Synthesis and properties of fluorene‐based fluorinated polymers

Fluorene‐based polymers containing various fluorinated benzene (fluorobenzene, p‐difluorobenzene, and tetrafluorobenzene) moieties were synthesized. In addition, perfluorooctylation of poly‐[(9,9‐dioctylfluorene‐2,7‐diyl)‐co‐(fluorene‐2,7‐diyl)] was carried out to afford fluorene‐based polymers with perfluorooctyl moiety at the 9‐position on the fluorene ring. To evaluate the effect of fluorine moiety, polymers containing nonfluorinated benzene moieties and nonfluorinated octyl groups were synthesized. The photoluminescence measurements indicated that all these polymers exhibited blue emission in solution, but a polymer containing a perfluorooctyl group did not emit in the film state. Polymers containing various fluorinated benzene moieties showed higher fluorescence quantum yields and thermal stability than those containing nonfluorinated benzene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3143–3150, 2001     

Photoinitiated polymerization of aryl cyclic sulfonium salts

Polymers are produced by direct photolysis of substituted aryl cyclic sulfonium Zwitterionic salts in solution or film. Analysis of zwitterionic monomers via ¹³C NMR, UV, and IR spectroscopy as well as X‐ray diffraction clearly identifies the structures taking part in the photoinduced polymerization in the solid crystalline films. The protonated form of the zwitterionic monomers, however, fails to produce detectable amounts of polymer upon photolysis under any conditions. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 571–584, 2001     

Synthesis and properties of amorphous blue‐light‐emitting polymers with high glass‐transition temperatures

A series of soluble poly(arylene ether)s containing the phenylphosphine oxide moiety were synthesized by the polymerization of substituted oligophenylene diols with bis(fluorophenyl)phenylphosphine oxide. These amorphous polyethers had well‐defined structures and showed blue photoluminescence combined with good thermal stability, especially when phenyl or ethoxy side groups were used. The glass‐transition temperatures increased when the size of the oligophenylene segment increased from three to five rings or when the length of the alkoxy substituents decreased. Polymers with glass‐transition temperatures up to 270 °C were obtained. The absorption and photoluminescent spectra shifted to longer wavelengths with an increase in the oligophenylene block. A redshift was also observed on photoluminescent spectra in the transition from solution to the solid state. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3168–3179, 2001     

Formation of regioregular head‐to‐tail poly[3‐(4‐butylphenyl)thiophene] by an oxidative coupling polymerization with vanadium acetylacetonate

The mechanism for the formation of head‐to‐tail (H–T) poly[3‐(4‐butylphenyl)thiophene] by oxidative coupling polymerization with a catalytic amount of vanadium acetylacetonate was investigated. Polymerization was carried out in the presence of vanadium acetylacetonate, trifluoromethane sulfonic acid, and trifluoroacetic anhydride under an oxygen atmosphere in 1,2‐dichloroethane at room temperature. Polymers and oligomers obtained after several polymerization times were characterized by gel permeation chromatography, IR, and NMR spectroscopies. With these findings and the reactivity of monomer and dimers based on ab initio density functional theory, the polymerization was found to proceed mainly through the formation of H–T linkages due to the high spin density at the 2‐position of 3‐(4‐butylphenyl)thiophene and the calculated total energy of dimers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2287–2295, 2001     

Synthesis and properties of poly(arylene ether)s bearing sulfonic acid groups on pendant phenyl rings

Two kinds of new aromatic poly(arylene ether)s containing sulfonic acid groups were synthesized. Polymer 1 composed of tetraphenylphenylene ether and perfluorobiphenylene units was sulfonated with chlorosulfonic acid. Sulfonation took place only at the para position of the pendant phenyl rings. The average degree of sulfonation per repeating unit (m) was controlled from 1 to 4. Sulfonated polymer 2 with m = 3 was soluble in methanol and dimethyl sulfoxide and swelled in water. Incorporating bis(3,5‐dimethylphenyl)sulfone moieties into the sulfonated polymer imparts less methanol affinity. Polymers 4 with 30–65 mol % tetrakis(sulfophenyl)phenylene ether units has high decomposition temperatures above 300 °C, hydrophilicity, and good hydrolytic stability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3211–3217, 2001     

Polymerizable anthracene derivatives for labeling emulsion copolymers

We describe the synthesis of three anthracene–methacrylate monomers [9‐methacryloxymethyl‐10‐methyl anthracene ( 4 ), 9‐methacryloxyethyloxymethyl‐10‐methyl anthracene ( 5 ), and 9‐methacryloxy‐10‐methyl anthracene ( 6 )] as well as their emulsion copolymers containing butylacrylate. When films prepared from latex dispersions containing 4 or 5 were heated, the anthracene (An) group was cleaved from the polymer at temperatures above 120 °C. Lower temperatures induced this reaction when strong acids were present. In 4 and 5 , the polymerizable group is connected to the An ring via a 9‐CH₂O? linkage. The cleavage reaction requires more stringent conditions when the connection involves a benzylic ether ( 5 ) instead of a benzylic ester. Polymers prepared from 6 , with an An? O? bond, were stable for 1 h at 150 °C in the presence of 0.5 wt % p‐toluene sulfonic acid. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1495–1504, 2001     

Multisensitive polymers based on 2‐vinylpyridine and N‐isopropylacrylamide *

Poly(2‐vinylpyridine) (P2VP) containing functionalized end groups was synthesized using nitroxyl‐mediated radical polymerization with a hydroxy‐functionalized stable free radical. It was shown that P2VP could be synthesized with variable molar masses and low polydispersities. The transformation of the hydroxy groups to an acrylic ester led to the formation of macromonomers. A free‐radical copolymerization of these macromonomers with N‐isopropylacrylamide gave a graft copolymer with a poly(N‐ispopropylacrylamide) backbone and P2VP side chains. Polymers containing different amounts of the monomers were synthesized. It was possible to vary both the amount of P2VP side chains at a constant chain length of the macromonomer and the chain length at a nearly constant chain number. The behavior of the multifunctional macromolecules at different temperatures and pH values was investigated using dynamic light scattering and DSC. The macromolecules were found to retain the specific properties of the homopolymers. The hydrodynamic radii of the synthesized graft copolymers were both dependent on the temperature and pH value. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3797–3804, 2001     

Use of β‐cyclodextrins to control the structure of water‐soluble copolymers with hydrophobic parts

In this article, we present the synthesis and characterization of water‐soluble polymers with hydrophobic moieties. The polymers were synthesized in aqueous solutions utilizing β‐cyclodextrins as solubility enhancers to bring the hydrophobic monomers into solution. Polymers were made with different spacing between polymer backbone and phenyl moiety by using styrene, allylbenzene, and 4‐phenyl‐1‐butene as hydrophobic moieties, respectively. The effect of the presence of CDs during synthesis as well as this difference in spacing was investigated by rebinding free β‐CDs to the polymers. The interactions between polymers and CDs were studied by ITC and this revealed some differences between the polymers. Polymers made in the presence of CDs showed a markedly stronger binding to free CDs. The same was observed with polymers with a longer spacing between backbone and phenyl moiety. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6619–6629, 2009     

Water‐soluble,thermoresponsive, hyperbranched copolymers based on PEG‐methacrylates: Synthesis,characterization, and LCST behavior

A series of water‐soluble thermoresponsive hyperbranched copoly(oligoethylene glycol)s were synthesized by copolymerization of di(ethylene glycol) methacrylate (DEG‐MA) and oligo(ethylene glycol) methacrylate (OEG‐MA, M_w = 475 g/mol), with ethylene glycol dimethacrylate (EGD‐MA) used as the crosslinker, via reversible addition fragmentation chain transfer polymerization. Polymers were characterized by size exclusion chromatography and nuclear magnetic resonance analyses. According to the monomer composition, that is, the ratio of OEG‐MA: DEG‐MA: EGD‐MA, the lower critical solution temperature (LCST) could be tuned from 25 °C to 90 °C. The thermoresponsive properties of these hyperbranched copolymers were studied carefully and compared with their linear analogs. It was found that molecular architecture influences thermoresponsive behavior, with a decrease of around 5–10 °C in the LCST of the hyperbranched polymers compared with the LCST of linear chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2783–2792, 2010     

Synthesis and properties of through‐space conjugated polymers based on cyano‐substituted poly(p‐arylenevinylene)s

New through‐space cyano‐substituted poly(p‐arylenevinylene)s containing a [2.2]paracyclophane unit were synthesized by the Knoevenagel reaction. Polymers 5 and 7 have cyano groups at α‐positions and β‐positions from the dialkoxyphenylene unit, respectively. Their optical and electrochemical behaviors were investigated in detail in comparison with their model compounds. Polymers 5 and 7 exhibited through‐space conjugation via the cyclophane units. Polymer 5 showed greenish blue emission (λ_max = 477 nm) in diluted solution with fluorescence quantum efficiency (?_F) of only 0.007, whereas polymer 7 emitted in the bluish green region (λ_max = 510 nm) with ?_F of 0.32. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5979–5988, 2009     

Optically active dimethylsiloxane copolymers with nucleophilic chiral sulfur groups pendant to the polysiloxane chain

Polydimethylsiloxanes with part of the siloxane units bearing an optically active sulfoxide group were synthesized. These copolymers had chiral sulfur centres connected to the siloxane chain by a dimethylene bridge. They were obtained mostly by the kinetically controlled anionic ring-opening polymerization of 1-(2-organothioethyl)1,3,3,5,5-pentamethylcyclotrisiloxanes, followed by stereoselective oxidation of prochiral groups to yield partially enantiomeric sulfoxide groups. Sulfoxides bearing cyclic monomers were also used. Polymers were characterized by spectroscopy and polarimetry. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 879–888, 1997     

End‐capped carbosilane dendrimers with benzoxazole,quinoline, and pyrone derivatives

Dendritic carbosilanes containing benzoxazole, quinoline, and pyrone derivatives on the periphery were prepared. The parent dendrimers in the inner shell were prepared by the use of iterative hydrosilation and alkenylation cycles. The end generations were obtained by the reaction of terminal Si? Cl groups on each periphery with HOR [HOR = 2‐(2‐hydroxyphenyl)‐benzoxazole, 8‐hydroxyquinoline, and 3‐hydroxy‐2‐methyl‐4‐pyrone] in the presence of amine. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2308–2314, 2001     

Synthesis,characterization, and thermal properties of ladderlike polyepoxysiloxanes

Starting from trichlorosilanes and using 1,4‐phenylenediamine as a template, we have synthesized some ladderlike poly(glycidyl‐co‐alkyl/aryl)siloxanes (polyepoxysiloxanes or polyepoxies for short). The structures of copolymers were confirmed through IR, ¹H NMR, elemental analyses, and gel permeation chromatography. Curing behaviors of these polyepoxies in the absence and presence of a curing agent have been studied with DSC. It was shown that these epoxies could be cured without any curing agent. Copolymers having aromatic groups showed higher curing reactivity than those having alkyl groups. The experimental results also demonstrate that the curing reaction occurred solely via epoxy functionality, not via the condensation reaction of the hydroxy groups located at the end of polymer main chains. The thermal stability of the cured polymers was examined by thermogravimetric analysis. The results confirm that polyepoxies with aromatic groups had better thermal stability than those with alkyl groups. It was also found that polyepoxies cured with a diamine have a higher thermal stability than those cured in the absence of a curing agent. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2215–2222, 2001     

Synthesis and mesomorphic behavior of a new series of side-chain liquid crystalline polymethacrylates bearing 2,6-naphthylene-based mesogen

A new homologous series of liquid crystalline (LC) polymethacrylates, the poly[ω-(2-phenoxycarbonyl-naphthalene-6-yloxy)alkyl methacrylate]s, in which the length of the alkyl spacer is varied between 3 and 12 methylene units, have been synthesized by free-radical polymerization. The prepared polymers were studied by IR and ¹H-NMR spectroscopy, viscosity measurements, differential scanning calorimetry (DSC), and polarized microscopy. Polymers with 3 or 4 methylene units spacer were glassy in nature, whereas those with 5–12 methylene units spacer exhibited smectic behavior. The glass transition temperatures decrease on increasing spacer length. The isotropization temperatures and the corresponding transition entropies showed an odd–even effect, with the odd members exhibiting the higher values. This effect attenuates on increasing spacer length. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2391–2399, 1999     

Triple responsive block copolymers combining pH‐responsive,thermoresponsive, and glucose‐responsive behaviors

Polymers with multiple tunable responses were achieved by incorporating boronic acid functionality along the backbone of a thermoresponsive polymer. The inherent Lewis acidity and diol‐sensitivity of boronic acid moieties allowed these polymers to respond to changes in pH and glucose concentration. Through reversible addition‐fragmentation chain transfer copolymerization of boronic acid‐containing monomers with N‐isopropylacrylamide, well‐defined block copolymers were synthesized containing a hydrophilic N,N‐dimethylacrylamide block and a second, responsive block with temperature‐dependent water solubility, making the resulting polymers capable of self‐assembly into nanostructures upon heating. By incorporating boronic acids within the thermoresponsive block, the cloud point of the polymer depended on the solution conditions, including pH and diol concentration, allowing tunable cloud point ranges. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2309–2317     

Substituent effect on the cationic ring‐opening polymerization of acyloxymethyl five‐member cyclic dithiocarbonates

Five‐member cyclic dithiocarbonates were synthesized by the reactions of carbon disulfide with benzoic, p‐anisic, p‐chlorobenzoic, 1‐naphthalenecarboxylic, p‐nitrobenzoic, and p‐(tert‐butyl)benzoic glycidyl esters, and their cationic ring‐opening polymerizations were carried out with methyl trifluoromethane sulfonate and trifluoromethane sulfonic acid as initiators at room temperature to 80 °C. Polymers with number‐average molecular weights of 3400–24,900 were obtained in high yields, and their structures were estimated by NMR and IR spectroscopy. The monomers showed a clear difference in the polymerization rate according to the substituents. The rate of polymerization decreased in the order of p‐chlorobenzoic ≥ benzoic > 1‐naphthalenecarboxylic > p‐nitro‐benzoic > p‐tert‐butylbenzoic > p‐anisic. The data of the reaction kinetics, NMR studies, and molecular orbital calculations proved a plausible mechanism involving the participation of p‐substituted benzoyloxymethyl groups to stabilize the cationic propagating end. The polymers showed decomposition temperatures with 5% weight loss ranging from 200 to 260 °C. No glass‐transition temperatures for the polymers were observed below 200 °C by differential scanning calorimetry. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3967–3980, 2001     

Synthesis and properties of a novel,liquid, trifunctional,cycloaliphatic epoxide

A novel cycloaliphatic triepoxide, 1,1‐bis(2′,3′‐epoxycyclohexyloxymethyl)‐3,4‐epoxycyclohexane ( II ), and its precursor, 1,1‐bis(2′‐cyclohexenyloxymethyl)‐3‐cyclohexene, were synthesized. Their chemical structures were confirmed with IR spectroscopy, elemental analysis, and ¹H NMR spectroscopy. II was easily cured with hexahydro‐4‐methylphthalic anhydride with 1,3,5‐triethylhexahydro‐s‐triazine as a curing accelerator. The physical properties of the cured product were examined with thermomechanical analysis, thermogravimetric analysis, and dynamic mechanical analysis. Compared with the commercial diepoxide ERL‐4221 under the same curing conditions, the cured product based on II showed a much higher glass‐transition temperature (198 °C), a higher crosslinking density (2.08 × 10^?3 mol/cm³), and a lower coefficient of thermal expansion [6.2 × 10⁵(/°C)]. II may become a promising candidate material for modern microelectronic packaging. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2799–2804, 2001     

Synthesis of aminosaccharide‐derived polymers with urea,urethane, and amide linkages

The synthesis of novel polyurethanes and polyureas based on modified glycosylamines and glucosamines has been successfully accomplished by catalytic polymerizations. Several modified glucosamine monomers were synthesized to study their reactivities during these polymerization reactions. It was found that the anomeric hydroxyl groups are more reactive than the amino groups. The resulting polymers were characterized by NMR and IR spectroscopy, elementary analysis, viscosimetry, and gel permeation chromatography. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2332–2341, 2001     

Design of polyethers,thioethers, and amines with pendent iron moieties

Soluble organoiron polyethers, thioethers, and amines were synthesized via nucleophilic aromatic substitution reactions. The synthesis of these classes of organometallic polymers involved either the reaction of cyclopentadienyliron complexes of dichloroarenes with various oxygen and sulfur dinucleophiles or the reaction of ether‐ or amine‐containing diiron complexes with dithiols. Polymerization reactions with the diiron complexes gave rise to organoiron polymers with alternating ether/thioether or amine/thioether bridges. Removal of the iron moieties from the backbone of these polymers allowed for the production of the corresponding organic materials. Furthermore, the organometallic polymers had much higher solubilities than their organic analogues. Thermogravimetric analysis of the organoiron polymers indicated that the polymers lost their metallic moieties at approximately 200 °C, whereas degradation of the polymer backbones occurred around 500 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1216–1231, 2001     

Morphology of micron‐sized,monomer‐adsorbed,crosslinked polymer particles having snowmanlike shapes prepared by the dynamic swelling method

A series of monomer‐adsorbed, crosslinked polystyrene/polydivinylbenzene composite particles having snowmanlike shapes were prepared by the dynamic swelling method that the authors had proposed in 1991. The morphology of the snowman‐shaped particles was estimated with the contact angle of the monomer phase on the polymer particle. Influences of the kind of monomers and polyvinyl alcohol colloidal stabilizer on the morphology were obviously observed and discussed from the viewpoint of thermodynamic stability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3106–3111, 2001