Synthesis and properties of PMR type poly(benzimidazopyrrolone‐imide)s

PMR type poly(benzimidazopyrrolone‐imide) or poly(pyrrolone‐imide) (PPI) matrix resin was synthesized using the diethyl ester of 4,4′‐(hexafluoroisopropylidene)diphthalic acid (6FDE), 3,3′‐diaminobenzidine, para‐phenylenediamine, and monoethyl ester of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic acid (NE) in anhydrous ethyl alcohol with N‐methylpyrrolidone. The homogeneous matrix resin solution (40–50% solid) was stable for a storage period of 2 weeks and showed good adhesion with carbon fibers, which ensured production of prepregs. The chemical and thermal processes in the polycondensation of the monomeric reactant mixture were monitored by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, etc. Thermosetting PPI as well as short carbon fiber‐reinforced polymer composites was accomplished at optimal thermal curing conditions. The polymer materials, after postcuring, showed excellent thermal stability, with an initial decomposition temperature > 540°C. Results of MDA experiments indicate that the materials showed > 70–80% retention of the storage modulus at 400°C and glass transition temperatures as high as 440–451°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1600–1608, 2001     

Lower-curing-Temperature PMR polyimides

Studies were performed to achieve lower-curing temperature PMR (polymerization of monomer reactants) polyimides. Partial substitution of a p-aminostyrene end-cap for the monomethyl ester of 5-norbornene-2,3-dicarboxylic acid lowered the final cure temperature of typical PMR resins from 600 to 500°F. The weight-loss characteristics of neat resins and graphite fiber composites prepared by using the mixed end-cap approach were determined at 600°F. The room temperature and short-term elevated temperature mechanical properties of the composites at 550°F and 600°F were determined. The mechanical-property-retention characteristics of the composites at 550°F and 600°F are also discussed.     

Crosslinking-property relationships in PMR polyimide composites. Part I

This study examines for the first time how matrix crosslinking affects the composite physical and mechanical properties of a graphite fiber reinforced PMR polyimide composite during long-term isothermal aging. Unidirectional composite specimens of Celion 6000/PMR-P1 were isothermally exposed at 288°C in air for various time periods up to 5000 h. The matrix crosslink densities were estimated from the kinetic theory of rubber elasticity and shifts in the glass transition temperatures (T_gs). The T_g, coefficient of thermal expansion, density, weight loss, moisture absorption, and elevated temperature flexural and interlaminar shear properties were also determined. Several linear relationships were found between the matrix crosslink density and composite physical and mechanical properties. The T_g, initial weight loss and density, and elevated temperature interlaminar shear strength increase with an increase in crosslink density. Conversely, the initial moisture absorption and coefficient of thermal expansion decrease with increasing crosslink density. As expected, the elevated temperature flexural strength and modulus show no direct correlations with crosslink density. Further, after achieving the highest matrix crosslink density, several of the composite properties begin to decrease rapidly. These findings suggest that time-temperature dependent nature of attaining the maximum matrix crosslinking is closely linked to the onset of the composite property degradation. Though much more work is needed, a fundamental understanding of the relationships between matrix crosslinking and composite physical and mechanical property can provide a scientific basis for the prediction of the extent of composite service life not only for PMR polyimides but also for other thermosetting matrix resins, such as epoxies and bismaleimides.     

Forced torsional properties of PMR composites with varying nadic ester concentrations and processing histories

PMR polyimide resin was prepared from 4,4′-methylenedianiline (MDA), the dimethyl ester of 3,3′,4,4′- benzophenonetetracarboxylic acid (BTDE) and the monomethyl ester of 5-norbornene-2,3-dicarboxylic acid (NE). The NE group serves as a chain terminator and crosslinking site. PMR/Celion 6000 composites were fabricated from resins having varying NE concentrations using two molding processes, and the laminates characterized in forced torsion. Glass transition temperatures (T_g) of 360–390°C were observed in the crosslinked resins, as compared with the literature value of 284°C reported for the uncrosslinked systemT_g did not decrease with decreasing NE concentrations over the range from 2.0 to 1.25 moles. Stoichiometry, within the range studied, showed little influence on shear properties; however, a 25% variation in matrix shear modulus with processing was observed. The G₁₂ values determined in forced torsion were in excellent agreement with those reported from tensile tests of ±45° laminates. A branching and possible secondary crosslink mechanism is proposed based on dynamic mechanical behavior and infrared spectra of the composites.     

Synthesis and properties of new polymerized monomer reactants matrix resins of pyrrolone–benzimidazole copolymers containing pyridine unit

A series of new polymerized monomer reactants (PMR) matrix resins of poly(pyrrolone‐benzimidazole)s containing a pyridine unit (PPBP) were synthesized by polycondensation of monoethyl ester of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic acid, 2,6‐diphenyl ester pyridinedicarboxylic acid or 3,5‐diphenyl ester pyridinedicarboxylic acid, and diethyl ester of 4,4′‐oxydiphthalic acid with 3,3′‐diaminobenzidine in a mixing solution of anhydrous ethyl alcohol and N‐methylpyrrolidone under given temperature and pressure conditions. The resulting resin solutions showed good solubility in polar organic solvents and stability at room temperature. The corresponding PPBP matrix resin, molded powder, and molded plate were prepared by undergoing amidation, imidization, cyclization, and crosslinking reactions when the reaction temperature was increased from 80 to 350°C, successively; the crosslinking structure was formed by the reverse Diels–Alder reaction at 270–290°C under 50 MPa pressure (2.5–3.5 MPa displayed by the pressure meter). The chemical reactions and properties of the resulting PPBP were studied by means of FTIR, TGA, and DMA methods, and the results indicated that the kinds of PPBP materials retain excellent thermal stability and processability; when the initial decomposition temperature was above 620°C the T_g was at 413.5°C for 3,5‐PPBP‐20 molded plate. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3981–3990, 2004     

New bismaleimide resin with improved tack and drape properties for advanced composites

In order to improve the tack and drape properties of prepregs based on bismaleimide (BMI) resins, a new allyl compound containing diglycidyl ether of bisphenol A backbone, designated as AE, was prepared by reacting m-allylphenol (1 mol) with an equimolar amount of diglycidyl ether of bisphenol A (0.5 mol). The copolymer of BMI/AE was prepared and characterized. The softening point of the copolymer is lower than room temperature. The prepregs based on BMI/AE have very good tack and drape properties and a long work life (three weeks) at room temperature. Thermogravimetric analysis (TGA) in nitrogen atmosphere revealed that the cured copolymer was stable up to 515°C. The hot/wet resistance properties of the cured copolymer were investigated by aging it in boiling distilled water. After aging for 100 h, the water absorption and heat defleation temperature (HDT) were 3.6% and 248°C, respectively. In addition, the cured copolymer has good mechanical properties at ambient and elevated temperature. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 273–279, 1997     

Synthesis and characterization of perfluorinated acrylate–methyl methacrylate copolymers

A novel perfluorinated acrylic monomer 3,5‐bis(perfluorobenzyloxy)benzyl acrylate (FM) with perfluorinated aromatic units was synthesized with 3,5‐bis(perfluorobenzyl)oxybenzyl alcohol, acryloyl chloride, and triethylamine. Copolymers of FM monomer with methyl methacrylate (MMA) were prepared via free‐radical polymerization at 80°C in toluene with 2,2′‐azobisisobutyronitrile as the initiator. The obtained copolymers were characterized by ¹H‐NMR and gel permeation chromatography. The monomer reactivity ratios for the monomer pair were calculated with the extended Kelen–Tüdos method. The reactivity ratios were found to be r₁ = 0.38 for FM, r₂ = 1.11 for MMA, and r₁r₂ < 1 for the pair FM–MMA. This shows that the system proceeded as random copolymerization. The thermal behavior of the copolymers was investigated by thermogravimetric analysis and differential scanning calorimetry (DSC). The copolymers had only one glass‐transition temperature, which changed from 46 to 78°C depending on the copolymer composition. Melting endotherms were not observed in the DSC traces; this indicated that all of the copolymers were completely amorphous. Copolymer films were prepared by spin coating, and contact angle measurements of water and ethylene glycol on the films indicated a high degree of hydrophobicity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Modification of cyanate ester resin by poly(ethylene phthalate) and related copolyesters

Aromatic polyesters were prepared and used to improve the brittleness of the cyanate ester resin. The aromatic polyesters include poly(ethylene phthalate) (PEP) and poly(ethylene phthalate‐co‐1,4‐phenylene phthalate). The polyesters were effective modifiers for improving the brittleness of the cyanate ester resin. For example, inclusion of 20 wt % PEP (MW 19,800) led to a 120% increase in the fracture toughness (K_IC) with retention in flexural properties and a slight loss of the glass transition temperature compared to the mechanical and thermal properties of the unmodified cured cyanate ester resin. The microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The thermal stability of the modified resins was lower than that of the unmodified resin as determined by thermogravimetric analysis. The water absorptivity of the modified resin increased significantly, compared to that of the unmodified cured cyanate ester resin. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified cyanate ester resin system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 208–219, 2000     

Glass‐transition temperature based on dynamic mechanical thermal analysis techniques as an indicator of the adhesive performance of vinyl ester resin

Vinyl ester resins are being used extensively as matrices in fiber‐reinforced polymer composite materials, but their use as a structural adhesive has been limited. Initial studies investigating the durability of a vinyl ester as a wood adhesive showed unsatisfactory performance in comparison with other adhesives. In this work, the glass‐transition temperatures (T_g's) of a vinyl ester and a E‐glass/vinyl ester composite material, fabricated by the Composites Pressure Resin Infusion System, were determined with dynamic mechanical thermal analysis. The results indicated that the resin cured under ambient conditions had a much lower T_g (～60°C) than the postcured material (～107°C). This suggested undercuring, that is, incomplete crosslinking, of the resin when it was cured at room temperature. E‐glass/vinyl ester samples, however, showed virtually no difference in T_g between room‐temperature‐cured and postcured samples. The exact reasons for this are not currently known but are thought to be both mechanical and chemical in nature. On the basis of the findings presented in this article, it can be concluded that if this vinyl ester resin is to be used as a structural adhesive, postcuring or formulation to ensure a high degree of crosslinking under ambient conditions is necessary. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2221–2229, 2005     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Effects of storage aging on the cure kinetics of T700/BMI prepregs for advanced composites

The effects of room temperature aging on the cure kinetics of a bismaleimide (BMI) matrix prepreg have been characterized by different time and storage conditions. The study has focused on the stability of BMI matrix carbon fiber prepregs, when exposed to controlled environmental conditions before being used in composite manufacturing. The effects of aging on reactivity, glass transition temperature, and process window have been investigated by differential scanning calorimetrer through dynamic and isothermal tests. A theoretical kinetic model for epoxy matrix prepregs, developed in previous studies, has been applied to the cure of both aged and virgin BMI matrix. The model is able to satisfactorily describe the effect of processing variables such as temperature and degree of cure during the curing of the composite under different conditions (curing temperature and heating rate). The effects of diffusion‐controlled phenomena on the cure kinetics, associated with changes in glass transition temperature as a function of the degree of cure, have been taken into account in the formulation of an nth‐order kinetic model. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Preparation and performance of urethane-modified polytriazole adhesives

Polytriazole adhesives are a new type of adhesives with excellent heat resistance, but the lap shear strength at room temperature is not ideal, which is about 15 MPa. In order to improve its adhesion performance at room temperature, a series of urethane-modified polytriazole (UPTA) adhesives were successfully synthesized via 1, 3-dipolar cycloaddition reaction between azides, and alkynes. Firstly, an alkynyl-terminated urethane monomer di(but-3-yn-1-yl) (1,3-phenylenebis(methylene)) dicarbamate (DBPMD) was synthesized and characterized. Then DBPMD was reacted with biphenyl dibenzyl azide (BPDBA) and N′,N′,N′,N′-tetrapropargyl-p,p′-diaminodiphenyl methane (TPDDM) to prepare UPTA adhesives. Curing behavior, thermal properties, bonding performance, and resistance to damp heat aging of UPTA adhesives were studied. The results show that the introduction of urethane group has almost no effect on the curing behavior. The glass transition temperature (T_g) and the 5% thermal weight loss temperature (T_d5) gradually decreased with the increased proportion of DBPMD added. T_g of UPTA adhesives ranged from 185 to 215°C and T_d5 of UPTA adhesives were all above 300°C, which indicated its outstanding thermal stability. The lap shear strength at room temperature of UPTA adhesives increased first and then decreased with the increasing amount of DBPMD, which ranged from 13.9 to 19.9 MPa. The highest lap shear strength of UPTA adhesives can reach 19.9 MPa, which was 31.8% higher than PTA adhesive. The lap shear strength retention rate of UPTA adhesives at 180°C was all over 75%. Lap shear strength retention rate of UPTA adhesives under 168 h damp heat aging time was all over 80%. UPTA adhesives have good bonding performance, heat resistance, and damp heat aging resistance, which can meet many complex construction requirements.     

Effect of the electron donor structure on the shelf‐lifetime of visible‐light activated three‐component initiator systems

In this study, we investigated the effect of electron donor structures on the shelf life of three‐component initiator systems which also included methylene blue (MB) as a photosensitizer and diphenyl iodonium salt (DPI) as an electron acceptor. For this research, N‐phenylglycine (NPG), N‐methyldiethanolamine (MDEA), N,N‐diisopropyl‐3‐pentylamine (DIPA), and 1,4‐diazabicyclo[2.2.2]octane (DABCO) were used as electron donors, with different of proton transfer efficiencies and radical/cation persistence. To aid characterization of the shelf‐life or dark storage stability of three‐component initiator systems, the relative polymerization kinetic profile of each freshly prepared initiator system was first obtained using photo‐DSC. The standardized photopolymerization reactions were repeated after various dark storage intervals. Thermal stability of each initiator system was compared by applying a ramped temperature program to monomer samples in the DSC in the dark. To analyze the kinetic changes as a function of storage time more quantitatively, we suggested an equation and characterized the shelf‐lifetime constant (k) of three‐component initiator systems. From the experiments and analysis, we conclude that the order of shelf‐life is consistent with the of radical cation (DH·⁺) persistence; DABCO > DIPA > MDEA > NPG, and inversely related to the proton transfer efficiency of the electron donor; NPG > MDEA > DIPA > DABCO. The effects of electron donor structures on thermal stability were consistent with the results of kinetic shelf‐life experiments. This investigation provides an effective means to characterize as well as predict shelf lifetimes of initiator systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Physico-chemical,thermal, and mechanical properties of PLA-nHA nanocomposites: Effect of glass fiber reinforcement

In this study, tri-layered composites were prepared by reinforcing poly-lactic acid (PLA) nano-hydroxyapatite (n-HA) (1 and 5 wt%) and 20 mol% continuous phosphate glass fibers (PGF). Initially, the effect of addition of 1 and 5% n-HA on the structural, thermal, mechanical, and thermo-mechanical properties of 100% PLA was investigated. With 5 wt% n-HA addition the tensile modulus (TM), flexural modulus (FM), tensile strength (TS), and flexural strength (FS) of 100% PLA was improve by 14.9, 47.4, 6, and 32.9%, respectively. Whereas, the un-notched impact strength of the nanocomposites suffer 2% deterioration. However, T _g decreased by 0.3°C and T _c increased by 10°C as 5 wt% n-HA was added to 100% PLA. Afterwards, the 5% n-HA/PLA composite were reinforced with 20 mol% continuous PGF and the TM, FM, TS, and FS of the tri-layered composites were 162.6, 412.5, 28.4, and 157.4% higher as compared to 100%PLA. Furthermore, the storage modulus of the 1% n-HA-filled composites was 500 MPa lower than 100%PLA, while 5 wt% n-HA-filled composites showed similar storage modulus as 100% PLA. 5 wt% n-HA-filled composite showed the highest peak of loss modulus which may be attribute to the chain segment of PLA matrix after the incorporation of HA. Thus, n-HA and PGF reinforcement resulted in improved mechanical properties of the composites and have great potential as biodegradable bone fixation device with enhanced load-bearing ability.     

Lignin valorization by forming thermally stimulated shape memory copolymeric elastomers—Partially crystalline hyperbranched polymer as crosslinks

Lignin based thermal‐responsive elastomers were produced by a melt polycondensation reaction with a long alkyl chain hyperbranched poly(ester‐amine‐amide) (B₃‐A₂‐CB₃¹). The effect of lignin content on elastomers properties was investigated. The thermal and mechanical properties of the copolymers were characterized by DMA, DSC, and TGA. The morphology of the copolymer was examined by SEM. Tensile properties were dominated by HBP <25% lignin content while lignin dominated >25% content. The copolymers glass transition temperature (T_g) increased with lignin content. The elastomer with 30% lignin content demonstrated optimal mechanical properties (tensile strength 5.3 MPa, Young's modulus 8.9 MPa, strain at break 301%, and toughness 1.03 GPa). Thermally stimulated dual shape memory effects (SME) of the copolymers were quantified by cyclic thermomechanical tests. The transition temperature (T_trans) of the polymer was able to be controlled (room to body temperature) by varying the amount of lignin added which broadens the range to medical applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41103.     

Preparation,characterization, and improvement of hollow epoxy particle‐toughened vinyl ester composites for high‐end applications

Spherical hollow epoxy particles (HEPs) that can serve as advanced reinforcing fillers for vinyl ester thermosets were prepared using the water‐based emulsion method. The HEP fillers were incorporated into the vinyl ester matrices at different loading amounts, ranging from 0 to 9 wt %, to reinforce and toughen the vinyl ester composite. The optimum mechanical properties of the HEP‐toughened epoxy composite can be achieved by the addition of 5 wt % HEP filler into the vinyl ester matrices. The toughening and strengthening of the epoxy composites involved the interlocking of vinyl ester resins into the pore regions on the HEP fillers. The toughening and interlocking mechanisms of HEP‐toughened vinyl ester composites were also proposed and discussed. The addition of HEP fillers into vinyl ester matrices increased the glass transition temperature (T_g) and thermal stability of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

New generation of thermally stable and conducting poly(azomethine‐ester)s: nano‐blend formation with polyaniline

A new dihydroxy monomer, (E)‐1‐(4‐(4‐(4‐hydroxybenzylidene)thiocarbamoylaminobenzyl)phenyl)‐3‐(4‐hydroxybenzylidene)thiourea, was synthesized and polymerized with thiophene‐2,5‐dicarbonyl/terephthaloyl chloride. The structural characterization of the resulting polymers was carried out using spectral techniques (Fourier transform infrared and ¹H NMR) along with a physical property investigation. Novel polyesters are readily soluble in various amide solvents and possess high molar mass of 112 × 10³–133 × 10³ g mol^?1. The thermal stability was determined via 10% weight loss to be in the range 519–523 °C and the glass transition temperature was 286–289 °C. Electrically conducting poly(azomethine‐ester)‐blend‐polyaniline blends were prepared using mash‐blending and melt‐blending techniques. Materials obtained using the conventional melt‐blending approach generated an efficient conductive network compared with those produced by mash blending. Field emission scanning electron microscopy revealed a nano‐blend morphology for the melt‐blended system owing to increased physical interactions (hydrogen bonding and π–π stacking) between the two constituent polymers. Miscible blends of thiophene‐based poly(azomethine‐ester)‐blend‐polyaniline had superior conductivity (1.6–2.5 S cm^?1) and thermal stability (T₁₀ = 507 °C) even at low polyaniline concentration relative to reported thiophene/azomethine/polyaniline‐based structures. The new thermally stable and conducting nano‐blends could be candidates for various applications including optoelectronic devices. © 2012 Society of Chemical Industry     

Application of polyhedral oligomeric silsesquioxane to the stabilization and performance enhancement of poly(4‐methyl‐2‐pentyne) nanocomposite membranes for natural gas conditioning

The application of octatrimethylsiloxy polyhedral oligomeric silsesquioxane (POSS) nanoparticles was investigated in the fabrication of novel reverse‐selective poly(4‐methyl‐2‐pentyne) (PMP) nanocomposite membranes for the separation of heavier hydrocarbons from methane. Generally, PMP and PMP–fumed silica (FS) nanocomposite membranes suffer severe physical aging with approximately 40% permeation flux reduction over 120 days. A straightforward strategy was introduced to suppress the physical aging of PMP and also to improve the thermal stability without compromising the selectivities and permeabilities through the incorporation of a functionalized POSS–FS binary filler system. Fourier transform infrared spectroscopy and scanning electron microscopy proved productive interactions between the fillers and polymer, with a fair compatibility between them. Thermogravimetric analysis confirmed that the thermal stability of the neat PMP was enhanced by the incorporation of the fillers into the nanocomposites. The addition of POSS and FS led to improved operational performance, such as in the permeability and selectivity, over the neat PMP. The permeation stabilities of the PMP–POSS and PMP–FS–POSS nanocomposite membranes were clearly improved over a long time (120 days). The permeation data indicated that the PMP–3 wt % POSS–20 wt % FS nanocomposite membrane is promising for C₃H₈/N₂ and C₃H₈/CH₄ separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45158.     

Heterophase polymerization of different methacrylates: Effect of alkyl ester group on kinetics and colloidal behavior

In this article, methyl‐ (MMA), ethyl‐ (EMA), n‐butyl‐ (BMA), n‐hexyl (HMA), and 2‐ethyl hexyl (2‐EHMA) methacrylates were homopolymerized in heterophase at 60°C using sodium dodecyl sulfate as surfactant and potassium persulfate as initiator. The effects of monomer content in the reaction mixture (2.5 and 3.5 wt %) and the alkyl ester groups of the methacrylates on the kinetics, average particle diameter (Dp), molar masses, tacticity, and glass transition temperature (T_g) were studied. The final weight average molecular weights were in the range of 4.53 × 10⁵ to 2.78 × 10⁶ g/mol with polydispersities between 1.7 and 3.1 for different methacrylates. For 2.5 wt % of monomer concentration, the order of increase in polymerization rate was Rp_HMA > Rp_BMA > Rp_2‐EHMA > Rp_EMA > Rp_MMA, whereas for 3.5 wt % of monomer concentration was Rp_BMA > Rp_HMA > Rp_2‐EHMA > Rp_EMA > Rp_MMA. This behavior was ascribed to the differences in the water solubility, monomer partitioning between the different phases, and monomers reactivity. The Dp values varied between 42 and 65 nm, increasing according to the hydrophobicity of each monomer. ¹³C‐NMR (nuclear magnetic resonance) and differential scanning calorimetry analysis demonstrated that 79–87% of syndiotactic configuration was obtained for the different polymers. The steric effect of the alkyl ester length in the methacrylates contributed directly to promote the syndiotactic configuration. Nevertheless, T_g values (between ?7 and 120°C) for these polymers decreased when the alkyl ester length increased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40191.     

Synthesis and characterization of liquid crystalline polymers containing aromatic ester mesogen and a nonmesogenic ferrocene unit in the spacer

A new series of liquid crystalline polymers containing aromatic triad ester mesogen and 1,1′‐disubstituted ferrocene as a nonmesogenic unit along with polymethylene spacer was synthesized. The polymer was synthesized by a room temperature polycondensation reaction between bis(4‐chloroformyl phenyloxy alkyl ferrocene dicarboxylate) and quinol. The alkyl groups have been varied by an even number of methylene groups with a range from two to ten groups. All the polymers were found to possess liquid crystalline properties. The identification of the mesophase is more transparent with an increase in the spacer. The thermal characteristics were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results reveal that the thermal stability of the polymers was decreased with increasing spacer length. The T_g, T_m, and T_i of the polymers decreased with increasing methylene groups. The incorporation of the ferrocene moiety also has a considerable effect on the glass transition temperature. The char yield of the polymer decreases with an increasing methylene chain length. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3494–3501, 2002