Polymer 3b Research Articles

New Polymer Syntheses Part 56: Novel Friedel-Crafts Polyketones Containing Naphthalene Moiety: Synthesis, Characterization and Antimicrobial Activity

Novel Friedel-Crafts polyketones containing naphthalene moiety were synthesized via the electrophilic Friedel-Crafts polycondensation method. The desired polyketones were obtained by the interaction of newly synthesized dinaphthylidenecycloalkanone monomers with different aliphatic and aromatic diacid chlorides. The structures of new monomers and polymers were confirmed by elemental and spectral analyses, besides X-ray single crystal data for the two new monomers. The new polyketones were characterized by solubility, viscometry, thermal properties, scanning electron microscopy and antimicrobial activity test. All the polyketones were soluble in formic acid as protonic solvent giving yellowish to brown colors. Some of the polyketones were partially soluble in n-hexane, benzene and chloroform. The thermal properties of those polymers were evaluated by TGA; DTG and DTA measurements. The desired polyketones have high thermal stability at T10 except polymer 3b which have low T10 value. FDT for all polyketones is nearly completed at around 522–677°C. The morphological properties of polyketone 2b were tested by SEM measurements. The synthesized monomers and polymers were screened for their antibacterial and antifungal activities. They showed a moderated antibacterial activity against tested Gram-negative and Gram-positive bacteria and no significant influence against the selected fungi species except monomer 1b and polymers 2a , 3b .

Membranes from Poly(aryl ether)-Based Ionomers Containing Randomly Distributed Nanoclusters of 6 or 12 Sulfonic Acid Groups

We report on the dependence of the properties on the morphologies of sulfonated polymers 3a and 3b (ηinh = 0.65−1.18) with segments containing clusters of 6 and 12 sulfonic acid groups, respectively. The larger sulfonated clusters in polymers 3b resulted in higher proton conductivity and much better cell performance than polymers 3a. The highest power density of a fuel cell using 3a-1 (IEC = 1.16 mequiv/g) and Nafion 117 was 0.23 and 0.21 W/cm2, respectively, at the effective work potential of 0.5 V, whereas that of 3b-1 (IEC = 1.16 mequiv/g) was 0.29 W/cm2 at even higher effective work potential of 0.6 V. The morphological structure of 3a-1 and 3b-1 was investigated by transmission electron microscopy (TEM) and compared with that of Nafion. TEM images of 3a-1 and 3b-1 revealed a phase separation similar to that of Nafion, which may explain their higher proton conductivities compared to those of randomly sulfonated copolymers.

Synthesis of new fluorine containing ring-opened polynorbornene dicarboximides using ruthenium alkylidene catalysts

The synthesis of new N-4-trifluoromethylphenyl-exo-endo-norbornene-5,6-dicarboximide (TFmNDI, 2a) and N-3,5-difluorophenyl-exo-endo-norbornene-5,6-dicarboximide (DFNDI, 2b) was carried out. Polynorbornene dicarboximides, 3a and 3b, were obtained via ring opening metathesis polymerization (ROMP) using bis(tricyclohexylphosphine) benzylidene ruthenium(IV) dichloride (I) and tricyclohexylphosphine [1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene] ruthenium dichloride (II), respectively. Tg’s for polymers 3a and 3b were observed at 155 C and 142 C, respectively. Compared to polymer 3b, polymer 3a with the bulky trifluoromethyl group showed the highest glass transition temperature and improved mechanical properties.

Synthesis and electrochromism of novel organosoluble polyarylates bearing triphenylamine moieties

AbstractA series of novel aromatic polyarylates with triphenylamine units in the main chain and as the pendent group were prepared from the dicarboxylic acid monomer, N,N‐bis(4‐carboxyphenyl)‐N′, N′‐diphenyl‐1,4‐phenylenediamine (1), and various bisphenols. These polyarylates were amorphous and readily soluble in common organic solvents. They had excellent levels of thermal stability associated with moderately high Tg values (182–263 °C). These polymers exhibited strong UV–vis absorption bands at 357–360 nm in toluene solution and the photoluminescence spectra showed maximum bands around 493–503 nm in the green region. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyarylates exhibited two reversible oxidation redox couples in acetonitrile solution at Eonset 0.77–0.79 V and 1.12–1.14 V, respectively. The typical polymer 3b film revealed good stability of electrochromic characteristics, with color change from colorless to green and blue at applied potentials ranging from 0.00 to 1.24 V. These anodically polymeric electrochromic materials not only showed excellent reversible electrochromic stability with good green coloration efficiency (CE = 159 cm2/C) and blue coloration efficiency (CE = 154 cm2/C) but also exhibited high contrast of optical transmittance change (ΔT%), 54% in 895 nm for green color and up to 84% in 595 nm for blue color. After over 100 cyclic switches, the polymer films still exhibited excellent stability of electrochromic characteristics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2004–2014, 2007

Synthesis and characterization of poly(diphenylacetylenes) containing both hydroxy and halogen/alkyl groups as gas separation membranes

Diphenylacetylene containing siloxy and halogen/alkyl groups ( P- t-BuMe 2SiO-C 6H 4C CC 6H 4- p-X, X = Cl, Br, I, Me, Et, 1b– f, respectively) were polymerized with TaCl 5- n-Bu 4Sn catalyst to provide high molecular weight polymers ( 2b– f) in good yields. These polymers afforded tough free-standing membranes by casting from toluene solution. Desilylation of these siloxy-containing polymer membranes was carried out with trifluoroacetic acid to give membranes of poly(diphenylacetylenes) having hydroxy and halogen/alkyl groups ( 3b– f). Polymers 2b– f were soluble in nonpolar solvents such as cyclohexane, toluene, and THF, while polymers 3b– f were insoluble in these solvents. The oxygen permeability coefficients ( P O 2 ) of membranes 2b– f and 3b– f were in the range of 140–280 and 12–190 barrers, respectively. The gas permeabilities of most membranes ( 2b– e and 3b– f) were higher than those of the corresponding polymer membranes without halogen/alkyl substituents ( 2a and 3a), suggesting that introduction of small spherical groups (halogen and methyl) into the polymers 2a and 3a enhances gas permeability. The incorporation of halogen atoms into the present membranes was more effective to improve gas permeability than methyl and ethyl groups. The points of 3b– e in the P C O 2 versus P C O 2 / P N 2 and P C O 2 / P C H 4 plots were located obviously above Robeson's upper bound.

Synthesis, Characterization, and Photophysical, Electrochemical, Electroluminescent, and Photovoltaic Properties of Yne-Containing CN−PPVs

Alkoxy-substituted CN-containing phenylene−vinylene−alt-phenylene−ethynylene hybrid polymers (CN−PPV−PPE), 3a, 3b, and 7a, were obtained from luminophoric dialdehydes 1 by step growth polymerization via Knoevenagel reaction as high molecular-weight materials. Corresponding CN-free polymers 3c and 7b and an ethynylene-free polymer 5 with similar side chains were synthesized for the purpose of comparison. The chemical structures of the polymers were confirmed by IR, 1H and 13C NMR, and elemental analysis. Thermal characterization was conducted by means of thermogravimetric analysis and differential scanning calorimetry. Morphology was investigated by means of optical microscopy and small-angle light scattering. The final morphologies are determined by the molecular characteristics (side chains volume fraction, backbone stiffness) of the studied polymers. All the CN-containing polymers 3b, 5, and 7a exhibit higher fluorescence quantum yield in solid state (50 to 60%), but lower quantum yields (12−40%) in dilute chloroform solution, in total contrast to CN-free polymers 3c, 3d, and 7b. Identical optical, Egopt, and electrochemical band gap energies, Egec, were obtained for 3b, 3c and 3d with intrinsic self-assembly ability, whereas a discrepancy, ΔEg, was observed in the cases of the fully substituted polymers 5, 7a, and 7b, whose values are dependent on the level of backbone stiffness and length of the side groups combined with the presence or absence of CN units. The incorporation of CN units in 3b and 7a lowers their respective LUMO level by 220 and 350 meV compared to their corresponding CN-free counterparts 3c and 7b, suggesting an improvement of the electron-accepting strength. Polymers 3b and 7a are efficient electron acceptors suitable for photovoltaic application. The experiments indicate that 3b is a better electron acceptor when used together with M3EH−PPV, but transport properties seem to be better for 7a. With 3b, high external quantum efficiencies of up to 23%, an open circuit voltage of up to 1.52 V, and a white light energy efficiency of 0.65% could be realized in bilayer solar cell devices. LED-devices of configuration ITO/PEDOT:PSS/polymer/Ca/Al from 3b, 3c, 7a, and 7b showed low turn-on voltages between 2 and 2.5 V. The CN-free polymers 3c and 7b exhibit far better EL parameters than their corresponding CN containing counterparts 3b and 7a.

Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

AbstractPoly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} (3a), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} (3b), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} (3c) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by 1H and 13C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004

Copper-Mediated Polycondensations of Substituted Diiodoferrocenes and Bis(stannyl)ferrocenes: Synthesis and Properties of Soluble Polyferrocenylenes Containing Trimethylsilyl or Methyl Groups

Low to moderate molecular weight substituted polyferrocenylenes [(η5-C5H3X)Fe(η5-C5H3X)]n (where 3a−3c, X = H, SiMe3, Me) were prepared from the Ullmann coupling reaction of the diiodoferrocenes, (η5-C5H3XI)2Fe (2a−2c), with an excess of copper metal or alternatively CuCl-facilitated coupling of the bis(stannyl)ferrocene, (η5-C5H3SiMe3SnBu3)2Fe (1b). The new monomers were characterized by 1H and 13C NMR spectroscopy, elemental analysis and mass spectrometry. A single-crystal X-ray diffraction study (η5-C5H3SiMe3I)2Fe (2b) shows the disubstituted cyclopentadienyl rings are eclipsed with the substituents staggered by 20°. The molecular weights (Mw) for the soluble homopolymers 3b and 3c were estimated by gel permeation chromatography in THF vs polystyrene standards and were found in the range from 2.0 × 103 to 1 × 104 with generally broad polydispersities (PDI > 2). Polymers 3b and 3c were characterized by 1H and 13C NMR spectroscopy and elemental analysis. The polymer thermal transition behavior and morphology of 3a−3c were examined by differential scanning calorimetry (DSC) and by powder X-ray diffraction (PXRD). The amorphous nature of the disubstituted polymers 3b and 3c was evident by the presence of weak glass transitions and the absence of any melt transitions. In contrast, the semicrystalline nature of the largely insoluble polyferrocenylene 3a led to the presence of a strong melt transition by DSC in addition to three sharp peaks in its the PXRD spectrum. The polymers 3b and 3c as well as their I2 and TCNE oxidized products (4b, 4c and 5b, 5c) were characterized by UV/vis/NIR spectroscopy. The neutral polymers 3b and 3c showed only weak d−d visible transition centered near λ = 480 nm, while the partially oxidized derivatives showed strong charge-transfer peaks in the visible λ = 630−700 nm) and broad intervalence charge-transfer transitions between λ = 850 and 1900 nm. Cyclic voltammetry of the neutral polymers 3b and 3c showed two well-separated oxidation waves with ΔE1/2 values of 485 and 460 mV s-1 respectively and were consistent with substantial interaction between neighboring metal centers. Mössbauer data of the partial oxidized dimethylferrocene polymer 5c with TCNE at room temperature indicates that electron transfer is valence trapped with distinct Fe2+ and Fe3+ sites.

Chirality Induction in Cyclocopolymerization. 14. Template Effect of 1,2-Cycloalkanediol in the Cyclocopolymerization of Bis(4-vinylbenzoate)s with Styrene

A series of chiral 1,2-cycloalkanediols including (1S,2S)-1,2-cyclopentanediol, (1S,2S)-1,2-cyclohexanediol, (1S,2S)-1,2-cycloheptanediol, and (1S,2S)-1,2-cyclooctanediol (a, b, c, and d) were used as chiral templates in the cyclocopolymerization of bis(4-vinylbenzoate)s (1a−d) with styrene. The copolymerizations of 1a with styrene produced an insoluble gel at a high mole fraction of 1a in the feed. On the other hand, the copolymerization of 1b−d with styrene proceeded homogeneously to yield polymers 2b−d, which were soluble in chloroform and tetrahydrofuran. After the removal of the chiral template from the resulting polymers 2a−d, polymers 3b−d exhibited optical rotations ([α]435, c 1.0, CHCl3) of −2.2 to −17.9° whose signs were opposite to those of polymers 2b−d, while polymer 3a showed little or no optical activity. Hence, the efficiency of templates on the chirality induction improved by expansion of the ring size of the chiral template; i.e., 1a ≪ 1b < 1c < 1d. The A values of the CD spectra of mono...

New Chiral Polyurethane Polymers Based on Functionalized Cyclotriphosphazenes

Novel hybrid polymers using chiral phosphaznes were prepared in the following way: Starting from hexachlorocyclofriphosphazene, N3,P3,Cl6, chelating phenolates were introduced by reaction with the corresponding sodium salt. Thus, reaction with two equivalents of atropisomeric binaphtolate yields chiral lb in high yield. Subsequently, p-methoxyphenolates were reacted with the remaining PCl2, functionality and the p-MeO groups were converted to hydroxy groups [I] to give bifunctional 2a,b. Finally, polyadditions to diisocyanates lead to new cyclolinear polyurethanes 3a,b which were characterized by thermal analysis [2,3]. The T10, is 320 and 240°C for 3a and 3b respectively. In particular, the chifal polymer 3b [α=lll°] may have interesting properties as catalyst support.

Kinetics and Thermodynamics of the Inclusion of Ionene-6,10 in α-Cyclodextrin in an Aqueous Solution

The kinetics of the inclusion of ionene-6,10 (3b) dibromide and of its monomeric model, 1,10-bis(trimethylammonium)decane (5) diiodide, by α-cyclodextrin (1a) were investigated by 1H NMR spectroscopy in an aqueous solution. The inclusion of the monomer 5 is unusually slow and shows a high activation energy, Ea = 63 kJ mol-1, which was attributed to a high steric hindrance for the threading caused by the terminal trimethylammonium groups. Microcalorimetric titration of 5 with 1a revealed a stability constant, KS = 1540 M-1, of the inclusion compound. Because of its high kinetic stability, 5·1a was termed a rotaxane. The inclusion of the ionene polymer by α-cyclodextrin takes days, months, or even years depending on the temperature. The kinetics could be described quantitatively by a Monte Carlo type of computer simulation of a consecutive hopping process of the rings along the polymer chain. The rate constants and activation energies for the polymer 3b were found to be similar to those for the monomer 5. A very high occupation of the polymer 3b (95% of the repeat units) was reached by the thermally induced threading of 1a. The resulting supramolecular structure of one polymer chain and about 65 rings was termed a polyrotaxane, as it can be isolated by GPC or dialysis.

Synthesis and properties of new crystalline poly(arylene ether)s containing pendant benzoyl groups

Poly(arylene ether)s (3) containing pendant benzoyl groups were prepared by the aromatic substitution reaction of 2,5-difluoro-4-benzoylbenzophenone (2) with hydroquinone (1a) and methylhydroquinone (1b) in the presence of potassium carbonate in N,N-dimethylacetamide. The polycondensation proceeded smoothly at 165°C and produced poly(arylene ether)s with inherent viscosities up to 0.8 dL/g. The polymer (3b) derived from methylhydroquinone was quite soluble in common organic solvents and could be processed into uniform films from solutions. On the other hand, the polymer (3a) derived from hydroquinone was only soluble in pentafluorophenol and methanesulfonic acid and had a high crystallinity. These polymers showed 10% weight losses at around 420 and 490°C in nitrogen. Polymer 3b also showed good tensile strength and tensile moduli. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 605–611, 1997

Synthesis and properties of new crystalline poly(arylene ether)s containing pendant benzoyl groups

Poly(arylene ether)s (3) containing pendant benzoyl groups were prepared by the aromatic substitution reaction of 2,5-difluoro-4-benzoylbenzophenone (2) with hydroquinone (1a) and methylhydroquinone (1b) in the presence of potassium carbonate in N,N-dimethylacetamide. The polycondensation proceeded smoothly at 165°C and produced poly(arylene ether)s with inherent viscosities up to 0.8 dL/g. The polymer (3b) derived from methylhydroquinone was quite soluble in common organic solvents and could be processed into uniform films from solutions. On the other hand, the polymer (3a) derived from hydroquinone was only soluble in pentafluorophenol and methanesulfonic acid and had a high crystallinity. These polymers showed 10% weight losses at around 420 and 490°C in nitrogen. Polymer 3b also showed good tensile strength and tensile moduli. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 605–611, 1997

Topologically unique side‐chain polyrotaxanes based on triacetyl‐β‐cyclodextrin and a poly(ether sulfone) main chain

AbstractThe synthesis and NMR‐spectroscopical characterization of the topological arrangements of new side‐chain polyrotaxanes (3a) bearing about 80% of peracetylated cyclodextrins in the side‐chains of a functionalized poly(ether sulfone) is described. The characterizations have been conducted in relation to a similar model compound bearing no cyclodextrins (3b). The results strongly indicate that the cyclodextrins are uniformly located on the side chains, with the bigger opening over the aromatic anilide components of the barrier group. The glass transition temperature (Tg) of the polyrotaxane 3a is in the region of 143°C, which is significantly higher than that of the model polymer 3b having a value of 111°C.

Synthesis of photoreactive poly(ether ether ketone)s containing alkyl groups

Poly(ether ether ketone)s containing alkyl groups were prepared by nucleophilic substitution reaction of alkyl-substituted difluoro diaryl ethers with hydroquinone or by electrophilic substitution reaction of alkyl-substituted diaryl ether with 4,4′-oxydibenzoic acid in PPMA. Polycondensations proceeded smoothly and produced polymers having inherent viscosities up to 0.5-–1.6 dL/g. The polymers were quite soluble in strong acid, dipolar aprotic solvents, and chloroform at room temperature. Thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight loses of the polymers were observed in the range above 450°C in nitrogen atmosphere. The glass transition temperatures of the polymers ranged from 128 to 146°C. Furthermore, Polymer 3b functioned as a photosensitive resist of negative type for UV radiation. The resist had a sensitivity of 42 mJ/cm2 and a contrast of 2.5, when it was postbaked at 100°C for 10 min, followed by development with THF/acetone at room temperature. © 1996 John Wiley & Sons, Inc.

Nonlinear optically active polymethacrylates with high glass transition temperatures

AbstractA number of novel nonlinear optically (NLO) active polymethacrylates were prepared from the NLO active methacrylates 2a–d with azobenzene side groups and the bulky comonomer 1‐adamantyl methacrylate. The polymers exhibit unusually high glass transition temperatures between 160°C and 190°C. The copolymerization parameters of the monomer pair 1‐adamantyl methacrylate (1)/Disperse red methacrylate 2b (r1 = 1,1 ± 0,2, r2 = 0,8 ± 0,2) show that the two monomers are incorporated almost statistically into the polymer chain. Polymers 3a–d are soluble in common organic solvents and excellent films can be obtained by spin coating. After poling in an electric field of 120 V/μm polymer 3b shows a large electrooptic (EO) coefficient (r33) of 25 pm/V at 633 nm. Within two weeks, only a negligible decay of 7% of the EO coefficient was observed at room temperature. On‐line monitoring of the second harmonic generation (SHG) at 100°C showed a fast initial drop (10%) of the SHG signal and subsequently a slow decay of 20% within 10 h. Afterwards, the signal remained almost constant for further 5 h at 100°C. The novel polymers can thus be considered as easy processible NLO materials with a high thermal stability of the chromophore orientation obtained by poling.

Effect of Metal Complexation on the Behavior of Liquid Crystalline Polymer

Abstract Liquid crystalline side-chain polymers (3b-3f) crosslinked by a trans Pt(II) complex were synthesized by a ligand exchange reaction with dichlorobis(benzonitrile)platinum(II) and poly(methylsiloxane) (3a) bearing a p-cyanobiphenyloxy mesogen unit attached to the polymer backbone by a flexible spacer group. The amount (x) of p-cyanobiphenyloxy mesogen coordinating to the Pt(II) ion in polymers 3b, 3c, 3d, 3e, and 3f was 4.9, 9.7, 14.8, 20.2, and 49.6 mol%, respectively. The effect of Pt(II) coordination on the thermotropic liquid crystalline behavior of 3a was examined by DSC, x-ray diffraction, and polarizing microphotography. Polymers 3a-3d exhibited a nematic mesophase between Tg and Tc. On the other hand, 3e-3f, which have a large amount of Pt(II)-coordinating mesogen, did not show a definite nematic mesophase, but exhibited an ambiguous one. The introduction of Pt(II) ion into 3a resulted in a crosslinked structure and consequently prevented the formation of the ordered nematic mesophase.

Novel monomeric and polymeric azo initiators

Abstract1‐Methyl‐1‐(3‐vinylphenylazo)ethyl acetate (1a), diphenyl‐(3‐vinylphenylazo)methyl acetate (1b), and α‐phenylazo‐α‐(4‐vinylphenyl)benzyl acetate (2) were prepared and copolymerized with styrene using AIBN as initiator at 50°C. The azo functions of the monomers remain unaltered during the polymerization process at this temperature. The resulting copolymers 3a, 3b, and 4 were used as initiators for the polymerization of methacrylonitrile (MAN). The grafted copolymers of styrene and MAN were separated from polystyrene and poly(methacrylonitrile). The different rates of polymerization of MAN, initiated by the azo group containing polymer 3b or 4 or by diphenylphenylazomethyl acetate, a low molecular model initiator, and the different molar masses obtained allow a discussion of the mechanism involved.

Donor acceptor interactions in polymeric systems, 2. Polyesters from N‐[5,5‐bis(hydroxymethyl)hexyl]carbazole

AbstractPolyesters with a pendant 9‐carbazolyl group were prepared by polycondensation of 9‐[5,5‐bis(hydroxymethyl)hexyl]carbazole (1a) with diethyl malonate, dimethyl terephthalate, and adipoyl chloride. Charge transfer complex formation of these polyesters and their monomeric model compound with 2,4,7‐trinitrofluorenone (TNF) was investigated by means of absorption spectroscopy in 1,2‐dichloroethane.Stability constants (K) of the polymeric systems were always larger than that of the monomeric system in the following order: polymer 3c (with the terephthaloyl unit) &gt; polymer 3a (with the malonyl unit) ≈ polymer 3b (with the adipoyl unit) &gt; 9‐[5,5‐bis‐(acetoxymethyl)hexyl]carbazole (2b).From the measurements of monomer and excimer emission in dilute solutions, interactions between the 9‐carbazolyl groups are discussed for the polymers and the monomeric model compound. For the polymer 3c (containing the terephthaloyl unit), exciplex formation between the 9‐carbazolyl group and the terephthaloyl group was demonstrated. Polymer effects on K are discussed based on the structural information obtained from fluorescence measurements.