Synthesis and characterization of side‐chain liquid‐crystalline ionomers containing quaternary ammonium salt groups

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 (T_c) 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     

Synthesis and characterization of chiral smectic side‐chain liquid crystalline polysiloxanes and ionomers containing sulfonic acid groups

The synthesis of new chiral smectic A (S_A) side‐chain liquid crystalline polysiloxanes (LCPs) and ionomers (LCIs) containing 4‐allyloxy‐benzoyl‐4‐(S‐2‐ethylhexanoyl) p‐benzenediol bisate (ABB) as mesogenic units and 4‐[[4‐(2‐propenyloxy)phenyl]azo]benzenesulfonic acid (AABS) as nonmesogenic units is presented. The chemical structures of the monomers and polymers are confirmed by FTIR spectroscopy or ¹H–NMR. Differential scanning calorimetry (DSC), optical polarizing microscopy, and X‐ray diffraction measurements reveal that all the polymers P_I–P_IV and ionomers P_V–P_VI exhibit S_A texture. The results seem to demonstrate that the tendency toward the S_A‐phase region increases with increasing sulfonic acid concentration, and the thermal stability of the S_A phase is determined by the flexibility of the polymer backbones and the interactions of sulfonic acid groups. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2335–2340, 2001     

Surface characterization and study of Langmuir films of poly(4‐vinylpyridine) quaternized with n‐alkylbromide

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, γ_c, and the dispersion force and polar contributions to SE, γ_D and γ_P, 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     

Synthesis and phase behavior of cholesteric liquid crystal polymers containing glutamic acid in main‐chain

Four polymers (P₀–P₃) containing peptide chain as polymer backbone were synthesized by condensation reaction with bis(trichloromethyl)carbonate and triethylamine. The chemical structures of the monomers M₀–M₃ were confirmed by FTIR and ¹H‐NMR. The structure–property relationships of the monomers and polymers are discussed. Their phase behavior and optical properties were investigated by differential scanning calorimetry, thermogravimetric analysis, and polarizing optical microscopy. Monomers M₁–M₃ and polymers P₁–P₃ displayed cholesteric phases. The results demonstrated that the melt temperature and clear point of monomers (M₁–M₃) and polymers (P₁–P₃) decreased with the increase of the flexible spacer length in the side‐chain, and the mesophase temperature range of the polymers increased with the increase of the flexible spacer length. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and solid‐state properties of crosslinked alternating copolymers of phenyl vinylethylene carbonate and N‐substituted maleimides

The copolymers of phenyl vinylethylene carbonate (PVEC) and N‐phenylmaleimide were prepared with various monomer feeds by using a radical initiator. These copolymers were crosslinked by aminolysis between hexamethylenediamine (HMDA) and cyclic carbonate moiety in the side‐chain to obtain the networked polymers having the hydroxyurethane structure. Furthermore, the crosslinked copolymers having the polar cyclic carbonate in the side‐chain were synthesized from PVEC and several bifunctional maleimides, and their double networked polymers were prepared with HMDA. These copolymers and networked polymers exhibited color changes depending on their structures based on the acid–base switching in the solid‐state. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45247.     

Thermotropic main‐chain liquid‐crystalline photodimerizable poly(vanillylidenealkyloxy alkylphosphate ester)s containing a cyclopentanone moiety

A new class of main‐chain liquid‐crystalline photodimerizable vanillylidene‐containing alkylpolyphosphate esters were synthesized from 2,5‐bis[m‐hydroxyalkyloxy(vanillylidene)] cyclopentanones with various alkylphosphoro‐ dichloridates by solution polycondensation in chloroform at ambient temperature. Their chemical structures were confirmed by FT‐IR, ¹H, ¹³C and ³¹P NMR spectroscopic analysis. Dilute‐solution viscosity values were measured in order to obtain the intrinsic viscosities of the synthesized polymers. Mesogenic properties and phase behavior were investigated by the use of hot‐stage optical polarized microscopy and differential scanning calorimetry. Thermogravimetric analysis revealed that all of the polymers were stable up to 170–230 °C and decomposed with high char yields. The shorter methylene‐chain‐containing polymers did not show a liquid‐crystalline phase, while the longer methylene‐chain‐ containing polymers showed grainy and nematic textures. The T_g, T_m and T_i values of the polymers decreased with increasing flexible methylene chain length in the polymer backbones. The photocrosslinking properties of the polymers were studied by UV light/UV spectroscopy; the crosslinking proceeds via 2π–2π cycloaddition reactions of the vanillylidene exocyclic double bonds of the polymers. The rate of crosslinking was faster for the pendant ethoxy‐containing polymers than that of the pendant methoxy‐containing polymers. Copyright © 2005 Society of Chemical Industry     

Influence of chirality on phase behaviour of side chain liquid crystalline polymers

Summary Two kinds of chiral side chain liquid crystalline polyacrylates were synthesized and characterized by DSC, POM and x-ray diffraction. The results indicated that chirality of side chain end group and spacer length strongly influence the phase behaviour of the polymers. The polymer P-I with one asymmetric carbon atom of end group exhibits enantitropic Smectic S_A and S_C phases. The polymer P-III having two asymmetric carbon atoms displays enantitropic Smectic S_A and S_B phases. Formation of liquid crystalline polymorphism of polymers depends on spacer length of side chains.     

Synthesis and characterization of α‐methylstilbene‐ and azobenzene‐based thermotropic liquid crystalline polymers

A series of combined liquid crystalline poly(bis‐4,4′‐oxy‐α‐methylstilbene‐4‐substituted (X) phenylazo‐4′‐phenyloxydecylphosphate ester)s bearing photoreactive mesogenic units were synthesized. FTIR and ¹H NMR spectroscopy confirmed the structures of these polymers. The inherent viscosities of the polymers were found to be in the range 0.45–0.65 dL g^?1. Polarizing optical microscopy (POM) exhibited birefringent liquid crystalline melt properties. The thermal properties of all of the polymers were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The photochemical properties of these polymers were studied by UV‐visible and fluorescence spectroscopy. The influence of the photoinduced E–Z (trans–cis) isomerization of the various terminal substituents of the side‐chain azobenzenes was investigated. The kinetics of the photoisomerization process reveal the switching times for the conversion between the trans‐ and cis‐ forms of the azobenzene units. The photo‐optical properties of these polymers exhibited layered smectic phases and showed good photoinduced properties in their mesomorphic states. Copyright © 2005 Society of Chemical Industry     

Influence of azobenzene units on imidization kinetic of novel poly(ester amic acid)s and polymers properties before and after cyclodehydration

In this article, the imidization reaction kinetic of novel poly(ester amic acid)s with azobenzene units as side groups was studied by dynamic experiments by means of differential scanning calorimetry. Polymers differ in the number of chromophore moieties in their repeating unit and position in which azobenzene group is attached to the polymer chain. The kinetic parameters of poly(ester amic acid)s conversion to poly(ester imide)s was compared with data calculated for parent polymer, that is, without azobenzene groups. For the first time to our knowledge, the imidization kinetic of polymers with side azobenzene groups was studied. Kinetic parameters, such as the activation energy and frequency factor were estimated with the by Ozawa model [(E(O) and A(O)), respectively] and Kissinger model [(E(K) and A(K), respectively]. The values of activation energy determined with both models were in the range 167.1–198.3 kJ/mol. The lowest activation energy of imidization reaction exhibited polymer in which azobenzene units were placed between amide linkages. Polymers were characterized by FTIR, ¹H‐NMR, X‐ray, and UV–vis methods. The glass transition temperature of resultant poly(ester imide)s was in the range of 217–237°C. The presence of chromophore units slightly decreased T_g and significantly improved their solubility and optical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Understanding excitons in optically active polymers

We review the solid‐state physics approach to electronic and optical properties of conducting polymers, and bring together the languages of solid‐state theory for polymers and the quantum chemistry of oligomers. We consider polymers as generic one‐dimensional semiconductors with specific features of strongly correlated electronic systems. Our model combines the large distance electron–hole motion within an exciton, governed by long‐range Coulomb attraction with strong intramonomer electronic correlations, which results in effective intramonomer electron–hole repulsion. We exploit the dielectric screening to go beyond the single chain picture and to compare excitons for polymers in solutions and in films. Our approach allows the connecting, explaining, exploiting and organizing of such different experimental and numerical findings as shallow singlet and deep triplet excitons in phenylenes, anomaly in singlet–triplet exciton formation ratio, A_g–B_u crossing in polyenes and common 1/N energy dependencies in oligomers. Copyright © 2007 Society of Chemical Industry     

Synthesis and phase behavior of chiral side‐chain liquid‐crystalline polysiloxanes containing two mesogenic groups

The synthesis of chiral side‐chain liquid‐crystalline polysiloxanes containing both cholesteryl undecylenate (M_I) and 4‐allyloxy‐benzoyl‐4‐(S‐2‐ethylhexanoyl) p‐benzenediol bisate (M_II) 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 M_I 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     

Synergistic effect of alkyl lactate functional groups on properties of methacrylate polymers

In this work, four novel different alkyl lactate methacrylate monomers were synthesized through azeotropic esterification method by reacting methyl, ethyl, propyl and butyl lactates with methacrylic acid. The prepared monomers were polymerized through solution polymerization technique and both monomers and polymers were analyzed by FTIR, ¹H NMR and ¹³C NMR spectroscopy techniques to elucidate the structure and to confirm their formation. Increasing the number of methylene units in alkyl lactate side chain decreases the glass transition temperature (T_g) of the polymers. Average molecular interchain spacing (〈R〉) of polymers was obtained from the wide-angle X-ray diffraction measurement and the values ranged from 6.26 to 7.18 Å based on the length of alkyl lactate group. The prepared polymers showed hygroscopic property and their moisture absorption was in the range of 10–24% (w/w) depending upon the length of alkyl lactate moiety, relative humidity and time. These polymers have the potential for hydrogel applications owing to their increased moisture absorption capacity. Both polymethyl and propyl lactate methacrylate showed two distinct and prominent thermal degradations whereas polyethyl and butyl lactate methacrylates showed only a single distinct and prominent thermal degradation step. An interesting result of as-synthesized polymers showed odd–even chain length effect in the properties of 〈R〉, moisture uptake and thermal stability.

     

Synthesis and characterization of new conjugated soluble polythiophenes with excellent reversible electrochemical properties

A series of five new conjugated polythiophene (PT) derivatives containing piperidinyl groups as a side chain were synthesized by ferric trichloride oxidization. All of the polymers were soluble in common organic solvents, and their high regioregularity were confirmed by ¹H‐NMR. The weight‐average molar masses ranged from 5931 to 22,955 g/mol with a low polydispersity index ranging from 1.18 to 1.79. The fluorescence emission maximum of poly[3‐(N‐methyl propionate–4′‐piperidine)methylene–thiophene] in the films was 725 nm in the yellow–red region, higher than that of the other PT derivatives. All five polymers exhibited reversible p‐doping/dedoping (oxidation/reneutralization) processes; this indicated that these polymers could be applied in electrical equipment in the doping state. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigation of liquid crystalline and photocrosslinkable poly[4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamate]s

Three series of liquid‐crystalline‐cum‐photocrosslinkable polymers were synthesized from 4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamates (x = ? H, ? OCH₃ and ? CN; m = 6, 8 and 10) by free radical solution polymerization using azobisisobutyronitrile as an initiator in tetrahydrofuran at 60 °C. All the monomers and polymers were characterized using intrinsic viscosity, and FTIR, ¹H NMR and ¹³C NMR spectroscopy. The liquid crystalline behavior of these polymers was examined using a hot stage optical polarizing microscope. All the polymers exhibited liquid crystalline behavior. The hexamethylene spacer‐containing polymers exhibited grainy textures; in contrast, the octamethylene and decamethylene spacer‐containing polymers showed nematic textures. Differential scanning calorimetry data confirmed the liquid crystalline property of the polymers. Thermogravimetric analysis revealed that all the polymers were stable between 236 and 344 °C in nitrogen atmosphere and underwent degradation thereafter. As the methylene chain length increases in the polymer side‐chain, the thermal stability and char yield of the polymers decrease. The photocrosslinking property of the polymers was investigated using the technique of exposing the polymer solution to UV light and using UV spectroscopy. The crosslinking reaction proceeds via 2π–2π cycloaddition reactions of the ? CH?CH? of the pendant cinnamate ester. The polymers containing electron‐releasing substituents (? OCH₃) showed faster crosslinking than the unsubstituted polymers and those containing electron‐withdrawing substituents (? CN). Copyright © 2007 Society of Chemical Industry     

Correlations between alkyl side chain length and dynamic mechanical properties of poly(n-alkyl acrylates) and poly(n-alkyl methacrylates)

In the present paper, dynamic mechanical properties of poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) with different alkyl side chain length were studied. The results show that with the increase of alkyl side chain length, the storage modulus changes more steadily, and the loss modulus peak and the tanδ peak become broader for PnAA and PnAMA. At the same time, the tanδ peak is more and more apart from the loss modulus peak and the point where the storage modulus begins to drop. For quantitative discussion, three variables, the steepness index (S), the transition wideness (W) of storage modulus and the integration area (A) of tanδ were defined to investigate the potential correlation between the dynamic mechanical properties and alkyl side chain length. It can be observed that S decreases while W and A increase with increasing alkyl side chain length. Moreover, the relaxation spectra of the two series of polymers are calculated from the corresponding mechanical spectra. The shapes of the relaxation spectra are broader and broader with the increase of the alkyl side chain length. These phenomena are interpreted by the perspective of fragility, molecular packing efficiency and intermolecular coupling.     

Preparation and electro‐optic properties of novel Y‐type polyimides with highly enhanced thermal stability of second harmonic generation

BACKGROUND: In the development of nonlinear optical (NLO) polymers for electro‐optic device applications, stabilization of electrically induced dipole alignment is one of the important criteria. Polyimides for NLO applications have attracted attention because of their high T_g values and high thermal stability. In this work we designed and synthesized a new type of NLO polyimide, in which the pendant NLO chromophores are parts of the polymer backbone. These mid‐type NLO polymers are expected to have the merits of both main‐chain and side‐chain NLO polymers: stabilization of dipole alignment and good solubility. RESULTS: 3,4‐Bis‐(3,4‐dicarboxyphenylcarboxyethoxy)‐4′‐nitrostilbene dianhydride was prepared and reacted with the corresponding aromatic diamine to yield unprecedented Y‐type polyimides containing 3,4‐dioxynitrostilbenyl groups as NLO chromophores, which constituted parts of the polymer backbones. The resulting polyimides are soluble in polar solvents such as dimethylformamide and dimethylsulfoxide. These polymers showed a thermal stability up to 320 °C in thermogravimetric thermograms with T_g values obtained from differential scanning calorimetry thermograms in the range 143–164 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at the 1064 nm^?1 fundamental wavelength were around 9.45 × 10^?18 C. CONCLUSION: The dipole alignment exhibited exceptionally high thermal stability even at 30 °C higher than T_g. There was no SHG decay below 180–190 °C because of the partial main‐chain character of the polymer structure, which is acceptable for NLO device applications. Copyright © 2007 Society of Chemical Industry     

Synthesis and chemical properties of dielectric polyphenylenes with nitro group

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 (M_n) 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     

Synthesis and characterization of organic–inorganic hybrid polymers with a well‐defined structure from diamines and epoxy‐functionalized polyhedral oligomeric silsesquioxanes

A new class of organic‐inorganic hybrid polymers with well‐defined structure was prepared by reacting diepoxyhexavinyl polyhedral oligomeric silsesquioxanes (DehvPOSS) with diamines of different chain lengths. The structures and properties of these hybrid polymers were well characterized by FTIR, ²⁹Si‐NMR, GC‐MS, and TGA. A modeling characterization was employed to help identify the structures of organic tethers linked between the POSS cages. The results indicated that at the stoichiometric ratio of DehvPOSS to diamine, well‐defined organic–inorganic hybrid polymers with controlled variation of the organic tether architecture can be made, and each organic tether connected four POSS cages. Thermal stability (T_dec) increased with an increase in the tether length of the diamine molecules, and the highest T_dec was obtained with butanediamine (rather than propanediamine or ethanediamine) as the organic tether. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3730–3735, 2006     

Novel copolyesters containing naphthalene structure III. Copolyesters prepared from 2,6‐dimethyl naphthalate,ethylene glycol,and 2,2‐dialkyl‐1,3‐propanediols

Poly(ethylene naphthalate) (PEN) copolymers were prepared by melt polycondensation of dimethyl naphthalate and excess ethylene glycol with 5–40 mol % (in feed) of 1,3‐propanediol or 2,2‐dialkyl‐1,3‐propanediols, where the dialkyl groups are dimethyl, diethyl, and butyl‐ethyl. No significant depression of reduced specific viscosity was observed. The comonomer contents in the copolymers are considerably higher than those in the feed. The effects of the copolymer composition on the structures of the films were investigated using thermal analyses, density measurements, X‐ray diffraction methods, and other physical tests. The crystallinities and densities of heat‐treated films decreased with increasing content of comonomer and length of alkyl side chain in the comonomer. The glass transition temperature (T_g) and melting temperature (T_m) were decreased by the copolymerization, while an increase in the length of the alkyl side chain hardly affected T_ms of the heat‐treated films. Alkali resistance, moisture resistance, dye ability, and thermal shrinkage were increased by the incorporation of comonomer having an alkyl side chain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2754–2763, 2001     

Synthesis of poly(epichlorohydrin‐g‐methyl methacrylate) graft copolymers by the combination of cationic and atom transfer radical polymerization

Poly(epichlorohydrin) possessing chloromethyl side groups in the main chain was used in the atom transfer radical polymerization of methyl methacrylate and styrene to yield poly(epichlorohydrin‐g‐methyl methacrylate) and poly(epichlorohydrin‐g‐styrene graft copolymers. The polymers were characterized by ¹H NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and fractional precipitation method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2725–2729, 2006