerized by gamma irradiation. The dimensional stabilities and the resistance against the biodegradation of the wood (oak and cedar)/(co)polymer composites were determined. The water uptake capacity of the wood/(co)polymer composites is up to 50% lower than that of the original wood, for P(AGE/MMA) and P(AGE/AN) copolymers lower than for PAN and PMMA. Artificial raining did not change the structure of wood/(co)polymer composites and no biodegradation occurred. Eichen- und Zedernholz wurde mit Acrylnitril (AN), Methylmethacrylat (MMA) und Mischungen von Allylglycidylether (AGE) mit AN und MMA impragniert, um es zu konservieren und verfestigen. Die Monomeren wurden anschliesend durch Gammastrahlen polymerisiert. Die Formstabilitat und die Verrottungsbestandigkeit wurden untersucht. Die Wasseraufnahmefahigkeit liegt bis zu 50% unter derjenigen der unbehandelten Holzer, mit P(AGE/MMA) und P(AGE/AN) ist sie niedriger als mit PAN und PMMA. Kunstliche Beregnung fuhrte nicht zu einer Anderung der Struktur der Composite, und sie zeigten keine Anzeichen von Verrottung.

Improvement of the mechanical stability of oak by radiation-induced in-situ copolymerization of allyl glycidyl ether with acrylonitrile and methyl methacrylate

This study deals with the improvement of the mechanical stability of oak, which belongs to the hardwoods, by radiation-induced in-situ copolymerization of certain monomers. Acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether/acrylonitrile (AGE/AN), and allyl glycidyl ether/methyl methacrylate (AGE/MMA) monomers and monomer mixtures were employed to conserve and consolidate the wood. After impregnating oak with these monomer mixtures, polymerization was accomplished by γ-irradiation. The relationships between the mechanical properties of the wood/(co)polymer composites and the anatomic structure of the wood, the types and the quantity of the polymer and copolymer, the irradiation dose and the aging process were explored. The fine structure of the wood/(co)polymer composites and the compatibility of wood with polymer and copolymer were investigated by scanning electron microscopy. The existence of polymer and copolymer in the wood enhanced the mechanical durability of the wood. The results of the hardness and the compressive strength tests applied in the parallel and perpendicular directions to the fibers of the wood/(co)polymer composites show that P(AGE/MMA), P(AGE/AN) copolymers are effective in raising the mechanical durability. In the case of P(AGE/MMA), the increase in the compressive strength perpendicular to the fibers in the oak wood is 179% at highest conversion. Similar results were also acquired from hardness tests. The decrease in the mechanical durability after aging for 28 d was very little.

Improvement of the mechanical stability of oak by radiation-induced in-situ copolymerization of allyl glycidyl ether with acrylonitrile and methyl methacrylate

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