Synthesis of optically active polymers bearing amino acid moieties by atom transfer radical polymerization

We report here an approach toward the synthesis of optically active polyacrylamide bearing amino acid moieties, poly[Nmethacryloyl L-leucine methyl ester] （PMALM）, with controlled average number molecular weight （Mn） and relatively narrow polydispersity index （PDI, Mw/Mn 〈 1.3） by atom transfer radical polymerization （ATRP） using initiating system methyl 2-bromopropionate/CuBr/tris（2-dimethylaminoethyl） amine. The optical properties of the resulting polymers were evaluated from specific optical rotation value and CD spectra.

RAPID SYNTHESIS OF NOVEL OPTICALLY ACTIVE POLY(AMIDE-IMIDE)S DERIVED FROM N,N'-(PYROMELLITOYL)-BIS-L-ALANINE DIACID CHLORIDE AND HYDANTOIN DERIVATIVES UNDER MICROWAVE IRRADIATION

Eight novel poly(amide-imide)s were synthesized under microwave irradiation by using a domestic microwaveoven from the polycondensation reactions of N.N'-(pyromellitoyl)-bis-L-alanine diacid chloride(1)with eight differentderivatives of hydantoin compounds(2a-h)in the presence of a small amount of a polar organic medium such as o-cresol.The polycondensation proceeded rapidly,compared with the conventional solution polycondensation and was completedwithin 8-10 min,producing a series of new poly(amide-imide)s(3a-h)with inherent viscosities about 0.35-0.68 dL/g inhigh yields.The obtained PAIs(3a-h)were fully characterized by means of FT-IR spectroscopy,elemental analyses,inherentviscosity(ηinh),solubility and specific rotation measurements.All of the resulting polymers show optical rotation and areoptically active.Thermal properties of the poly(amide-imide)s were investigated by using thermal gravimetric analysis(TGA).

SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLYAMIDES BASED ON 2-(1,3-ISOINDOLINEDIONE-2-YL)GLUTARIC ACID BY DIRECT POLYCONDENSATION

Five new optically active polyamides （PAs） 6a-6e were prepared by direct polycondensation reaction of 2-（1,3- isoindolinedione-2-yl）-glutaric acid 4 as a new chiral diacid with various aromatic diamines 5a-Se in a medium consisting of triphenyl phosphite （TPP）, calcium chloride, pyridine （Py） and N-methyl-2-pyrrolidone （NMP）. The polycondensation reaction produced a series of polyamids 6a-6e in quantitative yields with inherent viscosities of 0.26-0.39 dL/g. The resulting polymers were fully characterized by means of ^1H-NMR, FT-1R spectroscopy, elemental analysis, inherent viscosity and specific rotation. Thermal properties of these polymers were investigated using thermal gravimetric analysis （TGA） and differential thermal gravimetry （DTG）. Phthalimide rings as a bulky pendent group in the polymer chains disturb the interchain and intrachain interactions and make these PAs readily soluble in polar, aprotic solvents such as N,N-dimethyl acetamide （DMAc）, N,N-dimethyl formamide （DMF）, dimethyl sulfoxide （DMSO）, N-methyl-2-pyrrolidone （NMP） and sulfuric acid.

SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(AMIDE-IMIDE)S CONTAINING PHOTOSENSITIVE CHALCONE UNITS IN THE MAIN CHAIN

A series of new optically active poly（amide-imide）s were synthesized by direct polycondensation reaction of 4,4＇-diaminochalcone with several N-trimellitylimido-L-amino acids using a tosyl chloride （TsCl）, pyridine （Py） and dimethylformamide （DMF） system as condensing agent. The resulting thermally stable poly（amide-imide）s were obtained in good to high yields and inherent viscosities ranging between 0.35 dL/g and 0.58 dL/g and were characterized with FTIR, IH-NMR, CHN, Ultraviolet, TGA and DTG techniques.

POLYMERIZATION OF N,N'-(PYROMELLITOYL)-BIS-L-LEUCINE DIACID CHLORIDE WITH HYDANTOIN DERIVATIVES BY MICROWAVE IRRADIATION

Facile and rapid polycondensation reactions of N,N'-(pyromellitoyl)-bis-L-leucine diacid chloride 1 with eight different derivatives of hydantoin compounds 2a-h were developed by using a domestic microwave oven in the presence of a small amount of polar organic medium such as o-cresol. The polycondensation reactions proceeded rapidly, compared with the conventional solution polycondensation, and was completed within 7-10 min, producing a series of novel optically active poly(amide-imide)s 3a-h with high yield and inherent viscosity of 0.35-0.65 dL/g. All of the above polymers were fully characterized by FT-IR, elemental analyses, inherent viscosity (η inh ), solubility test and specific rotation. Some structural characterization and physical properties of these optically active poly(amide-imide)s are reported.

POLYMERIZATION OF 1-AZABICYCLO[4.2.0]OCTANE WITH CHIRAL TRICYCLIC AMINO ACID ESTERS FOR OBTAINING BIOMEDICAL MATERIALS

The cationic ring-opening polymerization of 1-azabicyclo[4.2.0]octane, commonly called conidine （1） was studied with some chiral tricyclic amino acid esters （6a-6f） as acylation agents to obtain optically active biopolymers （Sa-8f） of the different masses. The structures of the new compounds were confirmed by FT-IR, UV and NMR, and the distribution index of the molecular weights of the polymers was determined from SEC measurements.