Synthesis and Polymerization of Poly(N-substituted maleimide) Macromonomers

J of Applied Polymer Sci

Nakashima

Onimura

et al. 2003

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ABSTRACT:A new chiral methacrylate, (S)-(ϩ)-1-cyclohexylethyl-(2-methacryloyloxyethyl)urea (CEMOU), was synthesized from 2-methacryloyloxyethyl isocyanate (MOI) and (S)-(ϩ)-cyclohexylethylamine. Radical homopolymerization of CEMOU was performed in several solvents to obtain the corresponding chiral polymers having hydrogen bonds based on urea moieties. Specific optical rotations of poly(CEMOU) were slightly changed by the measurement temperature, which may be attributed in part to a change of conformation caused by hydrophobic interaction between the cyclohexyl groups. From the results of radical copolymerization of CEMOU (M 1 ) with styrene (ST, M 2 ) or methyl methacrylate (MMA, M 2 ), monomer reactivity ratios (r 1 , r 2 ) and Alfrey-Price Q-e values were determined: r 1 ϭ 0.89, r 2 ϭ 0.12, Q 1 ϭ 2.45, e 1 ϭ 0.68 for the CEMOU-ST system; r 1 ϭ 0.48, r 2 ϭ 0.18, Q 1 ϭ 8.39, e 1 ϭ 1.97 for the CEMOU-MMA system. The chiroptical property of the poly(CEMOU-co-ST) was slightly influenced by the co-units. Poly(CEMOU)-bonded silica gel as the chiral stationary phase (CSP) was prepared for high-performance liquid chromatography (HPLC). The CSP resolved trans-2-dibenzyl-4,5-di(o-hydroxyphenyl)-1,3-dioxolane in normal phase such as n-hexane/2-propanol by HPLC.

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of novel polymethacrylate bearing an (S)‐(+)‐1‐cyclohexylethyl urea group in the side chain and its chiral recognition ability

J of Applied Polymer Sci

Nakashima

Onimura

et al. 2003

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“…From this point of view, many studies have been reported so far 1–5. Previously, we reported the synthesis and polymerization of new N ‐substituted maleimide (RMI) macromonomers from RMI polymers and unsaturated isocyanate, that is, methacryloyloxyethyl isocyanate (MOI) 6…”

Section: Introductionmentioning

confidence: 99%

Syntheses and polymerizations of novel chiral poly(acrylamide) macromonomers and their chiral recognition abilities

Oishi

J. Polym. Sci. A Polym. Chem.

Nakagawa

et al. 2002

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Chiral poly(acrylamide) macromonomers (PMB-1, PMB-2, PPAE-1, and PPAE-2) were synthesized from 2-methacryloyloxyethyl isocyanate and prepolymers, that is, poly[(S)-methylbenzyl acrylamide] or poly(L-phenylalanine ethylester acrylamide with a terminal carboxylic acid or hydroxy group. Radical homopolymerizations of poly(acrylamide) macromonomers were carried out under several conditions to obtain the corresponding optically active polymers. A strong temperature dependence on the specific optical rotation was observed for poly(PPAE-2) in comparison with that for the corresponding prepolymer. This might have resulted from a change in the conformation caused by hydrogen bonds between polymer-graft branches in the polymacromonomer. Radical copolymerizations of poly(acrylamide) macromonomers with styrene and methyl methacrylate were performed with azobisisobutyronitrile in tetrahydrofuran at 60°C. Chiroptical properties of the copolymers were slightly influenced by comonomer units. Chiral stationary phases were prepared by the radical polymerization of poly-(acrylamide) macromonomers in the presence of silica gel containing vinyl groups on the surface. Some racemic compounds such as menthol and mandelic acid were resolved on the chiral stationary phases for high-performance liquid chromatography. The conformation based on hydrogen bonds between polymer-graft branches in the polymacromonomers may play an important role in chiral discrimination.

“…3 We synthesized and polymerized Nsubstituted maleimide (RMI) macromonomers and examined from the view point of thermal stability of the polymers obtained. 4 However there have been few reports on synthesis of MOI derivatives bearing an optically active group. Bamford et al 5 synthesized MOI derivatives from α-amino acid and D-glucosamine, and examined applications of the polymers to blood compatibility.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Novel Chiral Poly(methacrylate)s Having Urea Moieties and (S)-Methylbenzyl or l-Phenylalanine Methyl Ester Groups and Their Chiral Recognition Abilities

Hisamitsu

Onimura

et al. 2002

Polym J

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ABSTRACT:New chiral methacrylates, (S )-methylbenzyl methacryloyloxyethyl urea (MBMOU) and (S )-methoxycarbonylbenzylmethyl methacryloyloxyethyl urea (MCMOU) were synthesized from 2-(methacryloyloxy)ethyl isocyanate (MOI) and (S )-methylbenzylamine and L-phenylalanine methyl ester, respectively. Radical polymerizations of MBMOU and MCMOU were performed under several conditions to obtain the corresponding polymers whose specific optical rotations ([α] 25 435 ) were −13.5• to −10.9• and 30.8• to 31.5• , respectively. From the results of radical copolymerizations of RMOU (MBMOU and MCMOU, M 1 ) with styrene (ST, M 2 ) or butyl methacrylate (BMA, M 2 ), monomer reactivity ratios (r 1 , r 2 ) and Alfrey-Price Q-e were determined. The chiroptical properties of poly(MBMOU-co-M 2 )s were strongly influenced by co-units. Poly(RMOU)-bonded-silica gel as chiral stationary phase (CSP) was prepared for high performance liquid chromatography (HPLC). The CSPs resolved some racemates such as ketoprofen and ethyl mandelate. The enantiorecognition ability may be based on higher-ordered structures of the polymer. KEY WORDS 2-(Methacryloyloxy)ethyl isocyanate / Radical Polymerization / Monomer Reactivity Ratios / Chiral Stationary Phase / Optical Resolution / 2-(Methacryloyloxy)ethyl isocyanate (MOI) is a bifunctional monomer with both a reactive isocyanate group and a polymerizable double bond, and is convenient and widely used for crosslinking agents and materials for molecular design of new polymers. 1 Many kinds of MOI derivatives have been synthesized from several alcohol and amine compounds and polymerized. 2 MOI is also useful for preparation of macromonomer. 3 We synthesized and polymerized Nsubstituted maleimide (RMI) macromonomers and examined from the view point of thermal stability of the polymers obtained. 4 However there have been few reports on synthesis of MOI derivatives bearing an optically active group. Bamford et al. 5 synthesized MOI derivatives from α-amino acid and D-glucosamine, and examined applications of the polymers to blood compatibility. Chiral stationary phase (CSP) for high performance liquid chromatography (HPLC) was prepared from MOI and cyclodextrin. 6 To our knowledge, no chiroptical properties of MOI derivatives with optically active groups have been reported. Thus, we lately reported on synthesis and polymerizations of some chiral methacryloyloxyethyl carbamates (RMOC) from MOI and chiral alcohols such as cholesterol, L-menthol, amino acid derivatives, and 2-hydroxy-2 -methoxy-1,1 -binaphthalene, and chiroptical properties of the polymers. [7][8][9] Recently, a wide variety of CSPs have been developed for the separation of enantiomers by HPLC. 10 Although many kinds of synthetic chiral polymers have been applied to the CSPs, there have been few reports on preparation of CSPs for HPLC from poly(methacrylate)s bearing a chiral pendant group. 11 The reason may be that low chiral recognition ability of the chiral pendant group used and/or the absence of stable higher-ordered structures of the...