Fast switching immobilized photochromic dyes

A novel photochromic dye conjugate architecture is described, which allows both covalent tethering to a polymeric host matrix and fast photochromic switching. The new conjugates consist of a photochromic dye covalently bound to two different substituents via a Y‐branching linker (hetero Y‐branching), one being a polymerizable methacrylate moiety and the other a soft (low T_g) poly(dimethylsiloxane) oligomer. The novel conjugates gave faster photochromic decoloration in the host lens matrix compared with the electronically equivalent nonmatrix‐bound and unconjugated parent control dyes. In addition, further acceleration of fade speed kinetics was observed with a longer linker between photochromic dye and methacrylate moiety. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

The effect of molecular structure on the secondary transitions and their influence on the decoloration kinetics of photochromic dyes in co‐polycarbonates

Photochromic dyes have restricted use in rigid polycarbonates because of slow coloration and decoloration kinetics. In this study, it is shown that the decoloration kinetics of two photochromic dyes can be controlled by tuning the chain stiffness and free volume of the host matrix. The introduction of flexible moieties in rigid BPA‐based polycarbonate chain accelerates the decoloration of these dyes whereas a rigid co‐monomer delays the decoloration kinetics. Although T_g might be used as a parameter to improve photochromism in polymer matrices, dynamic mechanical analysis demonstrates that the decoloration kinetics of the dyes in host polymer matrices having similar T_g depends primarily on the secondary relaxations and, thus, on the polymer architecture. The effect of the co‐monomer type on the characteristic ratio is also discussed underlining the potential relationship between the free volume and chain stiffness. These results open the possibility to develop transparent or semitransparent photochromic materials based on tailor‐made co‐polycarbonates. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1593–1601     

Synthesis and properties of polyacetylenes with salicylideneaniline groups

Acetylenes containing salicylideneaniline groups—N‐salicylidene‐3‐ethynylaniline ( 1 ), N‐(3‐t‐butylsalicylidene)‐3‐ethynylaniline ( 2 ), and N‐(3‐t‐butylsalicylidene)‐4‐ethynylaniline ( 3 )—polymerized smoothly and gave yellow to red polymers in excellent yields when a rhodium catalyst was employed. Polymers with alkyl substituents on the aromatic rings [poly( 2 ) and poly( 3 )] were soluble in CHCl₃, tetrahydrofuran, and so forth, whereas the polymer without alkyl substituents [poly( 1 )] was insoluble in any solvent. N‐(3‐t‐Butylsalicylidene)propargylamine did not provide any polymer. Thermogravimetric analyses of the resultant polymers exhibited good thermal stability (T_o, onset temperature of weight loss > 300 °C). The ultraviolet–visible spectra of the polymers showed absorption maxima and cutoff wavelengths around 360 and 520 nm, respectively. The polymers exhibited largely Stokes‐shifted fluorescence (emission wavelength ? 550 nm) upon photoexcitation at 350 nm, which resulted from the photoinduced intramolecular proton transfer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2458–2463, 2002     

Quadruple click reactions for the synthesis of cysteine‐terminated linear multiblock copolymers

Synthesis of cysteine‐terminated linear polystyrene (PS)‐b‐poly(ε‐caprolactone) (PCL)‐b‐poly(methyl methacrylate) (PMMA)/or poly(tert‐butyl acrylate)(PtBA)‐b‐poly(ethylene glycol) (PEG) copolymers was carried out using sequential quadruple click reactions including thiol‐ene, copper‐catalyzed azide–alkyne cycloaddition (CuAAC), Diels–Alder, and nitroxide radical coupling (NRC) reactions. N‐acetyl‐L ‐cysteine methyl ester was first clicked with α‐allyl‐ω‐azide‐terminated PS via thiol‐ene reaction to create α‐cysteine‐ω‐azide‐terminated PS. Subsequent CuAAC reaction with PCL, followed by the introduction of the PMMA/or PtBA and PEG blocks via Diels–Alder and NRC, respectively, yielded final cysteine‐terminated multiblock copolymers. By ¹H NMR spectroscopy, the DP_ns of the blocks in the final multiblock copolymers were found to be close to those of the related polymer precursors, indicating that highly efficient click reactions occurred for polymer–polymer coupling. Successful quadruple click reactions were also confirmed by gel permeation chromatography. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Heteroarm H‐shaped terpolymers through the combination of the Diels–Alder reaction and controlled/living radical polymerization techniques

Heteroarm H‐shaped terpolymers (PS)(PtBA)–PEO–(PtBA)(PS) and (PS)(PtBA)–PPO–(PtBA)(PS) [where PS is polystyrene, PtBA is poly(tert‐butyl acrylate), PEO is poly(ethylene oxide), and PPO is poly(propylene oxide)], containing PEO or PPO as a backbone and PS and PtBA as side arms, were prepared via the combination of the Diels–Alder reaction and atom transfer radical and nitroxide‐mediated radical polymerization routes. Commercially available PEO or PPO containing bismaleimide end groups was reacted with a compound having an anthracene functionality, succinic acid anthracen‐9‐yl methyl ester 3‐(2‐bromo‐2‐methylpropionyloxy)‐2‐methyl‐2‐[2‐phenyl‐2‐(2,2,6,6‐tetramethylpiperidin‐1‐yloxy)ethoxycarbonyl]propyl ester, with a Diels–Alder reaction strategy. The obtained macroinitiator with tertiary bromide and 2,2,6,6‐tetramethylpiperidin‐1‐oxy functional end groups was used subsequently in the atom transfer radical polymerization of tert‐butyl acrylate and in the nitroxide‐mediated free‐radical polymerization of styrene to produce heteroarm H‐shaped terpolymers with moderately low molecular weight distributions (<1.31). The polymers were characterized with ¹H NMR, ultraviolet, gel permeation chromatography, and differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3947–3957, 2006     

Investigation of catalyst‐transfer condensation polymerization for the synthesis of n‐type π‐conjugated polymer,poly(2‐dioxaalkylpyridine‐3,6‐diyl)

Kumada‐Tamao coupling polymerization of 6‐bromo‐3‐chloromagnesio‐2‐(3‐(2‐methoxyethoxy)propyl)pyridine 1 with a Ni catalyst and Suzuki‐Miyaura coupling polymerization of boronic ester monomer 2 , which has the same substituted pyridine structure, with ^tBu₃PPd(o‐tolyl)Br were investigated for the synthesis of a well‐defined n‐type π‐conjugated polymer. We first carried out a model reaction of 2,5‐dibromopyridine with 0.5 equivalent of phenylmagnesium chloride in the presence of Ni(dppp)Cl₂ and then observed exclusive formation of 2,5‐diphenylpyridine, indicating that successive coupling reaction took place via intramolecular transfer of Ni(0) catalyst on the pyridine ring. Then, we examined the Kumada‐Tamao polymerization of 1 and found that it proceeded homogeneously to afford soluble, regioregular head‐to‐tail poly(pyridine‐2,5‐diyl), poly(3‐(2‐(2‐(methoxyethoxy)propyl)pyridine) (PMEPPy). However, the molecular weight distribution of the polymers obtained with several Ni and Pd catalysts was very broad, and the matrix‐assisted laser desorption ionization time‐of‐flight mass spectra showed that the polymer had Br/Br and Br/H end groups, implying that the catalyst‐transfer polymerization is accompanied with disproportionation. Suzuki‐Miyaura polymerization of 2 with ^tBu₃PPd(o‐tolyl)Br also afforded PMEPPy with a broad molecular weight distribution, and the tolyl/tolyl‐ended polymer was a major product, again indicating the occurrence of disproportionation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and properties of carbamate‐ and amine‐containing poly(phenylacetylenes)

The 3‐ and 4‐aminophenylacetylenes protected by t‐butoxycarbonyl (t‐Boc) and 9‐fluorenylmethoxycarbonyl (Fmoc) groups ( 3a – 6a ) were synthesized and polymerized using [(nbd)RhCl]₂ ( 1 ) and [(nbd)Rh⁺‐η⁶‐PhB^?Ph₃] ( 2 ) catalysts. The t‐Boc‐containing polymers [poly( 3a ) and poly( 4a )] were obtained in high yield (82–91%). Among the Fmoc‐protected monomers, the para‐derivative polymerized well [poly( 6a ); yield = 85–94%], whereas its meta‐substituted analogue did not afford high molecular weight polymer in good yield [poly( 5a ); yield = 10–15%]. The use of KN(SiMe₃)₂ as a cocatalyst in conjunction with 1 led to a dramatic increase in the molecular weight of the polymers. The acid‐ and base‐catalyzed removal of the t‐Boc and the Fmoc groups, respectively, generated primary amine‐containing polymers [poly( 3b )–poly( 6b )] which cannot be obtained directly by the polymerization of the corresponding monomers. The solubility characteristics of the polymers bearing protected amino groups were quite different from those of the unprotected ones, the former being soluble in polar solvents, whereas the latter displayed poor solubility even in polar protic or highly polar aprotic solvents. The attempts to accomplish the free‐standing membrane fabrication by solution casting were successful only for poly( 3a ), and an augmentation in the gas permeability and CO₂/N₂ permselectivity was discerned in comparison with the unsubstituted poly(phenylacetylene) and poly(m‐t‐butyldimethylsiloxyphenylacetylene). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1853–1863, 2009     

Simultaneous dual end‐functionalization of peg via the passerini three‐component reaction for the synthesis of ABC miktoarm terpolymers

In this article, we demonstrate the Passerini three‐component reaction as a simple, effective method for the synthesis of polymers with double functional end groups, which are key precursors for the preparation of ABC miktoarm terpolymers. Thus, via the one‐step Passerini reaction of monomethoxy poly(ethylene glycol)–propionaldehyde (PEG‐CHO) with 2‐bromo‐2‐methylpropionic acid and propargyl isocyanoacetamide, the PEG chain end was simultaneously functionalized with one atom transfer radical polymerization (ATRP) initiating site and one alkynyl group. The resulting PEG(‐alkynyl)‐Br was then used for the synthesis of three types of miktoarm ABC terpolymers via two approaches. First, we conducted ATRP of N‐isopropylacrylamide (NIPAM), then click reaction with azido‐terminated polystyrene (PS‐N₃) or poly(tert‐butyl acrylate) (PtBA‐N₃) and obtained two ABC miktoarm terpolymers PEG(‐b‐PNIPAM)‐b‐PS and PEG(‐b‐PNIPAM)‐b‐PtBA. Alternatively, we conducted single electron transfer living radical polymerization of tBA and click reaction with PS‐N₃ simultaneously to give PEG(‐b‐PtBA)‐b‐PS. All the polymer precursors and miktoarm terpolymers have been characterized by ¹H NMR, Fourier transform infrared, gel permeation chromatography, demonstrating that both approaches provided well‐defined ABC miktoarm terpolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Multiarm star block copolymers via Diels‐Alder click reaction

Two types of multiarm star block copolymers: (polystyrene)_m‐poly(divinylbenzene)‐poly(methyl methacrylate)_n, (PS)_m‐polyDVB‐(PMMA)_n and (polystyrene)_m‐poly(divinylbenzene)‐poly(tert‐butyl acrylate)_k, (PS)_m‐polyDVB‐(PtBA)_k were successfully prepared via a combination of cross‐linking and Diels–Alder click reactions based on “arm‐first” methodology. For this purpose, multiarm star polymer with anthracene functionality as reactive periphery groups was prepared by a cross‐linking reaction of divinyl benzene using α‐anthracene end functionalized polystyrene (PS‐Anth) as a macroinitiator. Thus, obtained multiarm star polymer was then reacted with furan protected maleimide‐end functionalized polymers: PMMA‐MI or PtBA‐MI at reflux temperature of toluene for 48 h resulting in the corresponding multiarm star block copolymers via Diels–Alder click reaction. The multiarm star and multiarm star block copolymers were characterized by using ¹H NMR, SEC, Viscotek triple detection SEC (TD‐SEC) and UV. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 178–187, 2009     

Synthesis of sulfonated poly(diphenylacetylene)s with high CO2 permselectivity

High‐molecular‐weight poly[1‐phenyl‐2‐(4‐t‐butylphenyl)acetylene], poly[1‐phenyl‐2‐(4‐trimethylsilylphenyl) acetylene], and their copolymers were synthesized by the polymerization with TaCl₅–n‐Bu₄Sn. The obtained polymers were sulfonated by using acetyl sulfate to give sulfonated poly(diphenylacetylene)s with different degrees of substitution. The degrees of sulfonation of poly[1‐phenyl‐2‐(4‐t‐butylphenyl)acetylene] and copolymers were in the range of 0.57–0.85. When poly[1‐phenyl‐2‐(4‐trimethylsilylphenyl)acetylene] was sulfonated, the sulfonated poly(diphenylacetylene) with the highest degree of sulfonation was obtained among all the polymers in this study. Its degree of sulfonation was 1.55. All the sulfonated polymers exhibited high CO₂ permselectivity, and their CO₂/N₂ separation factor were over 31. The sulfonated poly(diphenylacetylene) with the highest degree of sulfonation showed the highest CO₂/N₂ separation factor of 75. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6463–6471, 2009     

Enzymatic bioactivity investigation of glucose oxidase modified with hydrophilic or hydrophobic polymers via in situ RAFT polymerization

Biomacromolecules, such as enzymes are widely used for biocatalysis, both at academic and industrial level, due to their high specificity and wide applications in different reaction media. Herein, taking GOx as a representative enzyme, in‐situ RAFT polymerization of four different monomers including acrylic acid (AA), methyl acrylate (MA), poly (ethylene glycol) acrylate (PEG‐A) and tert‐butyl acrylate (TBA) were polymerized directly on the surface of GOx to afford GOx‐poly (PEG‐A)(GOx‐PPEG‐A), GOx‐poly(MA)(GOx‐PMA), GOx‐poly(AA)(GOx‐PAA), and GOx‐poly(TBA)(GOx‐PTBA) conjugates, respectively. Thereinto, PAA and PPEG‐A represent the hydrophilic polymers, while PMA and PTBA stand for the hydrophobic ones. Effects of different polymer on the properties of GOx were investigated by measuring the bioactivity and stability of the as‐prepared and different GOx‐polymer conjugates. Higher bioactivity was obtained for GOx modified with hydrophilic polymers compared with that modified with hydrophobic ones. All the tested polymers can enhance the stability of the GOx, while the hydrophobic GOx‐polymers conjugates exhibited much better stability than the hydrophilic ones. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1289–1293     

End‐group functionalization and postpolymerization modification of helical poly(isocyanide)s

This contribution presents the synthesis of helical alkyne‐terminated polymers using a functionalized Nickel complex to initiate the polymerization of menthylphenyl isocyanides. The resulting polymers display low dispersities and controlled molecular weights. Copper‐catalyzed azide/alkyne cycloadditions (CuAAC) are performed to attach various azide‐containing compounds to the polymer termini. After azido‐phosphonate moiety attachment the polymer displays a signal at 25.4 ppm in the ³¹P NMR spectrum demonstrating successful end‐group functionalization. End‐group functionalization of a fluorescent dye allows to determine the functionalization yield as 89% (±8). Successful ligation of an azide‐functionalized peptide sequence (M_KLA = 1547 g/mol) increases the M_n from 5100 for the parent polymer to 6700 for the bioconjugate as visualized by GPC chromatography. Analysis by CD spectroscopy confirms that the helical conformation of the poly(isocyanide) block in the peptide–polymer conjugate is maintained after postpolymerization modification. These results demonstrate an easy, generalizable, and versatile strategy toward mono‐telechelic helical polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2766–2773     

Synthesis of self‐assembled sphingolipid conjugates and their morphology effect on anticancer therapeutic potency

The shape of self‐assembling polymer–drug conjugates, influencing the cellular uptake, is one of the important factors to be considered for effective drug delivery. In this study, we described synthesis of polymeric drug conjugates of different morphologies with phytosphingosine (PHS) as a hydrophobic model drug and poly(amino acid) as a hydrophilic host polymer. By varying the amount of PHS grafted to poly(amino acid), PHS–poly(amino acid) conjugates exhibited morphological transition from spherical to worm‐like micellar aggregates in the aqueous media. We investigated the physicochemical properties of self‐assembled structures in terms of hydrodynamic size, surface charge, and critical aggregation concentration. The anticancer therapeutic potency of these self‐assembled structures was also discussed in terms of cellular uptake and cytotoxicity of prodrug micelles as a function of dose and time by in vitro cell study. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Syntheses and properties of hyperbranched polybenzoxazole by thermal cyclodehydration of hyperbranched poly[o‐(t‐butoxycarbonyl)amide] via A2 + B3 approach

The syntheses and properties of hyperbranched poly(o‐hydroxyamide) [poly(HAB‐BCC)‐ABP], poly[o‐(t‐butoxycarbonyl)amide] [poly(HAB‐BCC)‐ABP‐t‐BOC], and polybenzoxazole [poly(HAB‐cycloBCC)] were examined. Poly(HAB‐BCC)‐ABP was obtained from the polycondensation reaction of 3,3‐dihydroxy‐4,4′‐diaminobiphenyl (HAB) as an A₂‐monomer and 1,3,5‐benzenetricarboxylchloride (BCC) as a B₃‐monomer with 2‐amino‐4‐t‐butylphenol (ABP) in NMP in the presence of pyridine for 24 h. The reaction of poly(HAB‐BCC)‐ABP and di‐t‐buthylcarbonate (DiBOC) was performed to obtain the corresponding poly(HAB‐BCC)‐ABP‐t‐BOC with pendant t‐BOC groups. The thermal cyclodehydration of poly(HAB‐BCC)‐ABP‐t‐BOC was carried out in the film sate at 400 °C, affording the poly(HAB‐cyclo‐BCC) in quantitative yield. Furthermore, the solubilities and thermal properties of these polymers were examined. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3640–3649, 2006     

Well‐defined poly(oxazoline)‐b‐poly(acrylate) amphiphilic copolymers: From synthesis by polymer–polymer coupling to self‐organization in water

In this contribution, we report on the self‐assembly in water of original amphiphilic poly(2‐methyl‐2‐oxazoline)‐b‐poly(tert‐butyl acrylate) copolymers, synthesized by copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction. For such purpose, (poly(2‐methyl‐2‐oxazoline)) and (poly(tert‐butyl acrylate)) are first prepared by cationic ring‐opening polymerization and atom transfer radical polymerization, respectively. Well‐defined polymeric building blocks, ω‐N₃‐P(t‐BA) and α‐alkyne‐P(MOx), bearing reactive chain end groups, are accurately characterized by matrix‐assisted laser desorption ionization time‐of‐flight spectroscopy. Then, P(MOx)_n‐b‐P(t‐BA)_m are achieved by polymer–polymer coupling and are fully characterized by diffusion‐ordered NMR spectroscopy and size exclusion chromatography, demonstrating the obtaining of pure amphiphilic copolymers. Consequently, the latter lead to the formation in water of well‐defined monodisperse spherical micelles (R_H = 40–60 nm), which are studied by fluorescence spectroscopy, static light scattering, atomic force microscope, and transmission electronic microscopy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Facile synthesis of polymer–peptide conjugates via direct amino acid coupling chemistry

Polymer–peptide conjugates (also known as biohybrids) are attracting considerable attention as injectable materials owing to the self‐assembling behavior of the peptide and the ability to control the material properties using the polymer component. To this end, a simple method for preparing poly(ethylene oxide)‐oligophenylalanine polymer–peptide conjugates (mPEO_m‐F_n‐OEt) using isobutylchloroformate as the activating reagent has been identified and developed. The synthetic approach reported employs an industrially viable route to produce conjugates with high yield and purity. Moreover, the approach allows judicious selection of the precursor building blocks to produce libraries of polymer–peptide conjugates with complete control over the molecular composition. Control over the molecular make‐up of the conjugates allows fine control of the physicochemical properties, which will be exploited in future studies into the prominent self‐assembling behavior of such materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4853–4859     

Peptide‐poly(tert‐butyl methacrylate) conjugate into composite micelles in organic solvents versus peptide‐poly(methacrylic acid) conjugate into spherical and worm‐like micelles in water: Synthesis and self‐assembly

Peptide–polymer conjugates are versatile class of biomaterials composed of a peptide block covalently linked with a synthetic polymer block. This report demonstrates the synthesis of peptide‐poly(tert‐butyl methacrylate) (Peptide‐P^tBMA) conjugates of varying molecular weights via a “grafting from” atom transfer radical polymerization (ATRP) technique using as‐synthesized peptide‐based initiator in toluene. Peptide‐P^tBMA conjugate is soluble in many organic solvents and undergoes self‐assembly into micro/nanospheres in DMF/THF as observed from both FESEM and DLS results. The conjugate micro/nanospheres are nothing but the composite micelles formed by the secondary aggregation of primary micelles generated initially in these organic solvents. The hydrolysis of tert‐butyl groups of Peptide‐P^tBMA conjugate leads to the formation of peptide‐poly(methacrylic acid) (Peptide‐PMA) conjugate. The circular dichroism (CD) analysis exhibits the presence of β‐sheet conformation of peptide moiety in synthesized conjugates. The formed Peptide‐PMA conjugate is soluble in water and owing to its amphiphilic character, the conjugate molecules self‐assemble into spherical micelles as well as worm‐like micelles upon increasing the concentration of conjugate in water. However, the sodium salt of Peptide‐PMA conjugates (Peptide‐PMAS) self‐assembles into only spherical swollen micelles in water at higher (pH ～10). The critical aggregation concentrations (CACs) of both Peptide‐PMA and Peptide‐PMAS micelles are measured by fluorescence spectroscopy. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3019–3031     

Preparation of 3‐arm star polymers (A3) via Diels–Alder click reaction

Diels–Alder click reaction was successfully applied for the preparation of 3‐arm star polymers (A₃) using furan protected maleimide end‐functionalized polymers and trianthracene functional linking agent (2) at reflux temperature of toluene for 48 h. Well‐defined furan protected maleimide end‐functionalized polymers, poly (ethylene glycol), poly(methyl methacrylate), and poly(tert‐butyl acrylate) were obtained by esterification or atom transfer radical polymerization. Obtained star polymers were characterized via NMR and GPC (refractive index and triple detector detection). Splitting of GPC traces of the resulting polymer mixture notably displayed that Diels–Alder click reaction was a versatile and a reliable route for the preparation of A₃ star polymer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 302–313, 2008     

Hydroxyl‐terminated hyperbranched aromatic poly(ether‐ester)s: Synthesis,characterization, end‐group modification,and optical properties

Novel AB₂‐type monomers such as 3,5‐bis(4‐methylolphenoxy)benzoic acid ( monomer 1 ), methyl 3,5‐bis(4‐methylolphenoxy) benzoate ( monomer 2 ), and 3,5‐bis(4‐methylolphenoxy)benzoyl chloride ( monomer 3 ) were synthesized. Solution polymerization and melt self‐polycondensation of these monomers yielded hydroxyl‐terminated hyperbranched aromatic poly(ether‐ester)s. The structure of these polymers was established using FTIR and ¹H NMR spectroscopy. The molecular weights (M_w) of the polymers were found to vary from 2.0 × 10³ to 1.49 × 10⁴ depending on the polymerization techniques and the experimental conditions used. Suitable model compounds that mimic exactly the dendritic, linear, and terminal units present in the hyperbranched polymer were synthesized for the calculation of degree of branching (DB) and the values ranged from 52 to 93%. The thermal stability of the polymers was evaluated by thermogravimetric analysis, which showed no virtual weight loss up to 200 °C. The inherent viscosities of the polymers in DMF ranged from 0.010 to 0.120 dL/g. End‐group modification of the hyperbranched polymer was carried out with phenyl isocyanate, 4‐(decyloxy)benzoic acid and methyl red dye. The end‐capping groups were found to change the thermal properties of the polymers such as T_g. The optical properties of hyperbranched polymer and the dye‐capped hyperbranched polymer were investigated using ultraviolet‐absorption and fluorescence spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5414–5430, 2008     

An enhanced host–guest electro‐optical polymer system using poly(norbornene‐dicarboximides) via ROMP

High glass transition temperature poly(N‐cyclohexyl‐5‐norbornene‐2,3‐dicarboximide)s (NDI)s prepared by ring opening metathesis polymerization yielded polymers with a narrow polydispersity and well‐controlled molecular weight materials when using the Grubbs first generation initiator. Polymers produced using the Grubbs second generation initiator could not be controlled easily. By initiator selection it was also possible to synthesize polymers with either 98 or 52% trans microstructures. These materials were employed as electro‐optic (EO) polymer hosts for high molecular hyperpolarizability (β) phenyl vinylene thiophene vinylene bridge chromophores. This chromophore was modified by the incorporation of a tert‐butyldiphenylsilane group. The addition was able to further increase its EO coefficient (r₃₃) to reach 93 pm/V in a trans rich poly(NDI) produced by the Grubbs first generation initiator, compared to a benchmark chromophore / polymer combination. We investigated in detail the relationship between polymer microstructure and their absolute molecular weight on forming the best host–guest with the high β chromophore. Our results indicate that by utilizing a very simple host–guest system a high r₃₃ can be realized. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013