Side‐chain effects on the morphology and properties of fluorene‐based alternating copolymers

Soluble fluorene‐based alternating copolymers containing benzene as the comonomer were synthesized and characterized, in which three different side chains (hydrogen atom, linear octyloxy and bulky benzyloxy groups) were attached to the phenylene ring. The effect of the side chains with different steric hindrances on the photophysical, thermal and electrochemical properties as well as the morphology were investigated. Moreover, the chain conformation and spectroscopic properties in dilute solution were studied to understand the solvent effect. Aliphatic and aromatic solvents were demonstrated to have different influences on the spectra of the polymers owing to various interaction mechanisms in the excited states. Also, a significant decrease of up to 80 °C in the thermal degradation temperature was observed as a result of the introduction of large benzyloxy units. The energy levels of the highest occupied molecular orbital and the lowest unoccupied molecular orbital of the polymers were estimated to be ? 5.76 to ? 5.82 eV and ? 2.19 to ? 2.27 eV, respectively, from cyclic voltammetry measurements. In addition, the electronic structures of the polymers were described via quantum chemical calculations. Copyright © 2007 Society of Chemical Industry     

Preparation and characterization of alternating copolymers containing fluorene and hexyl‐ or perfluorohexyl‐substituted thiophene

Alternating copolymers containing fluorene and hexyl‐ or perfluorohexyl‐substituted thiophene were synthesized by a palladium‐catalyzed cross‐coupling reaction, and the structures of the polymers were confirmed using nuclear magnetic resonance spectroscopy. The absorption spectra of polymers containing perfluorohexyl substituents show shorter maximum wavelength due to the steric hindrance between fluorene and substituted thiophene units. In addition, the perfluorohexyl substituents can effectively interrupt the conjugation length of the polymers, which leads to an increase in the optical bandgap and decrease in the photoluminescence quantum yield. Solid‐state UV‐visible absorption and emission maxima of the polymers containing perfluorohexyl‐substituted thiophene units are blue‐shifted in comparison to those of polymers in solution due to the packing structure of perfluoroalkyl chains. © 2014 Society of Chemical Industry     

Miscibility,morphology and thermal properties of poly(para‐dioxanone)/poly(D,L‐lactide) blends

BACKGROUND: Poly(para‐dioxanone) (PPDO) is a biodegradable polyester with excellent biodegradability, bioabsorbability, biocompatibility and mechanical flexibility. However, its high cost and relatively fast degradation rate have hindered the development of commercial applications. Blending with other polymers is a simple and convenient way of modifying the properties of aliphatic polyesters. Poly(D ,L ‐lactide) (PDLLA) is another polyester that has been extensively studied for biomedical applications due to its biocompatibility and suitable degradation rate. However, to our knowledge, blends of PPDO/PDLLA have not been reported in the literature. RESULTS: A series of biodegradable polymers were blended by solution co‐precipitation of PPDO and PDLLA in various blend ratios. The miscibility, morphology and thermal properties of the materials were investigated. DSC curves for all blends revealed two discrete glass transition temperatures which matched the values for pure PPDO and PDLLA. SEM images of fracture surfaces displayed evidence of phase separation consistent with the DSC results. The contact angles increased with the addition of PDLLA. CONCLUSION: PPDO/PDLLA blends exhibit two distinct glass transition temperatures that remain nearly constant and correspond to the glass transition temperatures of the homopolymers for all blend compositions, indicating that blends of PPDO and PDLLA are immiscible. Images of the surface obtained using SEM were also suggestive of a two‐phase material. The crystallinity of the PPDO phase in the blends was affected by the PDLLA content. The mechanical properties of the blends changed dramatically with composition. Adding PDLLA makes the blends less hydrophilic than PPDO. Copyright © 2008 Society of Chemical Industry     

A novel polymer chemodosimeter for the detection of mercury ions: Synthesis and fluorescence “turn‐on” responses of fluorene‐based conjugated polymer with reactive pendent N,N‐diethyl‐2‐(4‐phenoxy)‐thioacetamide

A novel conjugating polyfluorene bearing N,N‐diethyl‐2‐(4‐phenoxy)‐thioacetamide as side chain was designed for the detection of Hg(II) ions. It was synthesized through postfunctionalization of acetamide‐based polyfluorene derivative. Upon the addition of Hg(II) ions, the thioacetamide groups of this polymer side chains were specifically reacted with Hg(II) ions, leading to this chemodosimeter with higher selectivity for Hg(II) over other metal ions tested under the same conditions. In addition, on the basis of the effect of fluorescent signal amplifications originated from electron transmission along the backbone, this designed conjugated polyfluorene with pendent reactive thioacetamide reached ultra high sensitivity for the detection of mercury ions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on the mesomorphic properties of ferrocenylene‐based organophosphorous liquid‐crystalline polymers containing phenyl and biphenyl pendant units

The synthesis, mesomorphic character, and effect of spacers in ferrocene‐containing main‐chain liquid‐crystalline polymers are reported in this article. Two different monomers containing ferrocene and phenyl/biphenyl phosphate groups possessing even numbers of spacers from 2 to 10 were prepared and polymerized by polycondensation at room temperature. All the polymers gave birefringent melt except one. The identification of the mesophase was transparent with an increase in spacers. The effect of substitution in the side chain with regard to bulkiness and spacers were studied with thermogravimetric analysis and differential scanning calorimetry. The results reveal that the thermal stability of the polymers increased with the increasing bulkiness of the side chain and decreased with increasing spacer length. The incorporation of the phosphorous moiety also had a considerable effect on the glass‐transition temperature. Char yield of the polymer decreased with increasing methylene chain length, and it did not vary much with the size of the pendent groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 831–841, 2002     

Morphology and photophysical properties of a thermally responsive fluorescent material based on a rod‐coil tri‐block copolymer

A thermally responsive rod‐coil poly[poly (N‐isopropylacrylamide)‐b‐polyfluorene‐b‐poly(N‐isopropylacrylamide)] triblock copolymer has been successfully synthesized by atom transfer radical polymerization from an end‐functionalized macroinitiator. The thermochromic behavior and relevant morphology of this polymer were investigated by UV‐vis spectra, DLS, and AFM, respectively, at various temperatures. A thermally responsive fluorescent material was achieved facilely by combining the optically active polyfluorene with temperature‐responsive poly(N‐isopropylacrylamide). All the measurements demonstrated that in the region of 25–45°C, the polymer underwent a phase transition and the corresponding change in optical properties in its water solution. However, the polymer did not show completely reversible behavior upon heating and cooling. On the basis of the comparison with two other thermally responsive conjugated polymers in literatures, a tentative mechanism has been proposed that π–π interaction induced rigid segments to remain chain conformation and packing styles as in collapsed state. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of novel polyamides containing sulfone‐ether linkages and xanthene cardo groups

In order to obtain polyamides with enhanced solubility and processability, as well as good mechanical and thermal properties, several novel polyamides containing sulfone‐ether linkages and xanthene cardo groups based on a new diamine monomer, 9,9‐bis[4‐(4‐aminophenoxy)phenyl]xanthene (BAPX), were investigated. The BAPX monomer was synthesized via a two‐step process consisting of an aromatic nucleophilic substitution reaction of readily available 4‐chloronitrobenzene with 9,9‐bis(4‐hydroxyphenyl)xanthene in the presence of potassium carbonate in N,N‐dimethylformamide, followed by catalytic reduction with hydrazine and Pd/C. Four novel aromatic polyamides containing sulfone‐ether linkages and xanthene cardo groups with inherent viscosities between 0.98 and 1.22 dL g^?1 were prepared by low‐temperature polycondensation of BAPX with 4,4′‐sulfonyldibenzoyl chloride, 4,4′‐[sulfonyl‐bis(4‐phenyleneoxy)]dibenzoyl chloride, 3,3′‐[sulfonyl‐bis(4‐phenyleneoxy)]dibenzoyl chloride and 4,4′‐[sulfonyl‐bis(2,6‐dimethyl‐1,4‐phenyleneoxy)]dibenzoyl chloride in N,N‐dimethylacetamide (DMAc) solution containing pyridine. All these new polyamides were amorphous and readily soluble in various polar solvents such as DMAc and N‐methylpyrrolidone. These polymers showed relatively high glass transition temperatures in the range 238–298 °C, almost no weight loss up to 450 °C in air or nitrogen atmosphere, decomposition temperatures at 10% weight loss ranging from 472 to 523 °C and 465 to 512 °C in nitrogen and air, respectively, and char yields at 800 °C in nitrogen higher than 50 wt%. Transparent, flexible and tough films of these polymers cast from DMAc solution exhibited tensile strengths ranging from 78 to 87 MPa, elongations at break from 9 to 13% and initial moduli from 1.7 to 2.2 GPa. Primary characterization of these novel polyamides shows that they might serve as new candidates for processable high‐performance polymeric materials. Copyright © 2010 Society of Chemical Industry     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry     

Physical properties of hydrogels of poly(2‐hydroxyethyl methacrylate) and copolymers with mono‐methyl itaconate synthesized by bulk and solution polymerization

The physical properties found during the swelling process of poly(2‐hydroxyethyl methacrylate) (PHEMA) and of copolymers of HEMA with mono‐n‐methyl itaconate, synthesized by solution and bulk polymerization, are reported. The swelling kinetics were followed at four different temperatures (295, 300, 305 and 310 K). Experimental data follow second‐order swelling kinetics, from where the kinetic rate constant k_∞ and the swelling capacity at equilibrium W_∞ were calculated as a function of temperature. The kinetic rate constant obeys Arrhenius behaviour. The following network parameters were determined for the hydrogels: Young's moduli E, effective crosslinking density v_e, molar mass per crosslink M_C, volume fraction ϕ₂ and polymer‐liquid interaction parameter χ. © 2000 Society of Chemical Industry     

Synthesis and solution properties of temperature‐sensitive copolymers based on NIPAM

A kind of temperature‐sensitive water‐soluble polymers P(NIPAM‐HEMA‐AM) of N‐isopropylacrylamide (NIPAM), hydroxyethyl methacrylate (HEMA) and acrylamide (AM) were synthesized by free radical aqueous solution copolymerization. The polymers were characterized by Fourier transform infrared spectrum (FTIR) method. Solution properties, such as the influences of monomer ratios and additives on the low critical soluble temperature (LCST) of the polymer solutions as well as the viscosity‐temperature properties were studied. The results show that the polymer concentrations have no significant influence on the LCST of polymer solutions. The incorporation of HEMA units leads to a lower LCST, while AM units to a higher LCST. The additions of small molecules such as salt and surfactant also have significant effect on the LCST, the addition of NaCl decreases the LCST, while the addition of sodium dodecylbenzenesulfonate (SDBS) increases the LCST. The apparent viscosity of polymer solutions depends on temperature. The 1.5 wt % aqueous solutions of P(NIPAM‐HEMA‐AM) exhibits good thermo‐thickening behavior over 55°C, whereas the 0.8 wt % aqueous solutions do not show this behavior during the heating process. The aqueous solutions of P(NIPAM‐HEMA‐AM) are viscoelastic fluids, and the viscoelasticities mainly depend on temperature. Both the storage modulus (G') and loss modulus (G'') of 1.5 wt % polymer solutions increase with temperature. Over 55°C, G' exceeds G'', and the polymer solutions are elasticity‐dominated. In contrast, below 55°C, G'' is larger than G', and the polymer solutions are viscosity‐dominated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly‐2‐oxazolidones with tailored physical properties synthesized by catalyzed polyaddition of 2,4‐toluene diisocyanate and different bisphenol‐based diepoxides

In the current study, we investigated poly‐2‐oxazolidones containing one of four different diglycidyl ethers carrying different bulky bisphenol centers. With increasing steric hindrance of the bisphenol‐based diepoxide from bisphenol F to bisphenol A, Z and TMC, the glass transition temperature (T_g) increased markedly from 156 to 211 °C, whereas the plateau modulus of the polymer, i.e. the chain flexibility as determined from rheological characterization, remained almost unchanged. This study demonstrates the general feasibility of the chemical design of poly‐2‐oxazolidones as an amorphous high‐performance thermoplastic. © 2016 Society of Chemical Industry     

Synthesis of tung oil–diacrylate copolymers via the Diels‐Alder reaction and properties of films from the copolymers

Copolymers were synthesized from tung oil and 1,6 hexanediol diacrylate or 1,4‐butanediol diacrylate via the Diels‐Alder reaction. The copolymers were completely soluble in common laboratory solvents, and had very broad molecular weight distributions. The residual double bonds in the copolymers were used to cure films by oxidative means. The films had good solvent resistance, good gloss, and a reasonable hardness–flexibility balance. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2369–2375, 2001     

Optical and electronic properties of 3,4‐dialkylthiophene‐based p‐/n‐alternating copolymers

Four novel highly soluble p‐/n‐poly[(2,5‐divinyl‐3,4‐dialkylthiophene)‐alt‐2,6‐pyridine] (PA₂TV‐Py) and poly[(2,5‐divinyl‐3,4‐dialkylthiophene)‐alt‐(2,5‐diphenyl‐1,3,4‐oxadiazole)] (PA₂TV‐OXD) are prepared by Heck coupling approach to compare their photoelectric properties. Characterizations of the copolymers include FT‐IR, ¹H‐NMR, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), UV–vis spectroscopy, photoluminescence (PL), and electroluminescence (EL). Four alt‐copolymers exhibit excellent solubility in common organic solvents (e.g., CHCl₃, THF) and good thermal stabilities, losing less than 5% on heating to ～ 250°C. The optical properties depict that the band‐gap energy of PA₂TV‐Py and PA₂TV‐OXD is similarly, ranging from 2.68 to 2.80 eV in solid film and 2.90–2.97 eV in CHCl₃ solution. PA₂TV‐Pys can emit bright turquoise light with quantum efficiencies (QE) of 30.6 and 53.9%, which about 10‐18 times higher than that of homopolymer in CHCl₃ solution. Furthermore, the QE of two PA₂TV‐OXDs (purple fluorescence) are increased to 43.6 and 68.5%, respectively, about 1.3–1.4 times higher than that of PA₂TV‐Pys. Electrochemical results indicate that the electron affinity (E_a) of four alt‐copolymers range from 2.79 to 3.09 eV, which are propitious to electrons injecting and transporting from the cathode. As a result, these novel copolymers present expected good electroluminescence(EL) performance in their single layer polymer light‐emitting device (PLED) with configuration of ITO/polymer/Al, which turn‐on voltages are between 4.0 and 5.8 V and emit bright green–yellow (538 nm) and yellow (545–552 nm) EL light. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and physical properties of liquid‐crystalline copolymers with azobenzene segments

To investigate the effects of photoisomerizable azobenzene segments on the liquid‐crystalline characteristics and thermal properties of polymers, a series of liquid‐crystalline homopolymers and copolymers with azobenzene segments was synthesized. The azobenzene contents of the copolymers were estimated with elemental analysis. The photoisomerization of the azobenzene derivatives was studied with ultraviolet–visible (UV–vis) spectroscopy. The UV–vis absorption of the copolymers was found to be parallel with the content of the azobenzene segments. UV irradiation was found to cause a decrease in the copolymer transmittance around 355 nm due to the photoinduced isomerization from entgegen (E) to zusammen (Z). The phase‐transition temperatures and molecular weights of the polymers were investigated with differential scanning calorimetry and gel permeation chromatography, respectively. The variation in the phase‐transition temperature of the homopolymers before and after UV (365 nm) irradiation was investigated. The bended Z structure was found to disturb the order of the orientation of liquid crystals and to lower the phase‐transition temperature. The appearance of the polymer film was changed from opaque to clear after sufficient UV irradiation. The image recording of the polymer films was achieved after UV irradiation through a mask with pictures. The stability and reliability of the Nematic‐Isotropic phase transition of the homopolymers was evaluated with repeated cycles of 365‐nm UV irradiation and heating at 130°C. After the recycle phase transition was repeated nine times, no significant decay in the response and transmittance could be found. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 2006     

Hyperbranched copolymers of p‐(chloromethyl)styrene and N‐cyclohexylmaleimide synthesized by atom transfer radical polymerization

The hyperbranched copolymers were obtained by the atom transfer radical copolymerization of p‐(chloromethyl)styrene (CMS) with N‐cyclohexylmaleimide (NCMI) catalyzed by CuCl/2,2′‐bipyridine (bpy) in cyclohexanone (C₆H₁₀O) or anisole (PhOCH₃) with CMS as the inimer. The influences of several factors, such as temperature, solvent, the concentration of CuCl and bpy, and monomer ratio, on the copolymerization were subsequently investigated. The apparent enthalpy of activation for the overall copolymerization was measured to be 37.2 kJ/mol. The fractional orders obtained in the copolymerization were approximately 0.843 and 0.447 for [CuCl]₀ and [bpy]₀, respectively. The monomer reactivity ratios were evaluated to be r_NCMI = 0.107 and r_CMS = 0.136. The glass transition temperature of the resultant hyperbranched copolymer increases with increasing f_NCMI, which indicates that the heat resistance of the copolymer has been improved by increasing NCMI. The prepared hyperbranched CMS/NCMI copolymers were used as macroinitiators for the solution polymerization of styrene to yield star‐shaped poly(CMS‐co‐NCMI)/polystyrene block copolymers by atom transfer radical polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1992–1997, 2000     

Synthesis and photovoltaic properties of two side‐chain polymeric metal complexes containing 8‐hydroxyquinoline and fluorene units with Zn(II) and Cd(II)

Two novel side‐chain polymeric metal complexes (PF1 and PF2) containing 8‐hydroxyquinoline and fluorene units with Zn(II) and Cd(II) having donor‐acceptor π‐conjugated structure have been synthesized and characterized using Fourier transform infrared, ¹H NMR, UV‐visible and photoluminescence spectroscopies, thermogravimetric analysis, differential scanning calorimetry, elemental analysis and cyclic voltammetry. Dye‐sensitized solar cells (DSSCs) based on PF1 and PF2 as the dye sensitizers exhibit good device performance with solar‐to‐electricity conversion efficiency up to 0.32% (J_sc = 0.83 mA cm^?2, V_oc = 0.62 mV and FF = 0.62) and 0.24% (J_sc = 0.69 mA cm^?2, V_oc = 0.59 mV and FF = 0.60), respectively, under simulated AM 1.5 G solar irradiation (100 mW cm^?2). The data show that these novel polymeric metal complexes are suitable for DSSCs. Copyright © 2012 Society of Chemical Industry     

A study of light‐emitting diodes constructed with copolymers having cyclohexyl thiophene and hexyl thiophene units

We report visible light emission from a diode made from copolymers of 3‐alkylthiophenes. These chemically synthesized copolymers exhibit improved electroluminescence and quantum efficiencies compared to poly (3‐cyclohexylthiophene). Good solubility of copolymers allows the fabrication of the light emitting diodes by spin‐cast polymer film. The devices emit greenish‐blue light in wavelength region of 550–580 nm, which is easily visible in poorly lighted room. The quantum efficiencies are in the range of 0.002 to 0.01% (photons per electron) at room temperature; which are significantly higher than corresponding values for poly(3‐cyclohexylthiophene) based light emitting diodes. The charge carrier mobility in the device is found to be 5.6 × 10⁻⁴ cm²/Vs. ©2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1051–1055, 2000     

Blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 toughened by maleated polystyrene‐based copolymers: Mechanical properties,morphology, and rheology

Poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6 30/70) blends were impact modified by addition of three kinds of maleated polystyrene‐based copolymers, i.e., maleated styrene‐ethylene‐butylene‐styrene copolymer (SEBS‐g‐MA), maleated methyl methacrylate‐butadiene‐styrene copolymer (MBS‐g‐MA), and maleated acrylonitrile‐butadiene‐styrene copolymer (ABS‐g‐MA). The mechanical properties, morphology and rheological behavior of the impact modified PPO/PA6 blends were investigated. The selective location of the maleated copolymers in one phase or at interface accounted for the different toughening effects of the maleated copolymer, which is closely related to their molecular structure and composition. SEBS‐g‐MA was uniformly dispersed in PPO phase and greatly toughened PPO/PA6 blends even at low temperature. MBS‐g‐MA particles were mainly dispersed in the PA6 phase and around the PPO phase, resulting in a significant enhancement of the notched Izod impact strength of PPO/PA6 blends from 45 J/m to 281 J/m at the MBS‐g‐MA content of 20 phr. In comparison, the ABS‐g‐MA was mainly dispersed in PA6 phase without much influencing the original mechanical properties of the PPO/PA6 blend. The different molecule structure and selective location of the maleated copolymers in the blends were reflected by the change of rheological behavior as well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 1. Preparation of narrow polydispersity copolymers of methyl methacrylate and 2‐hydroxyethyl methacrylate by atom‐transfer radical polymerization

Well‐defined methyl methacrylate (MMA) and 2‐(trimethylsiloxy)ethyl methacrylate (Pro‐HEMA) copolymers were prepared by atom‐transfer radical polymerization(ATRP), using CuCl/2,2′‐bipyridine as catalytic system and p‐toluenesulfonyl chloride as initiator. ATRP process of MMA and Pro‐HEMA was monitored by ¹H NMR, and the kinetic curves of the MMA/Pro‐HEMA copolymerization were plotted in terms of the ¹H NMR data. At low content of Pro‐HEMA in the feed composition, the copolymerization can be well controlled with the molecular weight, polydispersity and the monomer distribution in the copolymer chain. With the increase of Pro‐HEMA content in the feed mixture, the composition of the final copolymer deviates from the composition of the feed mixture gradually, and gradient copolymers of MMA/Pro‐HEMA can be obtained. Through the hydrolysis process, well‐defined copolymers of MMA/HEMA were obtained from poly(MMA/Pro‐HEMA). Copyright © 2003 Society of Chemical Industry     

Synthesis and characterization of alternate copolymers constructed by 1,3‐bis(diphenylsilyl)‐2,2,4,4‐tetraphenylcyclodisilazane units with oligo‐dimethylsiloxane segments

1,3‐Dichloro‐1,1,3,3‐tetraphenyldisilazane (DCTPS) with 71.6% yield was synthesized by the reaction of hexaphenylcyclotrisilazane (HPCT) with Ph₂SiCl₂ catalyzed by dibutyltin dilaurate. A ring‐closure reaction of DCTPS was carried out with BuLi in xylene–hexane mixture solvent; 1,3‐bis(chlorodiphenylsilyl)‐2,2,4,4‐tetraphenyl‐cyclodisilazane (BcPTPC) with 73.2% yield was obtained. Hydrolysis of BcPTPC in ether–triethylamine solvent resulted in 71.9% yield of 1,3‐bis(diphenylhydroxysilyl)‐2,2,4,4‐tetraphenylcyclodisilazane (B_HPTPC). By condensation polymerization of B_HPTPC with α,ω‐bis(diethylamino)‐oligo‐dimethylsiloxane, a kind of alternate copolymer constructed by 1,3‐bis(diphenylsilyl)‐2,2,4,4‐tetraphenylcyclodisilazane units with oligo‐dimethylsiloxane segments [P(BPTPC‐alt‐ODMS)] was synthesized. BcPTPC, B_HPTPC as well as P(BPTPC‐alt‐ODMS) were characterized by ²⁹Si‐NMR spectra, FT‐IR spectra, and elemental analysis. DGA study shows that P(BPTPC‐alt‐ODMS)s are thermally stable. The thermal decomposition onsets of P(BPTPC‐alt‐ODMS)s are all above 520°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1484–1490, 2005