Won-Chul Lee

SYNTHESIS AND ELECTRO-OPTICAL PROPERTIES OF POLY(2-ETHYNYLPYRIDINIUMTOSYLATE) HAVING PROPAGYL SIDE CHAIN

Novel conjugated ionic polymer was prepared by the polymerization of 2-ethynylpyridine with propargyl tosylate in refluxing methyl alcohol. The polymerization proceeded well in homogeneous manner to give a relatively high yield of polymer. The resulting poly(2-ethynylpyridinium tosylate) having propargyl side chain [poly(EPT-P)] were hygroscopic and soluble in water, methyl alcohol, DMF, and DMSO. The inherent viscosities of the polymers were in the range of 0.08-0.29dL/g. Instrumental analyses using NMR, IR, and UV-visible spectroscopies and elemental analyses indicated that the resulting poly(EPT-P) have a conjugated ionic polymer backbone carrying N-propargyl-2-pyridinium tosylate. Thermal and electro-optical properties of the polymers were also studied.

Polymerization of 4-dimethylamino-N-propargylpyridinium bromide by transition metal catalysts

The polymerization of an ionic propargyl derivative, 4-dimethylamino-N-propargylpyridinium bromide (DMAPPB), was carried out by palladium, platinum, and ruthenium chlorides. The polymerization of DMAPPB by these transition metal catalysts proceeded well to give a relatively high polymer yield. The chemical structure of the resulting polymer was characterized by such instrumental methods as elemental analysis, infrared, NMR, UV–visible spectroscopies to have conjugated polymer backbone system bearing 4-dimethylamino-N-methylenepyridinium bromide. The polymer was soluble in DMF, DMSO, and formic acid, and found to be less hygroscopic than those of similar homologues having more smaller substituents. The resulting polymers were mostly black powders and showed the amorphous morphology.

Polymerization of α-hydroxyacetylenes by transition metal catalysts

Abstract α-Hydroxyacetylenes (2-propyn-1-ol, DL-3-butyn-2-ol, 1-octyn-3-ol, 2-phenyl-3-butyn-2-ol) with a hydroxy functional group were polymerized by various Mo- and W-based catalysts. In general, the catalytic activities of Mo-based catalysts were greater than those of W-based catalysts for these polymerizations. In the polymerization of 2-propyn-l-ol, MoCl5 alone and the MoCl5-EtAlCl2 catalyst system gave a quantitative yield of polymer. In the polymerization of 2-propyn-l-ol and its homologues by Mo-based catalysts, the polymer yield decreased as the bulkiness of the substituent increased. On the other hand, the polymer yield increased as the bulkiness of the substituent increased in WCl6-EtAlCl2-catalyzed polymerization. Polymers with a bulkier substituent showed better solubility in organic solvents than those without a substituent [e.g., poly (2-propyn-l-ol)]. The structures of the resulting polymers were characterized by various instrumental methods such as 1H- and 13C-NMR, IR, and UV-visible spec...

Polymerization of tripropargylamine by transition metal catalysts and molecular structure of poly(tripropargylamine)

Abstract A novel highly conjugated polymer with two cyclic recurring units per monomeric unit was prepared from tripropargylamine using various transition metal catalysts. PdCl 2 , PtCl 2 , and RuCl 3 were found to be effective catalysts, whereas the tungsten-based and molybdenum-based catalysts gave a low yield of polymer. In the polymerization by PdCl 2 , DMF, DMSO, and pyridine were found to be good solvents. The resulting polymers were brown or black powders and mostly insoluble in organic solvents regardless of the polymerization conditions and the catalysts used. The solid-state 13 C-NMR spectrum of poly(tripropargylamine) showed the carbon peaks of the conjugated double bond on the polymer backbone at 110–150 ppm, which had been absent in the monomer. The chemical structure of polymer had a quasi-helical characteristic (TG 3 ). The calculated identity period was 11.97 A. Furthermore, this polymer possessed less than a three-dimensional order with a noncrystalline morphology.

POLYMERIZATION OF 4-HYDROXY-N-PROPARGYLPIPERIDINE BY TRANSITION METAL CATALYSTS

The polymerization of 4-hydroxy-N-propargylpiperidine, having 4-hydroxypiperidine moiety, was carried out with various transition metal catalysts. The polymerizations proceeded well to give a relatively high yield of polymer (maximum polymer yield: 93%). Palladium, platinum, and ruthenum chlorides were found to be generally effective for this polymerization. On the other hand, the group 5 and 6 transition metal catalysts such as WCl6, MoCl5, WCl6-organoaluminum compounds etc. fail to polymerize this monomer. The molecular structure of the resulting poly(4-hydroxy-N-propargylpiperidine) was characterized by the various instrumental analysis methods such as NMR (1H-and 13C-)IR, and UV-visible spectroscopies. The IR spectrum of polymer shows neither the acetylenic hydrogen stretching (3197 cm−1) nor the carbon-carbon triple bond stretching (2113 cm−1) frequencies presented in the IR spectrum of monomer. Instead, the carbon-carbon double bond stretching frequency at 1611 cm−1 was newly observed. These polymer...

POLYMERIZATION OF ACETYLENE DERIVATIVES BY METALLOCENE CATALYSTS: POLYMERIZATION OF PHENYLACETYLENE BY BIS(CYCLOPENTADIENYL)MOLYBDENUM DICHLORIDE-BASED CATALYST SYSTEM

Bis(cyclopentadienyl)molybdenum dichloride-based catalyst systems were used for the polymerization of phenylacetylene. The bis(cyclopentadienyl) molybdenum-based catalyst systems were found to be effective for the polymerization of phenylacetylene to give a relatively high yield of polymer. EtAlCl2 showed high cocatalytic activity for the polymerization of phenyl acetylene by Cp2MoCl2. The polymerization behaviors were studied according to such reaction variables as monomer to catalyst mole ratio, initial monomer concentration, polymerization temperature, time, etc. The polymer structure was characterized by various instrumental methods to be the conjugated polymer backbone structure having phenyl substituents. The resulting poly(PA)s were generally light-brown powers and soluble in common organic solvents. The physical and thermal properties of the resulting poly(phenylacetylene) were also investigated.

Double ring-forming cyclopolymerization of tripropargylammonium salts by transition metal catalysts

Double ring-forming cyclopolymerization of tripropargylammonium monomers having three polymerizable acetylene functionalities in the same monomer was carried out by various transition metal catalysts such as MoCl5-EtAlCl2, WCl6-EtAlCl2, PdCl2, PtCl2, RuCl3, etc. In general, the polymerization proceeded well to give a relatively high yield of polymers. Poly(tri-propargylammonium tosylate) and poly(tripropargyl-ammonium tetraphenylborate), having bulky counter anions such as tosylate and tetraphenylborate, were generally soluble in such organic solvents as DMF, DMSO, and formic acid, whereas the poly(tri-propargylammonium bromide) having Br- as counter anion was insoluble in any organic solvents. The instrumental analyses shows that the resulting poly(tripropargylammonium salt)s have a highly conjugated polymer backbone system having such counter ions as bromide, tosylate, and tetraphenylborate. Ther-mal and morphological properties of the polymers were also studied by TGA/DSC and X-ray diffraction analytic...

Synthesis and Properties of Poly(Phenyl Propargyl Ether) and Its Homologues

Abstract Various para-substituted phenyl propargyl ethers (substitutent = H, OMe, and CN) were synthesized and polymerized by transition metal catalyst systems including MoCl5, WC16, and PdCl2. The catalytic activity of MoCl5-based catalysts was greater than that of WCl6-based catalysts for the present polymerization. The polymer yield increased in the following order: H > OMe > CN, according to substitutents. The [poly-(pheny] propargyl ether) [poly(PPE)] and poly(methoxy phenyl propargyl ether) [poly(OMe-PPE)] obtained are completely soluble in various organic solvents such as chloroform, methylene chloride, THF, and 1,4-dioxane. However, poly(cyanophenyl propargyl ether) [poly(CN-PPE)] is partially soluble in various organic solvents such as those mentioned above. The electrical conductivities of the undoped and iodine-doped polymers and found to be about 10−13 and 10−4-10−5 S/cm, respectively. The solubilities, thermal properties, and morphologies of the resulting polymers were also studied.

Polymerization of Cyclohexene Oxide By Organoaluminum Compounds

Abstract The polymerization of cyclohexene oxide (CHO) by various organoaluminum compounds such as R3Al (R = Me, Et, i-Bu), Et2AlCl, and EtAlCl2 is reported. Ethyl-substituted aluminum compounds were found to be very effective for this polymerization. As more chlorine atom is substituted on the aluminum atom, the polymer yield was increased though the molecular weight was decreased. The polymer yields at varying monomer-to-catalyst mole ratios (M/C) were similar (80–93%). The temperature and solvent effect for the present polymerization were also studied. The present poly(CHO) was a less stereoregular (atactic) isomer, regardless of catalysts and polymerization conditions. The resulting poly(CHO) was a white powder ad was soluble in aromatic and halogenated hydrocarbon solvents such as benzene, chlorobenzene, CCl4, chloroform, etc.

Synthesis of Poly(2-ethynylpyridinum bromide) Containing Propargyl Side Chain and Its Photoluminescence Properties

Abstract Water-soluble conjugated ionic polymer was prepared by the polymerization of 2-ethynylpyridine with propargyl bromide in refluxing methanol. The polymerization proceeded well in homogeneous manner to give a high polymer yield (95%). The resulting poly(2-ethynylpyridinium bromide) having propargyl side chain was mostly brown powder and soluble in the polar solvents such as methanol, water, DMF, and DMSO. The inherent viscosities of the polymer were in the range of 0.10–0.21dL/g. This polymer exhibited good film surface by microscope, and characteristic UV-visible absorption band at 2.3 eV and red PL spectrum at 760nm corresponding to the photon energy of 1.63 eV.