Novel elastomeric polyurethanes with pendant epoxy groups as highly reactive auxiliary groups for further derivatizations

The introduction of pendant, reactive groups into polyurethane macromolecules is a challenging problem. A variant of the nondegradative modification of polyurethanes with epoxy groups attached to the urethane sites is proposed. Two types of commercial elastomeric segmented polyurethanes, represented by a poly(ether urethane) and a poly(urethane urea), were functionalized by base‐induced N‐glycidylation of the urethane hard segments with an excess of epibromohydrin in dimethylacetamide solutions at low temperatures. This resulted in the modification of polymers with 0.30–0.44 mmol/g of pendant epoxy groups. Lithium or potassium tert‐butoxides were used as bases to initiate the reaction. A nonpolymeric urethane model (ethyl N‐p‐tolylcarbamoate) was used to verify the course of glycidylation. One of the polymers was subjected to epoxy ring opening with 1‐propanethiol, demonstrating the versatility of pendant glycidyl groups as auxiliary groups for further bulk modifications of polyurethanes. These functionalized polyurethanes are useful for the further covalent attachment of suitable moieties (stabilizing or biocompatibility‐enhancing agents). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4378–4385, 2002     

Synthesis and properties of hyperbranched polyurethanes,hyperbranched polyurethane copolymers with and without ether and ester groups using blocked isocyanate monomers

Starting from 3,5‐diamino benzoic acid, 2‐hydroxy propyl[3,5‐bis{(benzoxycarbonyl)imino}]benzyl ether, an AB₂‐type blocked isocyanate monomer with flexible ether group, and 2‐hydroxy propyl[3,5‐bis{(benzoxycarbonyl)imino}]benzoate, an AB₂‐type blocked isocyanate monomer with ester group, were synthesized for the first time. Using the same starting compound, 3,5‐bis{(benzoxycarbonyl)imino}benzylalcohol, an AB₂‐type blocked isocyanate monomer, was synthesized through a highly efficient short‐cut route. Step‐growth polymerization of these monomers at individually optimized experimental conditions results in the formation of hyperbranched polyurethanes with and without ether and ester groups. Copolymerizations of these monomers with functionally similar AB monomers were also carried out. The molecular weights of the polymers were determined using GPC and the values (M_w) were found to vary from 1.5 × 10⁴ to 1.2 × 10⁶. While hyperbranched polyurethanes having no ether or ester group were found to be thermally stable up to 217 °C, hyperbranched poly(ether–urethane)s and poly(ester–urethane)s were found to be thermally stable up to 245 and 300 °C, respectively. Glass transition temperature (T_g) of polyurethane was reduced significantly when introducing ether groups into the polymer chain, whereas T_g was not observed even up to 250 °C in the case of poly(ester–urethane). Hyperbranched polyurethanes derived from all the three different AB₂ monomers were soluble in highly polar solvents and the copolymers showed improved solubility. Polyethylene glycol monomethyl ether of molecular weight 550 and decanol were used as end‐capping groups, which were seen to affect the thermal, solution, and solubility properties of polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3877–3893, 2007     

Preparation and characterization of N‐methyl‐substituted polyurethane

We prepared N‐methyl‐substituted polyurethanes with different substitution degrees from sodium hydride, methyl p‐toluene sulfonate, and polyether–polyurethane containing poly(oxytetramethylene) glycol, 4,4′‐diphenylmethane diisocyanate, and 1,4‐butanediol. The chemical structures were characterized with Fourier transform infrared and ¹H NMR. To investigate the effects of the N‐substitution degree on the morphology, thermal stability, and mechanical properties, we used differential scanning calorimetry, thermogravimetric analysis, and a universal testing machine. As the substitution degree increased, the new free (1708 cm^?1) and bonded (1650 cm^?1) carbonyl peaks increased. There was no bonded carbonyl peak in fully substituted polyurethane because the urethane groups had no hydrogen. At a small substitution degree, we observed a slight increase in the glass‐transition temperature and decrease in the endotherms of soft‐segment and hard‐segment domains due to the decrease in the hard‐segment domain and the increase in the urethane groups in the soft‐segment domain. The hard‐segment domain decreased and then disappeared as the N‐methyl substitution degree increased. These changes in the morphology resulted (1) in decreased modulus and tensile strength for the films because of the decrease in physical crosslinking points and (2) improved thermal stability as the substitution degree increased. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4077–4083, 2002     

An efficient nonisocyanate route to polyurethanes via thiol‐ene self‐addition

A novel and efficient strategy for the synthesis of nonisocyanate polyurethanes has been developed via thiol–ene self‐photopolymerization. An aliphatic thiol–ene carbamate monomer (allyl(2‐mercaptoethyl)carbamate, AMC) was synthesized by a one‐step synthesis procedure, from cysteamine and allyl chloroformate. The urethane group was therefore incorporated directly into the monomer precursor, avoiding the problems associated to toxic isocyanates. AMC was successfully stabilized with the radical inhibitor pyrogallol (1% wt). In addition, the use of phenyl phosphonic acid as coadditive allowed its stabilization for lower concentrations of pyrogallol (0.1% wt). AMC was directly transformed into thermoplastic polyurethane (TPU) through thiol–ene photopolymerization by UV‐irradiation at 365 nm. The obtained TPU presented semi‐crystalline nature and very high thermal stability (T_5% ～325 °C). It was found that high concentrations of pyrogallol decreased the reaction rate and final conversion of photopolymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3017–3025     

Poly(ester urethane)s with polycaprolactone soft segments: A morphological study

Two series of poly(ester urethane)s were prepared, containing polycaprolactone (PCL) as the soft segment with molecular weights of 530 and 2000. In each series, the soft‐segment/hard‐segment ratio was varied, and the morphological changes were monitored with differential scanning calorimetry, dynamic mechanical thermal analysis, wide‐angle X‐ray scattering, and scanning electron microscopy techniques. The polyurethanes with longer PCL segments retained their crystallinity, whereas those with shorter PCL segments did not. A morphological model is proposed, in which a continuous PCL‐rich matrix contains both PCL crystallites and domains of urethane hard segments. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4117–4130, 2002     

A versatile synthetic path to thiol containing polysiloxanes

A synthetic strategy to polydimethylsiloxanes and polymethylsiloxanes containing thiol functions as end‐ or side‐groups, respectively, is presented. Such polymers are important starting materials for elastomeric networks and postpolymerization modifications. The synthesis starts either with vinyl end‐functionalized polydimethylsiloxanes or with polymethylvinylsiloxanes. The vinyl groups are reacted either with thioacetic acid or with a thioacetic acid/butanethiol mixture via a UV‐initiated thiol‐ene reaction to form the respective thioester quantitatively within few minutes. The thioesters are subsequently deprotected to the respective thiols by reduction with LiAlH₄. The resulting thiol containing polysiloxanes can be used for the formation of networks or another functionalization. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2940–2948     

Tunable poly(hydroxyl urethane) from CO2‐Based intermediates using thiol‐ene chemistry

CO₂‐based, crosslinked poly(hydroxyl urethane)s (PHUs) are accessed via a set of efficient reactions based on the addition chemistry of thiol‐ene and amines‐cyclic carbonates. This strategy to utilize 5‐membered cyclic carbonates produced from CO₂ is robust, facile, modular, and atomically efficient in nature. The thiol‐ene reaction was utilized to access bis(cyclic carbonate), tris(cyclic carbonate), and tetrakis(cyclic carbonate) in quantitative yield from 4‐vinyl‐1,3‐dioxolan‐2‐one and thiols. Multi‐functional cyclic carbonates were simply mixed with diethylenetriamine and/or 1,6‐diaminohexane to generate crosslinked PHUs from 25 to 80 °C. These materials are easy to scale‐up and are potential candidates in many applications such as coatings, binders, and resins. The resulting polymers have glass transition temperatures between ?1 and 16 °C and thermal decomposition temperatures from 190 to 230 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Structural and end‐group effects on bulk and surface properties of hyperbranched poly(urea urethane)s

The hydroxy end groups of aromatic and aliphatic hyperbranched poly‐(urea urethane)s prepared with an AA* + B*B₂ one‐pot method were modified with phenylisocyanate, butylisocyanate, and stearylisocyanate. The success of the modification reaction was verified with ¹H NMR and IR spectroscopy. Linear model poly‐(urea urethane)s were prepared, too, for comparison. The bulk properties of OH functionalized hyperbranched poly(urea urethane)s, compared with those of linear analogues and modified hyperbranched poly(urea urethane)s, were studied with differential scanning calorimetry, thermogravimetric analysis, and temperature‐dependent Fourier transform infrared measurements. Transparent and smooth thin films could be prepared from all polymer samples and were examined with a light microscope, a microglider, and an atomic force microscope. The properties of the polymer surface were examined by measurements of the contact angle and zeta potential. For all samples, the properties were mainly governed by the strong interactions of the urea and urethane units within the backbone, whereas the influence of the nature of the end groups and of the branched structure was reduced in comparison with other hyperbranched polymer systems. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3376–3393, 2005     

Synthesis and properties of polymethacrylate bearing cyclic carbonate through urethane linkage

Polymethacrylates carrying cyclic carbonate through urethane linkage were prepared by radical (co)polymerizations of 2‐methacrylic acid 2‐(2‐oxo‐[1,3]dioxolan‐4‐ylmethoxycarbonylamino)ethyl ester (CUMA). Although brittleness of typical polymers bearing cyclic carbonate groups has been limited their practical applications, some copolymers from CUMA can be cast as films with good flexibility. The copolymers from CUMA and diethyleneglycol methyl ether methacrylate are miscible with lithium bis(trifluoromethanesulfone)imide. The coordination of the lithium cation to the carbonyl groups was confirmed by infrared spectrometry. © 2007 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 45: 5781–5789, 2007     

Synthesis and properties of waterborne self‐crosslinkable sulfo‐urethane silanol dispersions

A novel type of crosslinkable waterborne polyurethane ionomer was prepared by the acetone process. Two new types of sulfonated diols compatible with this process were synthesized from dimethyl 5‐sodium sulfo isophthalate using a one‐ or two‐stage method. Isocyanate‐terminated polyurethane oligomers were prepared from the sulfonated diols with various combinations of diols and diisocyanates and subsequently reacted with amino silane derivatives. Stable, low‐volatile organic chemical, waterborne dispersions of the sulfo‐urethane silanol polymers spontaneously crosslink upon drying without extra additives or processing steps. Despite the lack of organic coalescing solvents, the dispersions have minimum film‐forming temperatures below 10 °C, regardless of glass‐transition temperature. Tensile strengths up to 6000 psi with elongations between 300 and 600% were obtained for the crosslinked films. The hard‐segment content of the films can be controlled to produce films with a Sward–Rocker hardness value up to 42. Through silane end‐group modification, the crosslinking density of the films can also be modified to produce polyurethanes with a wide range of physical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3037–3045, 2002     

Catalysts and temperature driven melt polycondensation reaction for helical poly(ester‐urethane)s based on natural L‐amino acids

Catalyst and temperature driven melt polycondensation reaction was developed for natural L‐amino acid monomers to produce new classes of poly(ester‐urethane)s. Wide ranges of catalysts from alkali, alkali earth metal, transition metal and lanthanides were developed for the condensation of amino acid monomers with diols to yield poly(ester‐urethane)s. A‐B Diblock and A‐B‐A triblock species were obtained by carefully choosing mono‐ or diols in model reactions. More than two dozens of transition metal and lanthanide catalysts were identified for the polycondensation to yield high molecular weight poly(ester‐urethane)s. Theoretical studies revealed that the carbonyl carbon in ester possessed low electron density compared to the carbonyl carbon in urethane which driven the thermo‐selective polymerization process. Optical purity of the L‐amino acid residues in the melt polycondensation process was investigated using D‐ and L‐isomers and the resultant products were analyzed by chiral‐HPLC and CD spectroscopy. CD analysis revealed that the amino acid based polymers were self‐assembled as β‐sheet and polyproline type II secondary structures. Electron and atomic force microscopic analysis confirmed the formation of helical nano‐fibrous morphology in poly(ester‐urethane)s. The newly developed melt polycondensation process is very efficient and optimized for wide range of catalysts to produce diverse polymer structures from natural L‐amino acids. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1065–1077     

Design and Synthesis of Aromatic Polyesters Bearing Pendant Clickable Maleimide Groups

A bisphenol bearing pendant maleimide group, namely, N‐maleimidoethyl‐3, 3‐bis(4‐hydroxyphenyl)‐1‐isobenzopyrrolidone (PPH‐MA) was synthesized starting from phenolphthalein. Aromatic (co)polyesters bearing pendant maleimide groups were synthesized from PPH‐MA and aromatic diacid chlorides, namely, isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), and 50:50 mol % mixture of IPC and TPC by low temperature solution polycondensation technique. Copolyesters were also synthesized by polycondensation of different molar proportions of PPH‐MA and bisphenol A with IPC. Inherent viscosities and number‐average molecular weights of aromatic (co)polyesters were in the range of 0.52–0.97 dL/g and 20,200–32,800 g/mol, respectively indicating formation of medium to reasonably high‐molecular‐weight polymers. ¹³C NMR spectral analysis of copolyesters revealed the formation of random copolymers. The 10% weight loss temperature of (co)polyesters was found in the range 470–484 °C, indicating their good thermal stability. A selected aromatic polyester bearing pendant maleimide groups was chemically modified via thiol‐maleimide Michael addition reaction with two representative thiol compounds, namely, 4‐chlorothiophenol and 1‐adamantanethiol to yield post‐modified polymers in a quantitative manner. Additionally, it was demonstrated that polyester containing pendant maleimide groups could be used to form insoluble crosslinked gel in the presence of a multifunctional thiol crosslinker. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 630–640     

Clickable polyurethanes based on s‐triazine ring containing aromatic diisocyanate bearing pendent alkyne group: Synthesis and postmodification

A new s‐triazine ring containing aromatic diisocyanate bearing a pendent alkyne group, namely, 2,4‐bis(4‐isocyanatophenoxy)?6‐(prop‐2‐yn‐1‐yloxy)?1,3,5‐triazine was synthesized and reacted with various diols viz., 1,10‐decanediol, tetraethylene glycol and polyethylene glycols in the presence of dibutyltin dilaurate as the catalyst to obtain a series of linear polyurethanes. The selected polyurethanes possessing pendent alkyne groups were postmodified with chemically diverse azides viz., 1‐(azidomethyl)benzene, 1‐(azidomethyl)pyrene, and methoxy end‐caped poly(ethylene glycol) azide via copper‐catalysed azide‐alkyne Huisgen 1,3‐dipolar cycloaddition. FTIR and ¹H NMR spectra indicated quantitative click reaction. UV–vis and fluorescence spectroscopic analysis confirmed complete incorporation of pyrenyl groups indicating the formation of fluorescence active polyurethane by postmodification with 1‐(azidomethyl)pyrene. TG analysis of polyurethanes indicated two stage weight loss and their thermal stability, as judged by T ₁₀ values, was governed by weight percent of urethane linkages. The water contact angle measurements revealed improved wettability with increased content of PEG either in the backbone of polyurethanes or as grafted chains. DLS and TEM studies confirmed that certain polyurethanes possessing PEG segments displayed self‐assembly in aqueous solution, which was further supported by pyrene encapsulation studies using UV–vis spectroscopy. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1008–1020     

Poly(urethane‐co‐benzoxazine)s via reaction of phenol terminated urethane prepolymers and benzoxazine monomer and investigation of their properties

In the present work, a new method was developed for the combination of polyurethanes (PUs) and polybenzoxazine (PBz) to obtain novel thermoset poly(urethane‐co‐benzoxazine)s with good thermal, mechanical, and electrical properties as well as low temperature curing profile. Knowing the catalytic effect of compounds possessing free phenolic groups on ring opening polymerization of benzoxazine monomers, preparation of phenol terminated urethane oligomers (PTPU) as the macroinitiator for a benzoxazine monomer (Ba) was considered. Firstly, NCO‐terminated urethane prepolymers were prepared from the reaction of poly(tetramethyleneether glycol), and 2,4‐tolylene diisocyanate, and then end functionalized with bisphenol‐A under proper condition. DSC, DMTA, and gel content measurements were applied to find optimum ring opening polymerization condition (170°C for 1 hr and 200°C for 15 min). Various kinds of thermoset polymers were prepared by the reaction of PTPU at different molecular weights with variable contents of Ba. All of monomeric and polymeric materials were characterized by conventional spectroscopic methods and their thermal, mechanical, viscoelastic, and electrical properties were measured and properties were correlated to their structure. Due to the interesting properties of these new materials, the possibility of using them as electrical insulators with higher service temperature in comparison to common PUs were examined and their potential applicability was confirmed. Copyright © 2010 John Wiley & Sons, Ltd.     

Phase behavior and some calorimetric and physical properties of diurethanes from perfluoropolyether macromonomers

Density and calorimetric measurements have been carried out on copolymeric perfluoropolyethers of molecular weight ranging between 500 and 4700, terminated at both chain ends either with  CH₂OH or ethylurethane groups. Samples of the second series are models for perfluoropolyethers based polyurethanes. Density measurements point out that the terminal alcoholic group brings about a negative excess volume, which increases with decreasing the molecular weight; a lower excess volume is found for urethane‐terminated molecules. Calorimetric traces, T_g, and Δc_p at T_g show that alcoholic‐terminated molecules are amorphous and one phase systems, while urethane‐terminated compounds are crystalline; phase separation is observed for this last series when the molecular weight of the fluorinated segment is larger than 1000. The trend of T_g with molecular weight is discussed for one‐ and two‐phase systems in the light of current theories for the glass transition. The decrease of the melting point with increasing the molecular weight for the urethane series can be described by the Flory equation for random copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1609–1622, 1999     

Modular material system for the microfabrication of biocompatible hydrogels based on thiol–ene‐modified poly(vinyl alcohol)

Novel modifications of the synthetic polymer poly(vinyl alcohol) (PVA) were developed for application in the field of biomedical engineering. PVA was modified with allyl succinic anhydride, norbornene anhydride as well as with γ‐thiobutyrolactone to produce macromers with reactive ene and thiol groups, respectively. Cytotoxicity studies have shown that the material exhibits almost no cell‐toxicity, when used in concentrations of 1 and 0.1 wt % for 24 h. The obtained macromers were photocrosslinked via thiol–ene chemistry. Storage stability of the macromer mixtures with different concentrations of pyrogallol as stabilizer were investigated. Photorheometry was employed to optimize mixtures concerning reactivity based on their thiol‐to‐ene ratio, photoinitiator concentration, and macromer content. The crosslinked hydrogels were studied concerning their swellability. To form hydrogels with cellular structure two‐photon‐polymerization (2PP) was employed. Processing windows for 2PP of selected mixtures were determined. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2060–2070     

Melt polycondensation approach for reduction degradable helical polyester based on l‐cystine

Melt polycondensation approach is developed for new classes of reduction responsive disulfide containing functional polyesters based on l ‐cystine amino acid resources under solvent free process. l ‐Cystine was converted into multi‐functional ester‐urethane monomer and subjected to thermoselective transesterification at 120 °C with commercial diols in the presence of Ti(OBu)₄ to produce polyesters with urethane side chains. The polymers were produced in moderate to high molecular weights and the polymers were found to be thermally stable up to 250 °C. The β‐sheet hydrogen bonding interaction among the side chain urethane unit facilitated the self‐assembly of the polyester into amyloid‐like fibrils. The deprotection of urethane unit into amine functionality modified the polymers into water soluble cationic polyester spherical nanoparticles. The reduction degradation of disulfide bond was studied using DTT as a reducing agent and the high molecular weight polymers chains were found be chopped into low molecular weight oligomers. The cytotoxicity of cationic disulfide nanoparticle was studied in MCF‐7 cells and they were found to be biocompatible and non‐toxic to cells upto 50 μg/mL. The custom designed reduction degradable and highly biocompatible disulfide polyesters from l ‐cystine are useful for futuristic biomedical applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2864–2875     

L‐arabinitol‐based functional polyurethanes

Three new polymerizable diols, based on mono‐, di‐, and tri‐O‐allyl‐L ‐arabinitol derivatives, were prepared from L ‐arabinitol as versatile materials for the preparation of tailor‐made polyurethanes with varied degrees of functionalization. Their allyl functional groups can take part in thiol‐ene reactions, to obtain greatly diverse materials. This “click” reaction with 2‐mercaptoethanol was firstly studied on the highly hindered sugar precursor 2,3,4‐tri‐O‐allyl‐1,5‐di‐O‐trityl‐L ‐arabinitol, to apply it later to macromolecules. A polyurethane with multiple pendant allyl groups was synthesized by polyaddition reaction of 2,3,4‐tri‐O‐allyl‐L ‐arabinitol with 1,6‐hexamethylene diisocyanate, and then functionalized by thiol‐ene reaction. The coupling reaction took place in every allyl group, as confirmed by standard techniques. The thermal stability of the novel polyurethanes was investigated by thermogravimetric analysis and differential scanning calorimetry (DSC). This strategy provides a simple and versatile platform for the design of new materials whose functionality can be easily modified. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Modification of RAFT‐polymers via thiol‐ene reactions: A general route to functional polymers and new architectures

An investigation into the aminolysis of ω‐end groups of RAFT‐polymers and simultaneous thiol‐ene reactions with ene‐bearing compounds is described. Three different polymers, P(MMA), P(HPMA), and P(NIPAAm), with low PDIs were synthesized using dithiobenzoate and trithiocarbonate RAFT agents. P(NIPAAm) synthesized with trithiocarbonate RAFT agent and P(HPMA) synthesized with dithiobenzoate RAFT agent were both functionalized with a methacrylate‐modified mannose and a maleimide‐modified biotin via one‐pot simultaneous aminolysis and thiol‐ene reactions with product yields above 85%. The presence of ene‐compounds during aminolysis was shown to prevent the formation of disulfide interchain crosslinking. Using the same approach, P(MMA), P(HPMA), and P(NIPAAm) were converted to (meth)acrylate macromonomers with high yields (>80%). In the case of P(MMA), the simultaneous aminolysis and thiol‐ene addition prevented any intrachain side reactions, i.e., thiolactone formation. New architectures such as graft and block copolymers were successfully generated from the macromonomers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3773–3794, 2009     

Hydroxyl‐ and amine‐terminated hyperbranched polyurethanes using AB2‐type azide monomers: Synthesis,characterization, fluorescence,and charge‐transfer complexation studies

Novel AB₂‐type azide monomers such as 3,5‐bis(4‐methylolphenoxy)carbonyl azide (monomer 1) , 3,5‐bis(methylol)phenyl carbonyl azide (monomer 2) , 4‐(methylol phenoxy) isopthaloyl azide (monomer 3) , and 5‐(methylol) isopthaloyl azide (monomer 4) were synthesized. Melt and solution polymerization of these monomers yielded hydroxyl‐ and amine‐terminated hyperbranched polyurethanes with and without flexible ether groups. The structures of theses polymers were established using FT‐IR and NMR spectroscopy. The molecular weights (M_w) of the polymers were found to vary from 3.2 × 10³ to 5.5 × 10⁴ g/mol depending on the experimental conditions used. The thermal properties of the polymers were evaluated using TGA and DSC: the polymer obtained from monomer ( 1 ) exhibited lowest T_g and highest thermal stability and the polymer obtained from monomer ( 2 ) registered the highest T_g and lowest thermal stability. All the polymers displayed fluorescence maxima in the 425–525 nm range with relatively narrow peak widths indicating that they had pure and intense fluorescence. Also, the polymers formed charge transfer (CT) complexes with electron acceptor molecules such as 7,7,8,8‐tetracyano‐quino‐dimethane (TCNQ) and 1,1,2,2‐tetracyanoethane (TCNE) as evidenced by UV‐visible spectra. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3337–3351, 2009