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1.
A series of thermotropic side‐chain liquid‐crystalline ionomers (LCIs) containing 4‐(4‐alkoxybenzyloxy)‐4′‐allyloxybiphenyl (M) as mesogenic units and allyl triethylammonium bromide (ATAB) as nonmesogenic units were synthesized by graft copolymerization upon polymethylhydrosiloxane. The chemical structures of the polymers were confirmed by IR spectroscopy. DSC was used to measure the thermal properties of these polymers. The mesogenic properties were characterized by polarizing optical microscopy, DSC, and X‐ray diffraction. Homopolymers without ionic groups exhibit smectic and nematic mesophases. The nematic mesophases of the ionomers disappear and the mesomorphic temperature ranges decrease with increasing concentration of ionic units. The influence of the alkoxy chain length on clearing temperature (Tc) values of ionomers clearly shows an odd‐even effect, similar to that of other side‐chain liquid‐crystalline polymers. The mesomorphic temperature ranges increase with increasing alkoxy chain length when the number of alkoxy carbon is over 3. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2879–2886, 2003  相似文献   

2.
Side‐chain liquid crystalline ionomers containing M1 (4‐allyoxybenzoyloxy‐4′‐amylbenzoyloxy biphenyl) as mesogenic units and M2 (4‐undecylenicoxy‐4′‐phenylazobenzene sulfonic acid) as ionic units were synthesized by graft copolymerization. Their liquid crystalline properties were characterized by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The results showed that introduction of nonmesogenic ionic units into polymeric structure could cause additional reduction of the clearing point of the ionomers, compared with the corresponding nonion polymers. When the content of ionic units increased to 8.5%, the ionic clusters and mesogens in the ionomers may be dispersed each other to form multiple blocks, but the introduction of ionic groups in LCIs did not change their mesogenic type. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 304–309, 2007  相似文献   

3.
A novel thermotropic side-chain liquid crystalline ionomer (LCI) containing sulfonic acid groups on the side-chain was synthesized by graft copolymerization of mesogenic monomer 4-allyloxy-benzoxy-4′-methoxyphenyl (ABM) and nonemesogenic monomer 4-allyloxy-azobenzene sulfonic acid (AABS) upon polymethylhydrosiloxane (PMHS). The chemical structures of the polymers were confirmed by IR spectroscopy. DSC and TGA were used to measure the thermal properties of those polymers and the mesogenic properties were characterized by polarized optical micrography (POM), DSC, and WAXD. The clearing point temperature (Tc) of these liquid crystalline ionomers was enhanced 50–60°C compared with the polymer without ionic groups. The LCIs exhibit a broad smectic mesogenic region of 80–90°C; the thermal stability below 200°C of the polymers decreases with increasing sulfonic acid concentration. The inherent viscosity of 0.5% solutions decreased with increasing sulfonic acid concentration in the polymer chains. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1555–1561, 1998  相似文献   

4.
In this study, synthesis, characterization, partial hydrolysis, and salt formation of poly(2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine), (poly(HEMA)‐co‐poly‐(4‐VP)) copolymers were investigated. The copolymers were synthesized by free radical polymerization using K2S2O8 as an initiator. By varying the monomer/initiator ratio, chain lengths of the copolymers were changed. The copolymers were characterized by gel permeation chromatography (GPC), viscosity measurements, 1H and 13C NMR and FTIR spectroscopies, elemental analysis, and end group analysis methods. The copolymers were partially hydrolyzed by p‐toluene sulfonic acid monohydrate (PTSA·H2O) and washed with LiOH(aq) solution to prepare electrorheological (ER) active ionomers, poly(Li‐HEMA)‐co‐poly(4‐VP). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3540–3548, 2006  相似文献   

5.
Three series of main‐chain liquid‐crystalline polymers (P1, P2, and P3) were synthesized by an interfacial condensation reaction of sebacoyl dichloride with various amount of brilliant yellow, isosorbide, and 4,4′‐biphenydiol. P1 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol and isosorbide. P2 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol, brilliant yellow, and isosorbide. P3 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol and brilliant yellow. P2 and P3 are main‐chain liquid‐crystalline ionomers. P12 and P3 series were prepared as model polymers for comparison with the liquid crystalline behavior of ionomers, P2 series. The structures of the polymers were characterized by IR and UV spectroscopy. Differential scanning calorimetry was used to measure the thermal properties of the polymers. The mesogenic properties were investigated by polarized optical microscope, differential scanning calorimetry, and X‐ray diffraction measurements. The results show that P2 series are chiral smectic C (SmC*) and chiral smectic B (SmB*) liquid crystalline ionomers exhibiting broken focal‐conic texture and schlieren, as is the polymer P12, which has the same amount of 4,4′‐biphenydiol and isosorbide. The introduction of ionic units in P2 series leads to an increase of clearing point, but has not affected the mesogenic type and texture, as compared with the corresponding polymer P12. The introduction of chiral units in P2 series leads to a change of mesophase, as compared with P3 series, which exhibit smectic C mesogetic phase. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1254–1263, 2006  相似文献   

6.
Sulfonation of highly stereoregular syndiotactic polystyrene has been accomplished in 1,1,2‐trichloroethane and chloroform (60/40 v/v) mixed solvent. FTIR spectroscopy was used to confirm that the sulfonated syndiotactic polystyrene was the product of the sulfonation reactions. Sodium, potassium, zinc (II), manganese (II) and cobalt (II) salts of the sulfonated polymers exhibited behaviour indicative of strong interactions. FTIR spectroscopy and DSC data showed that the roles of the cation–anionic site interactions in alkali form and transition metal form ionomers are somewhat different. The DSC data also showed that the alkali metal cations had more pronounced effect on Tg than did the transition metal cations. In addition, the crystallization behaviour of the ionomers with a low degree of sulfonation also exhibited considerable differences in comparison with the neat syndiotactic polystyrene. The melting points (Tm) and the degree of crystallization (Xc) were significantly lowered by the presence of the sulfonic acid groups or the sulfonate metal groups. Moreover, the ionomers were more thermally stable and more hygroscopic than the unmodified polymer. © 2001 Society of Chemical Industry  相似文献   

7.
The synthesis of chiral side‐chain liquid‐crystalline polysiloxanes containing both cholesteryl undecylenate (MI) and 4‐allyloxy‐benzoyl‐4‐(S‐2‐ethylhexanoyl) p‐benzenediol bisate (MII) mesogenic side groups was examined. The chemical structures of the obtained monomers and polymers were confirmed with Fourier transform infrared spectroscopy or 1H‐NMR techniques. The mesomorphic properties and phase behavior of the synthesized monomers and polymers were investigated with polarizing optical microscopy, differential scanning calorimetry, and thermogravimetric analysis (TGA). Copolymers IIP–IVP revealed a smectic‐A phase, and VP and VIP revealed a smectic‐A phase and a cholesteric phase. The experimental results demonstrated that the glass‐transition temperature, the clearing‐point temperature, and the mesomorphic temperature range of IIP–VIP increased with an increase in the concentration of mesogenic MI units. TGA showed that the temperatures at which 5% mass losses occurred were greater than 300°C for all the polymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2670–2676, 2002  相似文献   

8.
The synthesis of hemiphasmidic monomers 4‐[(3,4,5‐triethoxy)benzoyloxy]‐4′‐[(p‐allyloxy)benzoyloxy]biphenyl (M1), 4‐[(3,5‐diethoxy)benzoyloxy]‐4′‐[(p‐allyloxy)‐benzoyloxy]biphenyl (M2), and of the corresponding side‐chain liquid‐crystalline polysiloxanes (P1, P2) was carried out. For comparison, rodlike monomer 4‐[(p‐ethoxy)‐benzoyloxy]‐4′‐[(p‐allyloxy)benzoyloxy]biphenyl (M3) and its polysiloxanes (P3) were also prepared. The chemical structures of the monomers and polymers obtained were confirmed by FTIR and 1H‐NMR spectra. Their mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The relationship between structures and properties was discussed. It was observed that M1 and M3 were enantiotropic nematic phase, M2 was monotropic mesophase, and their poly(methylsiloxanes) (P1–P3) possessed a broad range enantiotropic nematic phases and high thermal stability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 946–952, 2005  相似文献   

9.
The surface behaviour of poly(4‐vinylpyridine)s (P4VP) quaternized with four different alkyl chains (pentyl, hexyl, octyl and decy bromide) were studied. Surface pressure–area isotherms (π–A) at the air–water interface were determined. Depending on the length of the side‐chains, the π–A isotherms show a plateau region. An extensive plateau is observed for n > 6. The plateau pressures are similar for n = 8 and n = 10. The monolayers are stable and exhibit hysteresis phenomena. Brewster angle microscopy (BAM) is used to monitor the monolayer topography of the polymer on water subphase. To obtain information about the surface energy (SE) and the degree of hydrophobicity of these systems, we have estimated the critical surface tension, γc, and the dispersion force and polar contributions to SE, γD and γP, respectively, by measurements of the contact angle (CA) of water and bromobenzene on the polymer surface. The results obtained are depend on the length of the alkyl lateral chain of the functionalized polymers. © 2001 Society of Chemical Industry  相似文献   

10.
A series of sulfonated poly(arylene biphenylsulfone ether) polymers containing up to two pendant sulfonic acid groups per repeat unit were successfully synthesized from 4,4′‐bis[(4‐chlorophenyl)sulfonyl]‐1,1′‐biphenyl (BCPSBP), disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone (SDCDPS) and bisphenol A via aromatic nucleophilic displacement polycondensation. The resulting polymers were characterized by means of Fourier transform infrared and 1H NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis (TGA). The number‐average molecular weight (Mn) of the synthesized polymers was in the range 15 300–22 900 g mol?1, and the polydispersity indices (Mw/Mn) varied from 2.5 to 4.4. Tough membranes with SDCDPS/BCPSBP mole ratio up to 50:50 were successfully cast using N‐methyl‐2‐pyrrolidone (NMP). An increase of sulfonic acid groups in the polymer backbone resulted in increased solubility in aprotic polar solvents and glass transition temperature. The TGA curves of all the copolymers in acid form exhibited two distinct weight‐loss profiles. The influential characteristics of the polymer electrolyte membranes, such as tensile strength, water uptake, ion‐exchange capacity and proton conductivity, were characterized with respect to the pendant sulfonic acid groups. Atomic force microscopy phase images of the acid‐form membranes clearly showed the hydrophilic domains, with sizes increasing as a function of the degree of sulfonation. Copyright © 2010 Society of Chemical Industry  相似文献   

11.
Novel cyclomatrix phosphazene‐containing polyester polymers were synthesized through the reaction of a polyhydroxylated cyclotriphosphazene and a bifunctional acid chloride. To demonstrate the chemistry of the free hydroxyl of hexa‐[3‐tert‐butyl‐4‐hydroxyphenoxy]cyclotriphosphazene, nucleophilic displacement reactions were performed with both acetic anhydride and alkyl chlorides. This work compares favorably to literature data for the chemistry of hexa‐[4‐hydroxyphenoxy]cyclotriphosphazene, whose hydroxyl is not hindered by an adjacent substituent. The hindered site of hexa‐[3‐tert‐butyl‐4‐hydroxyphenoxy]cyclotriphosphazene was found to react with bidentate acid chlorides to yield new high polymers. The phosphazene‐containing polyesters were observed to have good solubility in polar organic solvents. Characterization of these new materials was performed using dilute solution laser light scattering techniques, thermal analysis, and NMR spectroscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 242–251, 2001  相似文献   

12.
GY Han  GQ Shi  LT Qu  JY Yuan  FE Chen  PY Wu 《Polymer International》2004,53(10):1554-1560
N‐Substituted pyrrole derivatives with chiral side groups have been synthesized and electrochemically polymerized in acetonitrile containing tetrabutylammonium perchlorate (TBAClO4) and (S)‐(+)‐camphor‐10‐sulfonic acid ((S)‐(+)‐CSA) or (R)‐(?)‐camphor‐10‐sulfonic acid ((R)‐(?)‐CSA). The resulting N‐substituted polypyrrole films were characterized by cyclic voltammetry, infrared, Raman and X‐ray photoelectron (XPS) spectroscopies. XPS results demonstrated that the as‐grown polymer films are preferably doped by CSA anions when the monomer and the CSA anion have the same optical rotation dispersion (ORD). Furthermore, the conductivities of the polymers synthesized in the media containing CSA with the same ORD of the corresponding monomers were measured to be about 2–10 times higher than those of polymers obtained from electrolytes without CSA. Copyright © 2004 Society of Chemical Industry  相似文献   

13.
The synthesis of new chiral side‐chain liquid‐crystalline polysiloxanes containing p‐(allyoxy)benzoxy‐p‐chlorophenyl (ABCH) as mesogenic units and undecylenic acid menthol ester (UM) as chiral nonmesogenic units is presented. The chemical structures of monomers and polymers are confirmed by IR spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) are used to measure thermal properties of those polymers. Mesogenic properties are characterized by polarized optical microscope (POM), DSC, and small‐angle X‐ray diffraction. Analytic results revealed that polymers P0–P6 are thermotropic liquid‐crystalline polymers with low glass transition; Polymers P2–P6 exhibit chiral smectic liquid‐crystalline properties with marble texture, optical rotation, and a sharp reflection at low angles in X‐ray diffraction; polymers P0, P1 only exhibit smectic liquid‐crystalline properties without chirality; and P7 only exhibits chirality without liquid‐crystalline properties. All the polymers exhibit good thermal stability with temperature of 5% mass loss over 297°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2845–2851, 2003  相似文献   

14.
Polyphenylenes consisting of nitrophenylene and didodecyloxy‐p‐phenylene units have been synthesized by Pd‐catalyzed organometallic polycondensation. The polymers showed good solubility and had number–average molecular weights (Mn) of 13,000–37,000. Their spin‐coated films showed fairly high dielectric constants (ε) of 3.75–6.36. The polymers were electrochemically active with electrochemical reduction peaks in the range of ?1.72 to ?1.99 V versus Ag+/Ag in an acetonitrile solution of [NEt4]BF4 (0.10M). The polymer composed of 2,3′‐dinitrobiphenyl and didodecyloxy‐p‐phenylene units showed thermotropic liquid crystalline phase at about 240°C. Cast films of the polymer had a birefringent phase at room temperature, suggesting self‐assembly of the polymer in the solid. XRD studies revealed that the polymers assumed an ordered structure assisted by aggregation of the long alkoxy side chains in the solid. The polymer main chain in the cast film is considered to be aligned parallel with respect to the surface of substrates. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

15.
[2,6‐Bis(4‐hydroxybenzylidene)cyclohexanone] (HBC) was prepared by reacting cyclohexanone and p‐hydroxybenzaldehyde in the presence of acid catalyst. Acrylated derivative of HBC, 4‐{[‐3‐(4‐hydroxybenzylidene)‐2‐oxocyclohexylidene]methyl}phenyl acrylate (HBA), was prepared by reacting HBC with acryloyl chloride in the presence of triethylamine. Copolymers of HBA with styrene (S) and methyl acrylate (MA) of different feed compositions were carried out by solution polymerization technique by using benzoyl peroxide (BPO) under nitrogen atmosphere. All monomers and polymers were characterized by using IR and NMR techniques. Reactivity ratios of the monomers present in the polymer chain were evolved by using Finnman–Ross (FR), Kelen–Tudos (KT), and extended Kelen–Tudos (ex‐KT) methods. Average values of reactivity were achieved by the following three methods: r1 (S) = 2.36 ± 0.45 and r2 (HBA) = 0.8 ± 0.31 for poly(S‐co‐HBA); r1 = 1.62 ± 0.06 (MA); and r2 = 0.12 ± 0.07 (HBA) for poly(MA‐co‐HBA). The photocrosslinking property of the polymers was done by using UV absorption spectroscopic technique. The rate of photocrosslinking was enhanced compared to that of the homopolymers, when the HBA was copolymerized with S and MA. Thermal stability and molecular weights (Mw and Mn) were determined for the polymer samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2494–2503, 2004  相似文献   

16.
A variety of fluoroalkyl end‐capped 3‐[N‐(3‐acrylamido)propyl‐N,N‐dimethylammonio]propanesulfonate polymers [RF–(APDAPS)n–RF] were prepared by the reactions of fluoroalkanoyl peroxides with the corresponding monomer under very mild conditions. Similarly, fluoroalkyl end‐capped 2‐vinylpyridinio propane sulfonate polymer was obtained by the use of fluoroalkanoyl peroxide. These fluoroalkyl end‐capped sulfobetaine polymers exhibited a good solubility in water; however, these polymers have a poor solubility in other solvents. In particular, RF–(APDAPS)n–RF polymers caused gelation in methanol, although RF–(VPPA)n–RF polymer showed no gelation in methanol. RF–(APDAPS)n–RF polymers were found to form the self‐assembled molecular aggregates with the aggregations of the end‐capped fluoroalkyl segments and the ionic interactions between sulfobetaine segments in aqueous solutions. On the other hand, it was suggested that RF–2‐vinylpyridinio propane sulfonate (VPPS)n–RF polymer is not likely to form the self‐assemblies in aqueous solutions because of the steric hindrance of pyridiniopropyl betaine units in polymer. We also studied the surfactant properties of RF–(APDAPS)n–RF and RF–(VPPS)n–RF polymers compared with those of other fluoroalkyl end‐capped betaine‐type polymers such as 2‐acrylamido‐2‐methylpropanesulfonic acid polymers and 2‐(3‐acrylamidopropyldimethylammonio) ethanoate polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1144–1153, 2004  相似文献   

17.
The synthesis of side chain cholesteric liquid‐crystalline polymers containing both 4‐cholesteryl‐4'‐acryloyloxybenzoate (MI) and 4‐methoxyphenyl‐4'‐acryloyloxybenzoate (MII) mesogenic side groups is described. The chemical structures of the obtained monomers and polymers are confirmed by Fourier transform infrared (FTIR) spectroscopy. The phase behavior and optical properties of the synthesized monomers and polymers were investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and thermogravimetric analyses (TGA). The homopolymer IP reveals a cholesteric phase and VIIP displays a nematic phase. The copolymers IIP–VIP exhibit, respectively, cholesteric oily‐streak texture and focal‐conic texture. The fixation of the helical pitch and oily‐streak texture of the cholesteric phase is achieved by quenching, and polymer films with different reflection colors are obtained. The experimental results demonstrate that the glass transition temperature (Tg) and the melting temperature (Tm) of the copolymers IIP–VIP decrease, whereas the isotropization temperature (Ti) and the mesomorphic temperature range (ΔT) increase with increasing content of mesogenic MII units. TGA results indicate that the temperatures at which 5% mass loss occurred (T5wt%) of all copolymers are >245°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1936–1941, 2003  相似文献   

18.
Poly (o‐toluidine) (POT) salts doped with organic sulfonic acids (β‐naphthalene sulfonic acid, camphor sulfonic acid, and p‐toluene sulfonic acid) were directly synthesized by using a new solid‐state polymerization method. The FTIR spectra, ultraviolet visibility (UV–vis) absorption spectra, and X‐ray diffraction patterns were used to characterize the molecular structures of the POT salts. Voltammetric study was done to investigate the electrochemical behaviors of all these POT salts. The FTIR and UV–vis absorption spectra revealed that the POT salts were composed of mixed oxidation state phases. All POT salts contained the conducting emeraldine salt (half‐oxidized and protonated form) phase; the pernigraniline (fully oxidized form) phase is predominant in POT doped with β‐naphthalene sulfonic acid, and POT doped with p‐toluene sulfonic acid had the highest doping level. The X‐ray diffraction patterns showed that the obtained POT doped with organic sulfonic acids were lower at crystallinity. The conductivity of the POT salts were found to be of the order 10?3‐10?4 S/cm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1630–1634, 2005  相似文献   

19.
Ultrafine well‐dispersed Fe3O4 magnetic nanoparticles were directly prepared in aqueous solution using controlled coprecipitation method. The synthesis of Fe3O4/poly (2‐acrylamido‐2‐methylpropane sulfonic acid) (PAMPS), Fe3O4/poly (acrylamide‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) poly(AM‐co‐AMPS) and Fe3O4/poly (acrylic acid‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) poly(AA‐co‐AMPS) ‐core/shell nanogels are reported. The nanogels were prepared via crosslinking copolymerization of 2‐acrylamido‐2‐methylpropane sulfonic acid, acrylamide and acrylic acid monomers in the presence of Fe3O4 nanoparticles, N,N′‐methylenebisacrylamide (MBA) as a crosslinker, N,N,N′,N′‐tetramethylethylenediamine (TEMED) and potassium peroxydisulfate (KPS) as redox initiator system. The results of FTIR and 1H‐NMR spectra indicated that the compositions of the prepared nanogels are consistent with the designed structure. X‐ray powder diffraction (XRD) and transmission electron microscope (TEM) measurements were used to determine the size of both magnetite and stabilized polymer coated magnetite nanoparticles. The data showed that the mean particle size of synthesized magnetite (Fe3O4) nanoparticles was about 10 nm. The diameter of the stabilized polymer coated Fe3O4 nanogels ranged from 50 to 250 nm based on polymer type. TEM micrographs proved that nanogels possess the spherical morphology before and after swelling. These nanogels exhibited pH‐induced phase transition due to protonation of AMPS copolymer chains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

20.
Single step chemical polymerization of N‐methyl aniline was carried out by using ammonium persulphate as an oxidizing agent. The conducting emeraldine salt phase of the polymers using camphor sulfonic acid and p‐toluene sulfonic acid as dopants was made by a direct process. The polymers were characterized by UV‐vis and FTIR spectroscopy, scanning electron microscopy, TGA, and conductivity measurements. The synthesized polymers were found to have very good physicochemical properties and good electrical conductivity. Conductivity measurements have shown “thermal activated behavior.” The change in resistance with respect to % relative humidity (RH) was observed, when pressed pellets of the polymer were exposed to the broad range of humidity (ranging between 20 and 100% RH). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 812–820, 2006  相似文献   

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