Synthesis and pyrolysis of a novel preceramic polymer PZMS from PMS to fabricate high‐temperature‐resistant ZrC/SiC ceramic composite

As a valuable ultra‐high‐temperature ceramic (UHTC), ZrC was introduced to SiC ceramic for the preparation of high‐temperature‐resistant ZrC/SiC composite by a polymer‐derived method through the reaction between Cp₂Zr(CH=CH₂)₂ and polymethylsilane (PMS). The composition, structure, element distribution and pyrolysis process of the preceramic polymer polyzirconomethylsilane (PZMS) were investigated by nuclear magnetic resonance, infrared, gel permeation chromatography, X‐ray photoelectron spectroscopy, energy‐dispersive X‐ray spectroscopy, scanning electron microscopy and thermogravimetric analysis. The obtained ZrC/SiC ceramic composites had very good high‐temperature resistance with a weight loss of 7.1% after being subjected to temperatures ranging from 1200 to 2200°C, as the introduction of ZrC prevented the fast growth of crystalline β‐SiC. The ceramic composites prepared by this method were homogeneous with well‐distributed element components, and the ceramic yield reached as high as 78.4%. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation of a liquid boron‐modified polycarbosilane and its ceramic conversion to dense SiC ceramics

A boron‐modified ethynylhydridopolycarbosilane (B‐EHPCS) was successfully prepared via the hydroboration reaction of ethynylhydridopolycarbosilane (EHPCS) with 9‐borabicyclo‐[3.3.1]nonane (9‐BBN). The as‐synthesized B‐EHPCS with a branched structure was characterized by means of gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR). The structural evolution of ceramic conversion of B‐EHPCS was investigated by solid‐state NMR. The ¹³C magic angle spinning (MAS) NMR results indicated that the C?C and C?C groups of B‐EHPCS take part in the hydrosilation cross‐linking at a relatively low temperature (170°C). According to the ²⁹Si MAS NMR analysis, the CSiH₃ end groups are most reactive hydride functionality involved in the hydrosilation cross‐linking. With increasing curing temperature, the C₂SiH₂ and CSiH₃ units are completely consumed, while C₃SiH units remain even after curing at 600°C. The TGA results show the 1200°C ceramic yield of B‐EHPCS reaches 86%, which is 10% higher than that of the parent EHPCS (76%). At high temperatures, the introduction of <1 wt% boron significantly inhibits silicon carbide (SiC) crystallization. The 1800°C ceramics derived from B‐EHPCS are found to be significantly denser than that from EHPCS. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of a novel precursor‐derived ZrC/ZrB2 ultra‐high‐temperature ceramic composite

ZrC and ZrB₂, two valuable members of ultra‐high‐temperature ceramics (UHTCs), are potentially useful as structural materials in aerospace engineering and hypersonic flight vehicles. This work focused on the preparation of ZrC/ZrB₂ UHTC composite by employing a precursor‐derived method. The precursor polymer PZCB was synthesized by the reaction between Cp₂Zr(CH═CH₂)₂ and borane. The composition, structure, element distribution and pyrolysis process of PZCB were investigated by NMR, IR, X‐ray photoelectron spectroscopy, scanning electron microscopy and TGA. The ceramic yield was 50% and the obtained well‐distributed ZrC/ZrB₂ ceramic composites had very good high‐temperature resistance. Copyright © 2012 John Wiley & Sons, Ltd.     

Novel propargyl‐substituted azo‐coupled phenolic resins

Novel propargyl that contains phenolic resins via azo‐coupling reaction was synthesized. Peculiarities of curing process were investigated by differential scanning calorimetry analysis. Polymerization of resins with azo groups was estimated to be affected by radicals obtained at resin decomposition causing 10°C peak shift to lower temperatures in comparison with resin containing only propargyl group. At the same time, polymerization of triple propargyl bond was shown to not proceed at radical initiation until Cleisen rearrangement and chromene formation. Thermogravimetric analysis revealed increase of thermal stability by 170–190°C and char yield by up to 20% for modified resins in comparison with original novolac resin. Heat deflection temperature estimated by dynamic mechanical analysis was also shown to be increased by at least 110°C for modified resins in comparison with novolac resin. All the synthesized resins are soluble in acetone and used for preparation of unidirectional glass fiber‐based composites. Flexural strength and modulus for modified resins‐based composites were shown to increase by at least 25% and 10% correspondingly in comparison with novolac‐based composite. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of nanosized zirconium carbide from preceramic polymers by the facile one‐pot reaction

A novel preceramic polymer, polyzirconoxanesal (PZS), was synthesized efficiently by one‐pot protocol. The PZS polymer was characterized by the techniques of Fourier transform infrared spectra (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR) and gel permeation chromatography (GPC). The precursor exhibited excellent solubility and rheology for the processing of ceramic matrix fiber composites. Pyrolytic conversion of the preceramic polymer was studied by means of thermogravimetric analysis (TGA), X‐ray diffraction (XRD), scanning electron microscope (SEM) and element analysis. It is suggested that the polymer decomposed completely at 600°C and nanosized ZrC is formed at 1300°C for 2 hr in argon atmosphere with a yield of 68.5%. To the best of our knowledge, this is the lowest temperature reported in the literatures for preparing ZrC ceramics from preceramic polymers. The obtained ZrC particles exhibit spherical morphology with size ranged in 20–100 nm. Copyright © 2010 John Wiley & Sons, Ltd.     

Temperature‐responsive “tadpole‐shaped” protein–polymer hybrids and their self‐assembly behavior

The temperature‐responsive poly (N, N‐diethylacrylamide) (pDEAAm) with narrower molecular weight distribution was prepared by the atom transfer radical polymerization and characterized by ¹HNMR and gel permeation chromatography. The temperature‐responsive “tadpole‐shaped” BSA–pDEAAm hybrids were fabricated via a free Cys‐34 residue of bovine serum albumin (BSA) site specifically binding to the end group disulfide bonds of pDEAAm and characterized by native‐polyacrylamide gel electrophoresis (Native‐PAGE) and matrix‐assisted laser desorption/ionization time of flight mass spectrometry. Their temperature‐responsive behaviors were measured by ultraviolet‐visible spectra (UV‐Vis). The lower critical solution temperature (LCST) of the pDEAAm was identified as 28°C, and the LCST of BSA–pDEAAm hybrids was identified as 31°C. The morphologies of BSA–pDEAAm hybrids self‐assembled in the aqueous solutions with two different temperatures at 25 °C and 40°C were investigated by transmission electron microscopy. Below the LCST of BSA–pDEAAm hybrids, the separate spherical nanoparticles were observed. In contrast, bundles and clusters were observed above the LCST of BSA–pDEAAm hybrids. The results suggested that the self‐assembly morphology of BSA–pDEAAm hybrids depended upon the pDEAAm block in BSA–pDEAAm hybrids, and the morphology transitions were effected by the LCST of BSA–pDEAAm hybrids. It would be expected to be used in biomedicine and materials science. Copyright © 2016 John Wiley & Sons, Ltd.     

Development and characterization of fully bio‐based polybenzoxazine‐silica hybrid composites for low‐k and flame‐retardant applications

In the present work, new classes of bio‐based polybenzoxazines were synthesized using eugenol as phenol source and furfurylamine and stearylamine as amine sources separately through solventless green synthetic process routes and were further reinforced with varying percentages (1, 3, 5, and 10 wt%) of silica (from rice husk) to attain hybrid composites. The molecular structure, cure behaviour, thermal stability, dielectric properties, and flame‐retardant behaviour of both benzoxazine monomers and benzoxazine composites were characterized using appropriate modern analytical techniques. The eugenol‐based benzoxazines synthesized using furfurylamine (FBz) and stearylamine (SBz) were cured at 223°C and 233°C, respectively. The differential scanning calorimetry (DSC) data reveal the glass transition temperatures (T_g) of FBz and SBz were 157°C and 132°C, respectively, and the maximum decomposition temperature (T_max) as obtained from thermogravimetric analysis (TGA), were found to be 464°C and 398°C for FBz and SBz, respectively. The dielectric constants for FBz and SBz obtained at 1 MHz were 3.28 and 3.62, respectively. Furthermore, varying weight percentages (1, 3, 5, and 10 wt%) of 3‐mercaptopropyltrimethoxysilane (3‐MPTMS) functionalized bio‐silica reinforced the composite materials as evidenced by their improved thermal stability and lower dielectric constant. Data obtained from thermal and dielectric studies suggested that these polybenzoxazines could be used in the form of adhesives, sealants, and composites for high performance inter‐layer low‐k dielectric applications in microelectronics.     

Diacetylene–siloxane–carborane thermosets and ceramic precursors

Thermosets and ceramic chars were prepared and characterized from a diacetylene–siloxane–carborane polymer, DSCS, and a diacetylene–siloxane polymer, DS. The goal was to incorporate the known thermo‐oxidative stability found in the siloxane–carborane elastomers into high‐performance thermosets and ceramic chars. The DSCS thermoset had excellent thermo‐oxidative stability as determined by a low weight loss and tough residue after annealing for 100 h in air at 300 °C, but it had a low glass transition temperature (94 °C). The DS thermoset did not undergo a glass transition below 350 °C and had a low weight loss on thermo‐oxidative aging, but the residue was quite brittle. Two random copolymers were made to optimize the thermo‐oxidative stability and toughness of the DSCS thermoset and the higher glass transition of the DS thermoset. Significantly, the 50:50 DSCS/DS random copolymer when cured to a thermoset did not undergo a glass transition below 350 °C, yet retained much of the strength, toughness and thermo‐oxidative stability of the DSCS thermoset. Heat treatment of the poly‐DSCS to elevated temperatures resulted in a ceramic material with improved properties relative to the ceramic derived from poly‐DS. Both polymers had similar char yields to 800 °C, but the poly‐DSCS solidified to a 15% denser ceramic. Copyright © 2000 John Wiley & Sons, Ltd.     

Mechanical,thermal, and UV‐shielding behavior of silane surface modified ZnO‐reinforced phthalonitrile nanocomposites

In the present work, zinc oxide nanoparticles were treated with aminopropyl trimethoxy silane‐coupling agent and used as a new kind of reinforcement for a typical high performance bisphenol‐A‐based phthalonitrile resin. The resulted nanocomposites were characterized for their mechanical, thermal, and optical properties. Results from the tensile test indicated that the tensile strength and modulus as well as the toughness state of the matrix were all enhanced with the increasing of the nanoparticles amount. Thermogravimetric analysis showed that the starting decomposition temperatures and the residual weight at 800°C were highly improved upon adding the nanofillers. At 6 wt% nanoloading, the glass transition temperature and the storage modulus were considerably enhanced reaching about 359°C and 3.7 GPa, respectively. The optical tests revealed that the neat resin possesses excellent UV‐shielding properties, which were further enhanced by adding the nanofillers. Furthermore, the fractured surfaces of the nanocomposites analyzed by scanning electron microscope exhibited homogeneous and rougher surfaces compared with that of the pristine resin. Finally, the good dispersion of the reinforcing phase into the matrix was confirmed by a high resolution transmission electron microscope. Copyright © 2015 John Wiley & Sons, Ltd.     

Reverse atom transfer radical random copolymerization of styrene and methyl methacrylate in the presence of diatomite nanoplatelets

Diatomite nanoplatelets were used for in situ random copolymerization of styrene and methyl methacrylate by reverse atom transfer radical polymerization to synthesize different well‐defined nanocomposites. Inherent features of the pristine diatomite nanoplatelets were evaluated by Fourier transform infrared spectroscopy, nitrogen adsorption/desorption isotherm, scanning electron microscope, and transmission electron microscope. Gas and size exclusion chromatography was also used to determine conversion and molecular weight determinations, respectively. Considerable increment in conversion (from 81% to 97%) was achieved by adding 3 wt% diatomite nanoplatelets in the copolymer matrix. Moreover, molecular weight of random copolymer chains was increased from 12 890 to 13 960 g·mol⁻¹ by addition of 3 wt% diatomite nanoplatelets; however, polydispersity index (PDI) values increases from 1.36 to 1.59. Proton nuclear magnetic resonance spectroscopy was used to evaluate copolymers composition. Thermal gravimetric analysis results indicate that thermal stability of the nanocomposites is improved by adding diatomite nanoplatelets. Differential scanning calorimetry shows an increase in glass transition temperature from 66°C to 71°C by adding 3 wt% of diatomite nanoplatelets.     

Large electro‐optic activity and enhanced temporal stability of methacrylate‐based crosslinking hyperbranched nonlinear optical polymer

A methacrylate‐based crosslinking hyperbranced polymers have been synthesized through initiator‐fragment incorporation radical polymerization and used for the temperature stable electro‐optic (EO) polymer application. This polymer consists of methyl methacrylate, 2‐metacryloxyethyl isocyanate, and ethylene glycol dimethacrylate (EGDMA) monomers. The use of EGDMA as a bifunctional unit resulted in the solvent‐soluble crosslinking hyperbranched chain, so that the EO polymer enhanced glass transition temperatures. A phenyl vinylene thiophene vinylene bridge nonlinear optical chromophore was attached to the polymer backbone as the side‐chain by a post‐functionalization reaction. The loading concentration of the chromophore was varied between 30 and 50 wt % by simply changing the mixing ratio of the precursor polymer to the chromophore. The synthesized EO polymers produced optical quality films with a light propagation loss of 0.61 dB/cm in a slab waveguide at 1.31 μm. The electrically poled film had an EO coefficient (r₃₃) of 139 pm/V at 1.31 μm. The EO crosslinking hyperbranced polymer had a high‐glass transition temperature of 170 °C, and exhibited excellent temporal stability of the EO activity at 85 °C for 500 h. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of poly(4‐alkyl‐4‐methyl‐2‐azetidinone)s

Poly‐β‐amides (nylons 3) were synthesized via the anionic polymerization of a series of 4‐alkyl‐4‐methyl‐2‐azetidinones where the alkyl group is a methyl, ethyl, propyl, butyl, or pentyl. The “non‐assisted” polymerization was conducted under vacuum, in the bulk, at 160°C, using potassium 2‐pyrrolidonate as catalyst, whereas the “assisted” polymerization was carried in dimethylsulfoxide, at room temperature, using N‐acetylpyrrolidinone‐2 as activator but it gave no polymer with a propyl or bulkier side group. Side reactions occur in all cases. X‐ray spectra showed that poly(4‐alkyl‐4‐methyl‐2‐azetidinone)s are amorphous with propyl, butyl, and pentyl groups, and semi‐crystalline with methyl or ethyl substituents. Both semi‐crystalline polyamides exhibit an extended planar zigzag conformation, with a fiber identity period along the c axis of 4.9 Å. Glass transition temperatures, melting temperatures, and/or decomposition temperatures are also reported. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 761–769, 1999     

Preparation and properties of high‐pretilt‐angle polyimides based on an alicyclic dianhydride and long alkyloxy side‐group‐containing diamines

A series of polyimides were prepared by a solution polycondensation reaction between 3‐carboxylmethylcyclopentane‐1,2,4‐tricarboxylic dianhydride and 4‐alkyloxybenzene‐1,3‐diamines in N‐methyl‐2‐pyrrolidone and chemical imidization with triethylamine and acetic anhydride. These polyimides possess great organo‐solubility, high optical transparency, and high pretilt angles. They are soluble not only in strong polar aprotic organic solvents such as N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, m‐cresol, and 1,4‐butyrolactone but also in common low‐boiling‐point solvents such as chloroform and tetrahydrofuran, and some are even soluble in acetone. They exhibit high transparency at wavelengths greater than 320 nm. They can generate pretilt angles greater than 5°, and some can even achieve pretilt angles greater than 10°. The pretilt angle of a polyimide increases with the increasing length of the alkyloxy side group. The polyimides possess glass‐transition temperatures between 180 and 230 °C and thermal decomposition temperatures (onset temperatures) of about 435 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1943–1950, 2000     

Morphology of epoxy/acrylic polymer‐dispersed liquid‐crystal film in DICY thermal cure

A polymer‐dispersed liquid‐crystal (PDLC) film was prepared from UV‐curable acrylic, thermally curable epoxy, and a liquid‐crystal (LC) mixture with a fixed LC content of 40 wt %. The UV irradiation and heat treatments were in sequential steps. At first, a phase diagram of a binary mixture of LC (E63) and epoxy [diglycidyl ether of polypropylene glycol (DER736)] was established to understand their miscibility. Then, the phase‐separation temperatures and morphologies of pre‐UV‐cured films with different equivalent DER736/dicyandiamide (DICY) molar ratios were observed. Finally, the polymerization‐induced phase‐separation behavior and morphology of the PDLC film were studied by real‐time observation while the film was maintained at 130 °C under the microscope. The results showed that the acrylic network would not affect the phase‐separation behavior of the E63/DER736 mixture. In both thermally induced and polymerization‐induced phase separations, the undissolved DICY particles acted as nucleation agents and were capable of inducing E63 to separate out early. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2033–2042, 2000     

Synthesis and characterization of poly (1‐vinyl‐3‐butylimidazolium‐co‐methyl methacrylate) gel polymer electrolytes for dye‐sensitized solar cells: Effect of structure and composition

Herein, three ionic liquid random copolymers (P) containing 1‐vinyl‐3‐butylimidazolium bromide (VBImBr) and methyl methacrylate (MMA) with various molar ratios were prepared using conventional free radical polymerization. Afterward, their corresponding chemically cross‐linked copolymers (XP) were formed similarly in the presence of polyethylene glycol dimethacrylate (PEGDMA). The synthesized copolymers were characterized using FT‐IR, ¹H NMR, and GPC. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) results showed that the rigidity and thermal stability of the copolymers depended on the ionic liquid content as well as the degree of cross‐linking. Gel polymer electrolytes were then prepared via obtained copolymers in the presence of a constant amount of synthesized imidazolium‐based ionic liquid. Among the copolymers, the P3 with in feed VBImBr:MMA molar ratio of 70:30 and the cross‐linked 1%‐XP3 copolymer prepared with 1 mol% of PEGDMA exhibited the highest conductivity and diffusion coefficients for I₃^¯ and I^¯. The power conversion efficiency of the optimized linear and cross‐linked copolymers (P3 and 1%‐XP3) under the simulated AM 1.5 solar spectrum irradiation at 100 mW cm^?2 were 3.49 and 4.13% in the fabricated dye‐sensitized solar cells (DSSCs), respectively. The superior long‐term stability and high performance of the gel electrolyte containing 1%‐XP3 suggested it as commercial gel electrolyte for future DSSCs.     

Enzymatic‐catalyzed polymerization of water‐soluble electrically conductive polymer PEDOT:PSS

Water‐soluble electrically conductive polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) was synthesized by the enzymatic‐catalyzed method using 3,4‐ethylenedioxythiophene (EDOT) as monomer, poly(styrenesulfonate) (PSS) as water‐soluble polyelectrolyte, horseradish peroxidase enzyme as catalyst, and hydrogen peroxide (H₂O₂) as oxidant. Fourier transform infrared spectra and UV–vis absorption spectra confirm the successful enzymatic‐catalyzed polymerization of PEDOT. Dynamic light scattering data confirm the formation of a stable PEDOT:PSS aqueous dispersion. The thermo gravimetric data show that the obtained PEDOT is stable over a fairly high range of temperatures. The atomic force microscopy height images show that the PEDOT:PSS aqueous dispersion can form excellent homogeneous and smooth films on various substrates by conventional solution processing techniques, which renders this PEDOT:PSS aqueous dispersion a very promising candidate for various application in electronic devices. This enzymatic polymerization is a new approach for the synthesis of optical and electrical active PEDOT polymer, which benefits simple setting, high yields, and environmental friendly route. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and properties of a new fluorine‐containing polybenzimidazole for high‐temperature fuel‐cell applications

An amorphous, organosoluble, fluorine‐containing polybenzimidazole (PBI) was synthesized from 3,3′‐diaminobenzidine and 2,2‐bis(4‐carboxyphenyl)hexafluoropropane. The polymer was soluble in N‐methylpyrrolidinone and dimethylacetamide and had an inherent viscosity of 2.5 dL/g measured in dimethylacetamide at a concentration of 0.5 g/dL. The 5% weight loss temperature of the polymer was 520 °C. Proton‐conducting PBI membranes were prepared via solution casting and doped with different amounts of phosphoric acid. In the methanol permeability measurement, the PBI membranes showed much better methanol barrier ability than a Nafion membrane. The proton conductivity of the acid‐doped PBI membranes increased with increasing temperatures and concentrations of phosphoric acid in the polymer. The PBI membranes showed higher proton conductivity than a Nafion 117 membrane at high temperatures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4508–4513, 2006     

Thermal radical initiator derivatives based on O‐imino‐isourea: Synthesis,polymerization, and characterization

The new thermal radical initiators (TRIs) with linear and cyclic type groups based on derivatives of O‐imino‐isourea have been designed and synthesized. The radical polymerization property of the synthesized TRI derivatives as a radical initiator in n‐butyl acrylate was monitored by differential scanning calorimetry analysis. TRI derivatives with linear type groups, such as 3‐PenDCC, 3‐HexDCC, and 4‐HepDCC, showed peak temperatures (T_peak) of 80–84 °C, whereas those with cyclic type groups, such as C‐PenDCC, C‐HexDCC, and C‐HepDCC, exhibited a wide T_peak distribution in the 74–87 °C range. The polymerization efficiency using new TRIs in n‐butyl acrylate was elaborately identified from the molecular weights and conversion obtained using gel permeation chromatography analysis and NMR spectroscopy. To consider their possible application to automotive clearcoats, the real‐time evolution of the rheological properties of clearcoat resins during the crosslinking process with newly synthesized TRI derivatives was measured, confirming the different crosslinking kinetics of TRI derivatives in real thermal curing process. The results were found to be well correlated with data from the radical polymerization experiments of TRIs. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3593–3600.     

Properties of Nylon‐6/Na+‐Montmorillonite Nanocomposites Obtained by Hydrolyzed Ring‐Opening Polymerization

Summary: Nylon‐6/Na⁺‐montmorillonite (MMT) nanocomposites (NNNs) are synthesized by a hydrolyzed ring‐opening polymerization. At a loading of only 2 wt.‐% MMT, the tensile modulus, the flexural modulus, and the heat distortion temperature of the NNNs exhibit increases of nearly 20%, 60%, and 63 °C, respectively. Compared with that of neat nylon‐6, the temperature of the main α‐relaxation (T_α) of the NNNs is shifted 3.6 °C toward higher temperatures and two β‐relaxation peaks are observed. Another interesting phenomenon is that there is a new melting peak (at about 206 °C) for the NNNs.

DSC second heating curves of neat nylon‐6 (N6), nylon‐6/Na⁺‐MMT nanocomposites with highly swollen Na⁺‐MMT (NHM), and nylon‐6/Na⁺‐MMT nanocomposites with slightly swollen Na⁺‐MMT (NSM) with various amounts of Na⁺‐MMT.     

Synthesis of norbornenes containing cationic mono‐ and di(cyclopentadienyliron)arene complexes and their ring‐opening metathesis polymerization

A number of classes of polynorbornenes containing cationic iron moieties within their side chains were prepared via ring‐opening metathesis polymerization with a ruthenium‐based catalyst. The iron‐containing polymers displayed excellent solubility in polar organic solvents. The weight‐average molecular weights of these polymeric materials were estimated to be in the range of 18,000–48,000. Thermogravimetric analysis of these polymers showed two distinct weight losses. The first weight loss was in the range of 204–260 °C and was due to the loss of the metallic moieties, whereas the second weight loss was observed at 368–512 °C and was due to the degradation of the polymer backbone. Cyclic voltammetry studies of the iron‐containing polymers showed that the 18 e^? cationic iron centers underwent a reduction to give the neutral 19 e^? complexes at half‐wave potential (E_1/2) = ?1.105 V. Photolysis of the metallated polymers led to the isolation of the norbornene polymers in very good yields. Differential scanning calorimetry studies showed a sharp increase in the glass‐transition temperatures up to 91 °C when rigid aromatic side chains were incorporated into the norbornene polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3053–3070, 2006