Polymers 2a Research Articles

Research on high-carbon ether-based oxygen additives: Catalytic transformation of 2-methylfuran and furfural to ethers via CuMgAlOx catalysts

The surge in aviation fuel consumption has intensified environmental concerns, driving research efforts towards discovering oxygen-enriched additives that can boost their performance. This investigation employs 2-methylfuran and furfural as precursors, undergoing catalytic conversion into high-performance high-carbon ethers. The study initiates by employing Amberlyst-15 resin as a catalyst, converting 2-methylfuran and furfural into a high-carbon polymer (1A). A continuous polymerization process in a fixed-bed reactor highlights the exceptional stability of Amberlyst-15, maintaining a conversion rate of approximately 70 % over 140 h. A kinetics model elucidates the temperature-dependent dynamics of the polymerization reaction. Following this, the polymer undergoes hydrogenation (HDO) using CuMgAlOx catalyst, yielding an ether compound (2A) with a remarkable selectivity of 95.7 % and a carbon yield of 95.5 %. Characterization techniques reveal uniform elemental distribution and a high abundance of mesopores in the CuMgAlOx catalyst, substantiating its superior hydrogenation efficiency. Notably, even after six cycles, the CuMgAlOx catalyst retains an impressive 94.8 % polymer conversion rate, underscoring its exceptional stability.

New hydrophilic mesoporous copper (II) coordination polymers obtained from poly(ethylene terephthalate) (PET) waste for diesel removal in water

Two new hydrophilic mesoporous copper (II) coordination polymers were synthetized from poly(ethylene terephthalate) waste by the coordination reaction under solvothermal conditions in only 60 min with quantitative yields. Both polymers and their aroyl hydrazone derivates were fully characterized by NMR (1H,13C, and 1H-15N HMBC), vibrational analysis, XPS spectroscopy, and high-resolution mass spectrometry. The XPS analysis of the new polymers 3a and 3b evidenced the formation of the N → Cu and O → Cu coordination bonds and the high-resolution mass spectrometry corroborates the presence of copper atoms in their molecular structure. The textural properties of 3a and 3b were analyzed by physisorption revealing that both materials can be classified as mesoporous materials with a pore size distribution of around 14.98 nm. Furthermore, the mesoporous copper (II) coordination polymer 3a exhibits a linear behavior with a maximum adsorption capacity of 743 and 1553 mg g−1 at 0.10 and 0.20 g/L, respectively. The adsorption/desorption cycles of 3a reveal that the novel copper (II) coordination polymers obtained from poly(ethylene terephthalate) (PET) waste had a greater adsorption capacity (1553 mg g−1); showing that structural modification of this type of coordination polymers can be a remarkable tool to increase the adsorption properties through the chemical modification to more hydrophilic, porous and crystalline coordination polymers.

Selective uptake and removal of aromatic and heterocyclic compounds by para-dicyanobenzene-linked, EFe3(CO)9-incorporated (E = Te, Se), semiconducting Cu chain polymers

The uptake and removal of volatile and toxic organic compounds is an important issue in modern industrial chemistry because these organic pollutants have long-term effects on public health and the global environment. In this work, we successfully synthesized two novel para-dicyanobenzene (p-DCB)-linked, EFe3(CO)9-incorporated (E = Te, Se) 1D polymers [EFe3(CO)9Cu2(p-DCB)1.5]n (E = Te, 1a; Se, 1b) from liquid-assisted grinding (LAG) of the di-Cu compounds [EFe3(CO)9Cu2(MeCN)2] with p-DCB. Polymers 1a and 1b had isomorphous structures with single- and double-p-DCB linkers alternatively connected to Cu atoms of EFe3(CO)9Cu2 (E = Te, Se) cores, in which two p-DCB of the double-p-DCB moiety were parallel-displaced with the π···π interaction on their benzene rings. The selective adsorption of C7−C10-alkyl aromatics, polycyclic aromatics, and heterocyclic compounds by 1a and 1b was accomplished via neat grinding or THF-aided LAG processes. These reactions led to the formation of the guest molecule (G)-intercalated products, i.e., 1a- and 1b-based polymers [EFe3(CO)9Cu2(p-DCB)1.5·(G)m]n [E = Te, 1a·mG; E = Se, 1b·mG; m = 0.5 or 1] and the THF-introduced single-p-DCB-bridged polymer [TeFe3(CO)9Cu2(p-DCB)·(THF)]n (2a·1THF). These adsorption activities of 1a and 1b were thoroughly evaluated by single-crystal and powder X-ray analysis and TGA and DSC measurement, where some C−H···π, π···π, and C−H···E (E = O, S) interactions between guest molecules and the p-DCB linkers were observed to stabilize polymer chains. The desorption of volatile heterocyclic (THF, furan, thiophene) or alkyl aromatic (toluene, m-xylene, mesitylene, durene) guest molecules to give the parent polymers 1a and 1b could be achieved by vacuum and recrystallization or stepwise LAG process in the Te system. Importantly, these EFe3(CO)9Cu2-incorporated (E = Te, Se) polymers 1a and 1b, as well as their host−guest adducts, exhibited semiconducting behaviors possessing tunable energy gaps (1.36−1.51 eV) with moderate electrical conductivities ((1.21−6.55)×10–7 S·cm–1), in which the guest molecules played a crucial role in modulating the electron transport in the solid state.

Bivalent monomer bearing styryl and five‐membered cyclic dithiocarbonate moieties for orthogonal radical and cationic ring‐opening polymerizations

AbstractWe synthesized a novel bivalent monomer 1 bearing 4‐vinylbenzyl group and five‐membered cyclic dithiocarbonate. This monomer 1 was polymerized orthogonally by free radical polymerization to afford polystyrene 1a bearing a five‐membered cyclic dithiocarbonate moiety in the side chain. On the other hand, cationic ring‐opening polymerization of five‐membered cyclic dithiocarbonate in the monomer 1 successfully proceeded, resulting in a narrow molecular weight distribution of polydithiocarbonate 1b bearing a 4‐vinylbenzyl group in the side chain. Furthermore, post‐polymerizations of 1a and 1b maintaining the polymerizable functionality were carried out respectively by suitable polymerization methods. The five‐membered cyclic dithiocarbonate of 1a underwent cationic ring‐opening polymerization with a high molar ratio of methyl trifluoromethanesulfonate at a high temperature compared to the case of monomer 1, whereas radical polymerization of the 4‐vinylbenzyl group of 1b successfully proceeded under the almost same conditions as the case of monomer 1. These post‐polymerizations achieved the synthesis of corresponding networked polymers 2a and 2b.

Synthesis of poly[1-phenyl-2-(fluoren-2-yl)acetylene]s bearing trimethylsilyl groups at the fluorene 9-position to give highly gas-permeable polymer membranes

Four types of 1-phenyl-2-(fluoren-2-yl)acetylene bearing SiMe3 groups at the 9-position of fluorene (1a–1d) were synthesized and polymerized in the presence of TaCl5/n-Bu4Sn to yield the corresponding polymers (2a–2d). Membranes fabricated from 2a–2c exhibited fairly high gas permeabilities (PO2: 1600–7000 barrer), while membrane 2d was too brittle for testing. As the number of SiMe3 groups in the monomer unit increased, the gas permeability of the polymer membrane increased. Desilylated membranes 3a–3c were obtained by the desilylation of membranes 2a–2c, respectively. Desilylated polymers 3a–3c possessed identical chemical structures but different gas permeabilities (PO2: 2500–5800 barrer). Highly gas-permeable polymers 2c and 3c exhibited good stabilities against physical aging in terms of their gas permeabilities.

Small Chains of Main Group Elements by BH3 Adduct Formation of tBu2E‐N(H)‐EtBu2 (E = P, As)

Borane adducts of bis(di‐tert‐butylphosphanyl)amine (1a) and bis(di‐tert‐butylarsino)amine (1b) are reported. Based on quantum‐chemical investigations in combination with experimental results, it is demonstrated that the tautomerism known for tBu2P‐N(H)‐PtBu2 (1a), can be observed for the mono adduct tBu2P‐N(H)‐P(BH3)tBu2 (2a) as well, whereas for the corresponding arsenic compound 2b only one stable isomer is found. The bis‐borane adduct tBu2(BH3)As‐N(H)‐As(BH3)tBu2 (3b) is a rare example of a structurally characterized, tertiary arsine borane adduct, which can be directly compared with the corresponding phosphorus compound tBu2(BH3)P‐N(H)‐P(BH3)tBu2 (3a). Deprotonation of mixtures containing 2a by nBuLi leads to the lithium‐containing coordination polymer 4a, in which the actual chain consists only of non‐carbon atoms.

Silver(I) Complexes of Two Flexible Bis-phospholane Ligands: Metallamacrocycles, Polymeric Chains, and Metallacryptands.

In a 2:2 reaction with silver(I) chloride or bromide, 1,5‐bis(1‐phospholano)pentane (1a) afforded frame‐like macrocyclic structures, with intra‐ (2, Cl) or intermolecular (3, Br) halido bridges. In contrast, 1,7‐bis(1‐phospholano)heptane (1b) formed coordination polymers 4a (Cl) and 4b (Br) with bridging bis‐phospholane and halido ligands. A unique paddle wheel‐type metallacryptand structure 5 was obtained from 1a and silver(I) bromide in a 2:3 reaction (M:L). All complexes were fully characterized by NMR, IR spectroscopy, mass spectrometry, and X‐ray crystallography.

Heterochiral or Homochiral Self‐Assembly: Mercury(II), Cadmium(II), and Spontaneous Resolution of Silver(I) Complexes Derived from a Racemic Bis(pyridyl) Ligand

A novel racemic bis(pyridyl) ligand (rac‐L) was designed and synthesized by Schiff condensation reaction. Five complexes, [Hg2(LR)(LS)Cl4]·2CH3CH2OH (1), [Cd(LR)(LS)Cl2]n (2), {[Cd(LR)(LS)SO4(H2O)]·11H2O}n (3), {[Ag(LR)2]NO3·CH3CN}n (4a) and {[Ag(LS)2]NO3·CH3CN}n (4b) have been synthesized and characterized. The different geometric features of complexes 1–4 were determined by single‐crystal X‐ray diffraction. The crystal structures show that the self‐assembly with racemic ligands can lead to homochiral or heterochiral complexes, through self‐recognition or self‐discrimination of the ligand units. Complex 1 exists as a 26‐membered binuclear heterochiral macrocycle. Complexes 2 and 3 form 1D mesomeric looped chain coordination polymers with different heterochiral self‐assembly types. More interestingly, two novel 2D homochiral coordination polymers 4a and 4b were obtained as racemic conglomerates via spontaneous resolution. Furthermore, the thermal stabilities and luminescence properties of complexes 1–4 were investigated.

Conjugated helical polymers: End-group control and coupling reactions

Telechelic helical poly(phenyleneethynylene)s 2 and 3 bearing end iodo and ethynyl groups were synthesized by the Sonogashira–Hagihara coupling reaction of prepolymer 1 with N-α-tert-butoxycarbonyl-3,5-diiodo-4-hydroxy-d-phenylglycine hexylamide (4) and p-diethynylbenzene (5), respectively. Polymer 2 was treated by Sonogashira–Hagihara coupling reaction with 1,6-diethynylpyrene (a) and 4,4-diethynylbiphenyl (b) to obtain the corresponding polymers 2a and 2b. Polymer 2 was also subjected to the Mizoroki–Heck coupling reaction with diphenyl(p-vinylphenyl)phosphine (e) to obtain the corresponding polymer 2e, and the incorporation of the phosphine moieties was confirmed by 31P NMR spectroscopy. In a similar fashion, polymer 3 was polymerized with 1,4-dibromonaphthalene (c) and 9,10-dibromoanthracene (d), but no concrete evidence for the formation of polymers 3c and 3d was observed. Circular dichroism (CD) spectroscopic analysis revealed that all the polymers adopted folded helical conformations with predominantly one-handed screw sense in CHCl3. The polymers exhibited photoluminescence (PL) depending on the incorporated functional groups.

Synthesis and Properties of N-Arylpyrrole-Functionalized Poly(1-hexene-alt-CO)

The 1,4-polyketone derived from 1-hexene and carbon monoxide, poly(1-hexene-alt-CO) (1), can undergo Paal–Knorr cyclization with substituted anilines to yield N-pyrrole-functionalized polyketones. A variety of pendant functionalities are introduced to 1, including azobenzene (6) and triarylamines (5a–e). The extent of incorporation depends on the nucleophilicity of the parent aniline. Polymer 6 exhibits a UV-induced trans → cis photoisomerization and has lower rates of photoinduced decomposition relative to parent 1. Triarylamine-containing polymers 5a–e are redox-active, forming optically active radical cations upon chemical oxidation. Compared with model N-arylpyrrole compounds 9a–e, polymers 5a–e demonstrate hypsochromic shifts in UV–vis absorptions and exhibit features between +0.5 and +1.2 V (vs Ag/AgCl) in solution-phase differential pulse voltammetry.

An Addition–Isomerization Mechanism for the Anionic Polymerization of MesP═CPh2 and m-XylP═CPh2

We report that the anionic polymerization of P-mesityl and m-xylyl-substituted phosphaalkenes follows an unusual addition–isomerization mechanism. Specifically, the polymerization of ArP═CPh2 [Ar = Mes (1a), m-Xyl (1b)] involves the hindered nucleophilic anion intermediate, Ⓟ–P(Ar)–CPh2–, which undergoes a proton migration from the o-CH3 of the Mes/m-Xyl moiety to the −CPh2 moiety to afford a propagating benzylic anion. This mechanism is supported by the preparation of model compounds MeP(CHPh2)-4,6-Me2C6H2–2-CH2–CPh3 (2a) or MeP(CHPh2)-6-MeC6H3–2-CH2–CPh3 (2b), which were both crystallographically characterized. Polymerization of 1a or 1b in THF solution using n-BuLi (2 mol %) revealed 1H and 13C NMR signals assigned to −CH2– and −CHPh2 groups consistent with an addition–isomerization polymerization mechanism to afford poly(methylenephosphine) 3a or 3b. A large kinetic isotope effect (≤23) was determined for the n-BuLi-initiated polymerization of 1a-d9 compared to 1a in THF at 50 °C, consistent with C–H ...

Poly(p-phenylenediethynylene phosphine)s and Related π-Conjugated Phosphine–Diyne Polymers: Synthesis, Characterization and Photophysical Properties

Despite the considerable synthetic challenge, polymers that incorporate phosphorus atoms within or adjacent to a π-conjugated backbone framework are of interest due to the ability to modulate the photophysical properties of the polymer based on the chemical environment at phosphorus. We report the synthesis and characterization of poly(p-phenylenediethlynylene phosphine)s, 1a–1e, a new class of σ–π conjugated polymer. Polymers 1a–1e were prepared by a Ni-catalyzed coupling of dialkynes with phenyldichlorophosphine in the presence of excess triethylamine and have molecular weights (Mw) up to 12,000 g mol–1 (vs. polystyrene). While the polymers 1b–1e are nonfluorescent, blue fluorescence is observed upon oxidation of the phosphorus centers (Φsoln = 0.12–0.28). Polymers 1b·O–1e·O also exhibit yellow/green fluorescence in the solid state (Φsolid = 0.04–0.08). These results introduce a fascinating new class of main group-containing macromolecule and lay the groundwork for their utilization in sensory applicati...

Synthesis and utility of 3-silylthiophenes having perfluoroalkyl groups

The synthesis of a novel class of 3-silyl substituted thiophenes possessing perfluoroalkyl groups on the silicon atom was investigated. The treatment of 3-bromothiophene with n-butyllithium followed by the reaction with halosilanes proceeded to afford the corresponding 3-silyl substituted thiophenes 1 in good yields. The chemical polymerization of the resulting 1 did not work well. However, the electropolymerization of 3-silylthiophenes 1a and 1b provided the corresponding polymers 5a and 5b with head-to-tail regioregularity. The cyclic voltammogram of the resulting polymers 5a and 5b indicated both n- and p-doping properties.

Synthesis and CO2 permeation properties of novel sulfonium-substituted poly(diphenylacetylene)s

Substitution of thiourea to poly(diphenylacetylene) having 2-bromoethoxy groups (2a) gave an sulfonium-containing poly(diphenylacetylene) [3a (Br − )]. The counteranions of 3a (Br − ) could be exchanged using CF3COOK and (CF3SO2)2NLi, and the polymers 3a (TFAc − ) and 3a (Tf 2 N − ) were obtained. Polymer 3a (Br − ) was hydrolyzed with NaOHaq to afford the polymer 4a possessing mercapto groups. The CO2 permeability coefficients (\(P_{{{\text{CO}}_{ 2} }}\)) and the separation factor (\(P_{{{\text{CO}}_{ 2} }} /P_{{{\text{N}}_{ 2} }}\)) of 3a (Br − ) were 15 barrers and 16, respectively. The selectivity was low compared to the analogous polymer, poly(diphenylacetylene) having imidazolium salts (\(P_{{{\text{CO}}_{ 2} }} /P_{{{\text{N}}_{ 2} }} = 4 4\)), because 3a (Br − ) interacted strongly with CO2, and the diffusion of CO2 was suppressed. The \(P_{{{\text{CO}}_{ 2} }}\) and \(P_{{{\text{CO}}_{ 2} }} /P_{{{\text{N}}_{ 2} }}\) of 3a (TFAc − ) were 43 barrers and 24, respectively, and those of 3a (Tf 2 N − ) were 52 barrers and 26, respectively. Both permeability and selectivity increased as the counteranion became bulkier. The mercapto group containing poly(diphenylacetylene) (4a) showed a relatively high CO2 permeability (\(P_{{{\text{CO}}_{ 2} }} = 1 30\) barrers).

Direct synthesis of polyaromatic chains of tribenzopentaphene copolymers through cyclodehydrogenation of their poly‐tetraphenylbenzene precursors

ABSTRACTThree polyaromatic‐based polymers are reported to contain co‐monomers of trapezoidal tribenzopentaphene (TBP) polycyclic aromatic hydrocarbons. The synthetic strategy consists of initially making highly soluble tetraphenylbenzene copolymers 4a–c, followed by a cyclodehydrogenation/aromatization reaction to obtain target polymers 5a–c. The polymers were characterized by gel permeation chromatography, FT‐IR, UV‐vis, emission, 1H‐, and 13C‐nuclear magnetic resonance spectroscopy. The target polymers 5a–c reveal emission spectra in the range of 430–480 nm; thus, qualifying them to act as blue emitters. Investigation of the polymers optical properties and their correlation with density functional theory calculations suggest a distorted TBP core from planarity caused by the introduction of a dodecyl group at its wide edge. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3565–3572

Eco-Friendly Polythiophene(keto-amine)s Based on Cyclopentanone Moiety for Environmental Remediation

Eco-friendly polythiophene(keto-amine)s 4 a–e containing thiophene-arylidene-thiophene tri-blocks moieties in polymers backbones have been synthesized and characterized for environmental remediation. The synthetic method has been carried out by the interaction of the monomer 2 with different aromatic, cyclic and aliphatic diamines. The polymerization had occurred using polycondensation process in dry benzene as solvent. A new monomer namely, 2,5-bis[4-choloro-acetyl(thiophen-2-ylmethylene)]cyclopentanone 2 was firstly synthesized using the normal condition of Friedel–Crafts reaction by the reaction of 2,5-bis(thiophen-2-ylmethylene)cyclopentanone 1 with chloroacetyl chloride in the presence of aluminum chloride anhydrous. The structure of the new monomer as well as polymers was confirmed by elemental and spectral analyses. Furthermore, solubility, viscometry, SEM and thermal characteristics for the new polymers were tested. All the polymers were freely soluble in formic acid as good example for polar protic solvents. PDTmax and FDT for all the polymers were detected and were in the range 434–467 and 487–533 °C respectively. On the other hand, the analytical competition of the newly synthesized PTKA polymers 4 a and 4 c was also evaluated for a selective extraction of metal ions prior to their determination by inductively coupled plasma-optical emission spectrometry mainly for environmental remediation. The selectivity of PTKA 4a and PTKA 4c towards different metal ions, including Cd(II), Co(II), Cu(II), Cr(III), Fe(III), Ni(II) and Zn(II), was studied. Results of the selectivity study demonstrated that 4 a and 4 c polymers was the most selective towards Cr(III) and Co(II). Adsorption capacity of 4a for Cr(III) was improved by 38.37% in comparison to that of 4 c for Co(II) after only 1 h contact time. Moreover, adsorption isotherm data provided that the adsorption process was mainly monolayer on homogeneous adsorbent surfaces of both PTKA 4 a and PTKA 4 c.

Solution‐processable and electroactive aromatic polyamides with 3,5‐bis(trifluoromethyl)triphenylamine moiety

AbstractNew fluorine‐containing, triphenylamine‐based diamine and dicarboxylic acid monomers, namely 3,5‐bis(trifluoromethyl)‐4′,4″‐diaminotriphenylamine and 3,5‐bis(trifluoromethyl)‐4′,4″‐dicarboxytriphenylamine, were synthesized and polymerized with commercially available aromatic dicarboxylic acids and diamines, respectively, leading to two series of aromatic polyamides, 5a–h and 7a–e. Most of the polyamides were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, flexible and strong films with good mechanical properties. The polyamides had useful levels of thermal stability associated with high glass transition temperatures of 273–305 °C and 10% weight‐loss temperatures in excess of 500 °C. Cyclic voltammograms of films of polymers 5a–h on indium–tin oxide‐coated glass substrates exhibited reversible oxidation redox couples with E1/2 around 1.15 V versus Ag/AgCl in tetrabutylammonium perchlorate/acetonitrile solution, accompanied by a color change from colorless neutral state to reddish brown oxidized state. The 7 series polymers displayed a higher oxidation potential and less electrochemical stability as compared to the 5 series analogues. © 2017 Society of Chemical Industry

Synthesis and characterization of novel anti-inflammatory poly(spiro thiazolidinone)s

A new series of spirothiazolidinone polymers has been accomplished by solution polycondensation of 4,12-dioxa-1,9-dithiadispiro[4.2.4.2]tetradecane-3,11-dione (3) with different aliphatic and aromatic diamines. A model compound 4 was prepared by the reaction of spiro-monomer 3 with benzyl amine and was characterized by elemental and spectral analyses. These polymers were characterized by elemental and spectral analyses. The thermal properties of these polymers were investigated by thermogravimetric analysis and differential thermal analysis measurements. The morphological properties of selected polymers 5c and 5e were tested using scanning electron microscope to study their surface morphology. The molar masses of polymers 5a, 5b, and 5d were determined by gel permeation chromatography. In addition, the anti-inflammatory activities were studied for these spiro-polymers in comparison with the model compound by determination in vivo using acute carrageenan-induced paw edema in rats.

Addition-Isomerization Polymerization of Chiral Phosphaalkenes: Observation of Styrene–Phosphaalkene Linkages in a Random Copolymer

These studies provide the first evidence for styrene–phosphaalkene connectivities in a phosphaalkene copolymer. The synthesis and structural characterization of new phosphaalkene–oxazolines, ArP═C(Ph)(3-C6H4Ox) [1a,b, Ar = Mes (1a), Mes* (1b), Ox = CNOCH(iPr)CH2], are reported. The radical-initiated homo- and copolymerization of 1a with styrene affords P-functional poly(methylenephosphine) (4a: Mn = 5300 g mol–1, PDI = 1.2) and poly(methylenephosphine-co-styrene) (5a: Mn = 4000 g mol–1, PDI = 1.1). Multinuclear NMR spectroscopic analyses of 4a and 5a provided evidence for the predominance of an addition-isomerization mechanism for the radical polymerization of 1a. In addition, signals could be assigned to CHPh–P(CHPhAr) (i.e., S–1a) and ArCH2–CH2 (i.e., 1a–S) linkages in copolymer 5a. With a monomer feed ratio of 1a:S (1:2, 33 mol % 1a) the inverse gated 13C{1H} NMR spectrum suggested an incorporation of 19 mol % 1a in copolymer 5a. Polymers 4a and 5a were further functionalized to Au(I)-containing macromolecules [4a·AuCl: Mn = 13 000, PDI = 1.2; 5a·AuCl: Mn = 7500, PDI = 1.1].

Metathesis polymerization of diphenylacetylenes possessing electron-donating and electron-withdrawing groups and emission properties of polymers

Diphenylacetylenes containing electron-donating groups (O-n-C8H17: 1A, OCH3: 1B, SCH3: 1C) and electron-withdrawing groups (COOCH3: 1a, COCH3: 1b, CF3: 1c, CN: 1d) were polymerized using TaCl5/n-Bu4Sn. The polymerization of diphenylacetylenes possessing both an n-octyloxy group and an electron-withdrawing group (1Aa, 1Ab, 1Ac) was also examined in the same conditions. Electron-donating group-containing monomers (1A–C) polymerized to afford relatively high-molecular-weight polymers (Mn=240,000–622,000). Ester-containing monomers (1a and 1Aa) also polymerized to give polymers with high molecular weights, while the polymerization of acetyl- and trifluoromethyl-containing monomers (1b, 1c, 1Ab, 1Ac) gave low-molecular-weight polymers. Cyano-containing monomer (1d) did not polymerize because cyano groups deactivated tantalum catalysts. Polymers having electron-donating groups (2A–C) emitted green-colored lights, and the emission maxima were around 505nm. Ester-containing polymers 2a and 2Aa showed yellow-colored emissions, and the emission maxima were 520nm. These polymers showed emission red-shifts between the solution and cast film.