Chemical modification of poly(vinyl chloroformate) and of its copolymers using phase transfer catalysis

Boivin, Sylviane; Chettouf, Abderrahmane; Hémery, Patrick; Boileau, Sylvie

doi:10.1007/bf00275577

Cited by 14 publications

(7 citation statements)

References 6 publications

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“…Substitution of chlorine in CholCl by M-PEG leads to the shift of the carbonyl absorption band from 1775 cm Ϫ1 to 1745 cm Ϫ1 (Fig. 1, spectra b-d), resulting from the change in the electronegativity of the neighboring ␣-atom of the carbonyl group (Boivin et al, 1983). The reaction was stopped after 7 days.…”

Section: Synthesis and Purification Of Monomethoxypoly(ethylene Glycol) Cholesteryl Carbonatementioning

confidence: 99%

“…Monomethoxypoly(ethylene glycol) cholesteryl carbonate (M-PEG-Chol) has been synthesized in one step by the reaction of M-PEG on CholCl, using moderate phase transfer catalysis conditions previously described for the nucleophilic substitution of poly(vinyl chloroformate) by phenol (Boivin et al, 1983(Boivin et al, , 1985(Boivin et al, , 1988. In a typical experiment, 2.5 mmol of polymer dissolved in 10 ml CH 2 Cl 2 was added dropwise to a magnetically stirred mixture containing 2.5 mmol of CholCl in 20 ml CH 2 Cl 2 , 0.125 mmol of Bu 4 N ϩ Cl Ϫ (5 mol% of each reagent), and 3.75 mmol of NaOH in water (33 weight %) as HCl scavenger.…”

Section: Synthesis and Purification Of Monomethoxypoly(ethylene Glycol) Cholesteryl Carbonatementioning

confidence: 99%

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New Sterically Stabilized Vesicles Based on Nonionic Surfactant, Cholesterol, and Poly(Ethylene Glycol)-Cholesterol Conjugates

Beugin

Edwards

Karlsson

et al. 1998

Biophysical Journal

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Monomethoxypoly(ethylene glycol) cholesteryl carbonates (M-PEG-Chol) with polymer chain molecular weights of 1000 (M-PEG1000-Chol) and 2000 (M-PEG2000-Chol) have been newly synthesized and characterized. Their aggregation behavior in mixture with diglycerol hexadecyl ether (C16G2) and cholesterol has been examined by cryotransmission electron microscopy, high-performance gel exclusion chromatography, and quasielastic light scattering. Nonaggregated, stable, unilamellar vesicles were obtained at low polymer levels with optimal shape and size homogeneity at cholesteryl conjugate/ lipids ratios of 10 mol% M-PEG1000-Chol or 5 mol% M-PEG2000-Chol, corresponding to the theoretically predicted brush conformational state of the PEG chains. At 20 mol% M-PEG1000-Chol or 10 mol% M-PEG2000-Chol, the saturation threshold of the C16G2/cholesterol membrane in polymer is exceeded, and open disk-shaped aggregates are seen in coexistence with closed vesicles. Higher levels up to 30 mol% lead to the complete solubilization of the vesicles into disk-like structures of decreasing size with increasing PEG content. This study underlines the bivalent role of M-PEG-Chol derivatives: while behaving as solubilizing surfactants, they provide an efficient steric barrier, preventing the vesicles from aggregation and fusion over a period of at least 2 weeks.

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Section: Synthesis and Purification Of Monomethoxypoly(ethylene Glycol) Cholesteryl Carbonatementioning

confidence: 99%

Section: Synthesis and Purification Of Monomethoxypoly(ethylene Glycol) Cholesteryl Carbonatementioning

confidence: 99%

New Sterically Stabilized Vesicles Based on Nonionic Surfactant, Cholesterol, and Poly(Ethylene Glycol)-Cholesterol Conjugates

Beugin

Edwards

Karlsson

et al. 1998

Biophysical Journal

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“…Vinyl carbamates, or enol carbamates, are useful intermediates for agricultural chemicals, pesticides, pharmaceutical products, monomers for transparent polymers and varnishes [102,103]. Generally, alkyl carbamates are synthesized by various methods like the addition of alcohols to isocyanates, the reaction of amines with chloroformates [104,105], the dehydrohalogenation of α-halogeno [106], β-halogenoalkyl carbamates [107] and addition of amines to vinyl chloroformates [108,109].…”

Section: Synthesis Of Vinyl Carbamatesmentioning

confidence: 99%

Carbon dioxide: a renewable feedstock for the synthesis of fine and bulk chemicals

Patil

Tambade

Jagtap

et al. 2009

Front. Chem. Eng. China

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The syntheses of carbon dioxide (CO 2 ) based industrially important chemicals have gained considerable interest in view of the sustainable chemistry and "green chemistry" concepts. In this review, recent developments in the chemical fixation of CO 2 to valuable chemicals are discussed. The synthesis of five-member cyclic carbonates via, cycloaddition of CO 2 to epoxides is one of the promising reactions replacing the existing poisonous phosgene-based synthetic route. This review focuses on the synthesis of cyclic carbonates, vinyl carbamates, and quinazoline-2,4(1H,3H)-diones via reaction of CO 2 and epoxide, amines/phenyl acetylene, 2-aminobenzinitrile and other chemicals. Direct synthesis of dimethyl carbonate, 1,3-disubstituted urea and 2-oxazolidinones/2-imidazolidinones have limitations at present because of the reaction equilibrium and chemical inertness of CO 2 . The preferred alternatives for their synthesis like transesterification of ethylene carbonate with methanol, transamination of ethylene carbonate with primary amine and transamination reaction of ethylene carbonate with diamines/β-aminoalcohols are discussed. These methodologies offer marked improvements for greener chemical fixation of CO 2 in to industrially important chemicals.

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“…Cependant, cet auteur a gCnCralement observk des rkactions secondaires d'hydrolyse conduisant a des polymkres rkticulCs dont le degrC de substitution ne dCpasse pas 30%. Nous avons mis au point des conditions opkratoires qui permettent d'Cviter les rkactions de dkgradation (6,(10)(11)(12). Les polymkres ainsi modifiCs sont solubles et les degrks de substitution sont excellents.…”

Section: Polymkres Derives Du Polychloroformiate De Vinyleunclassified

“…Ceci nous a incites a examiner en dttail la polyrntrisation de ce monomere (6-8) et de quelques dtrivts (6,8,9) ainsi que la modification chirnique du polychloroforrniate de vinyle (6,(10)(11)(12). L'ernploi de peroxydicarbonates cornrne arnorceurs de la polyrntrisation radicalaire du chloroforrniate de vinyle, en rnasse et en solution, conduit a des polyrneres de masses rnolaires Clevtes (7,8).…”

Section: Introductionunclassified

Polymérisation du chloroformiate de vinyle et de ses dérivés

Boivin¹,

Hémery²,

Boileau³

1985

Can. J. Chem.

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Requ le 19 juin 1984Cet article esr rle'die' a la mkmoire de Monsieur Li Xiao-Bni SYLVIANE BOIVIN, PATRICK HEMERY et SYLVIE BOILEAU. Can. J . Chem. 63, 1337Chem. 63, (1985 La polymCrisation radicalaire du chloroformiate de vinyle a CtC Ctudiee dans le chlorure de mtthylkne a 35"C, avec le peroxydicarbonate de dicyclohexyle comme amorceur. Dcs mesures cinetiques ont Ct C effectuCes par dilatomktrie dans des appareils entikrement scellts sous vide pousse. L'ordre de la rkaction de polymCrisation par rapport B la concentration en monomkre est Cgal a I et celui relatif i la concentration en amorceur est Cgal B 0,5.Par ailleurs, des polymkres nouveaux ont CtC prCparCs soit par polymCrisation radicalaire de monomeres dCrivCs du chloroformiate de vinyle, soit par modification chimique du polychloroformiate de vinyle par des amines, des alcools, des thiols, des acides carboxyliques, KCN . . . , par catalyse par transfert de phase. La structure de ces polymkres ainsi que leur comportement thermique ont Ct C examinks. SYLVIANE BOIVIN, PATRICK HEMERY, and SYLVIE BOILEAU. Can. J . Chem. 63, 1337Chem. 63, (1985. The free-radical polymerization of vinyl chloroformate has been studied in methylene chloride at 3S°C using dicyclohexyl peroxydicarbonate as initiator. Kinetic measurements performed by dilatometry under high vacuum have shown that the reaction order in monomer is equal to one whereas that in catalyst is equal to 0.5.New polymers have been prepared either by free-radical polymerization of monomers derived from vinyl chloroformate or by chemical modification of poly(viny1 chloroformate) with amines, alcohols, thiols, carboxylic acids. KCN . . . using phase transfer catalysis. The structure of these polymers as well as their thermal behaviour have becn studied.

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Chemical modification of poly(vinyl chloroformate) and of its copolymers using phase transfer catalysis

Cited by 14 publications

References 6 publications

New Sterically Stabilized Vesicles Based on Nonionic Surfactant, Cholesterol, and Poly(Ethylene Glycol)-Cholesterol Conjugates

New Sterically Stabilized Vesicles Based on Nonionic Surfactant, Cholesterol, and Poly(Ethylene Glycol)-Cholesterol Conjugates

Carbon dioxide: a renewable feedstock for the synthesis of fine and bulk chemicals

Polymérisation du chloroformiate de vinyle et de ses dérivés

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