Diels–Alder modification of poly(ethylene terephthalate‐co‐anthracene‐2,6‐carboxylate) with N‐substituted maleimides

Dimethyl 2,6‐anthracene dicarboxylate is used as a comonomer in the synthesis of functional copolymers that are subject to modification with Diels–Alder reactions. The formation of poly(ethylene terephthalate‐co‐2,6‐anthracenate), containing less than 20 mol % of the anthracene‐2,6‐dicarboxylate structural units, provides materials that are tractable and soluble. The anthracene units of the copolymers undergo Diels–Alder reactions with N‐substituted maleimides. The grafting of N‐alkylmaleimides affords soluble, hydrophobic polymers, whereas grafting with maleimide‐terminated poly(ethylene glycol) affords hydrophilic polymers. Because this reaction proceeds below the melting point of the copolymers, the procedure can be applied to thin films, whereby the surface properties are modified. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3256–3263, 2002     

Synthesis and properties of comb polymers with semirigid mesogen‐jacketed polymers as side chains

A series of novel comb polymers, poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene}‐g‐polystyrene (PMPCS‐g‐PS), with mesogen‐jacketed rigid side chains were synthesized by the “grafting onto” method from α‐yne‐terminated PMPCS (side chain) and poly(vinylbenzyl azide) (backbone) by Cu(I)‐catalyzed 1,3‐dipolar cycloaddition click reaction. The α‐yne‐terminated PMPCS was synthesized by Cu(I)‐catalyzed atom transfer radical polymerization initiated by a yne‐functional initiator. Poly(vinylbenzyl azide) was prepared by polymerizing vinylbenzyl chloride using nitroxide mediated radical polymerization to obtain poly(vinylbenzyl chloride) as the precursor which was then converted to the azide derivative. The chemical structure and architectures of PMPCS comb polymers were confirmed by ¹H NMR, gel permeation chromatography, and multiangle laser light scattering. Both surface morphologies and solution behaviors were investigated. Surface morphologies of PMPCS combs on different surfaces were investigated by scanning probe microscopy. PMPCS combs showed different aggregation morphologies when depositing on silicon wafers with/without chemical modification. The PMPCS comb polymers transferred to polymer‐modified silicon wafers using the Langmuir‐Blodgett technique showed a worm‐like chain conformation. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and self‐assembly of hyperbranched polymers with benzoyl terminal arms

Hyperbranched polyesters (HPs) with a variable content of benzoyl terminal groups were synthesized through the chemical modification of the HPs' cores by substituting a controlled fraction of the terminal hydroxyl groups with benzoyl chloride. The resulting hyperbranched polymers that were modified by benzoyl groups (HPs‐B) were characterized by ¹H NMR, FTIR, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). Research results revealed that self‐assembled structures could be formed in selected solvents (acetone/n‐hexane). It was found that the morphologies of self‐assembled structures could be adjusted by controlling the content of outside benzoyl terminal groups in the hyperbranched polymers, the volume ratio of acetone with n‐hexane, and the concentration of the hyperbranched polymers with benzoyl terminal arms. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5554–5561, 2005     

The influence of variant PE‐b‐PEO segments on physical properties of LLDPE graft copolymers

A method was adopted to fix a series of polymers of PE‐b‐PEO with different PEO/PE segments on the chains of LLDPE. Maleic anhydride (MA) reacting with hydroxyl group of PE‐b‐PEO (mPE‐b‐PEO) was used as the intermediate. The structures of intermediates and graft copolymers were approved by ¹H NMR and FTIR. XPS analysis revealed a great amount of oxygen on the surface of grafted copolymers although the end group of PEO was fixed on the LLDPE chains through MA. Thermal properties of the graft copolymers as determined by differential scanning calorimetry (DSC) showed that PE segments in the grafted monomers could promote the heterogeneous nucleation of the polymer, increase T_c, and crystal growth rate. While the amorphous PEO segments which attached to the crystalline PE segments in LLDPE, impaired their ability to fit the crystal lattice, and depressed the crystallization of LLDPE backbones. In this study, it was also verified through the dynamic rheological data that increasing M_n of grafted monomers significantly increased the complex viscosity and enhanced the shear‐thinning behavior. Long‐branched chains formed by grafted monomers enhanced the complex moduli (G′ and G″) value and retarded relaxation rate. However, there were little influence on the rheological properties when increasing the amounts of PEO segments (or decreasing PE segments) of grafted monomers with similar molecular weight. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 506–515, 2008     

Surface‐confined photopolymerization of single‐ and mixed‐monomer systems to tailor the wettability of poly(L‐lactide) film

The major objective of this research was to modify the surface characteristics of poly(L ‐lactide) (PLA) by grafting a combination of hydrophilic polymers to produce a continuum of hydrophilicity. The PLA film was solvent cast, and the film surfaces were activated by ultra violet (UV) irradiation. A single monomer or combination of two monomers, selected from vinyl acetate (VAc), acrylic acid (AA), and acrylamide (AAm), were then grafted to the PLA film surface using a UV induced photopolymerization process. The film surfaces resulting from each reaction step were analyzed using ATR‐FTIR spectroscopy and contact angle goniometry. Results showed that AAm dominated the hydrophilicity of the film surface when copolymerized with VAc or AA, while the water contact angles for PLA films grafted with poly(vinyl acetate‐co‐acrylic acid) varied more gradually with feed composition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6534‐6543, 2006     

Synthesis of three new 1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl) pyrrole‐based donor polymers and their bulk heterojunction solar cell applications

A series of three new 1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole‐based polymers such as poly[1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole] ( PTPT ), poly[1,4‐(2,5‐bis(octyloxy)phenylene)‐alt‐5,5'‐(1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole)] ( PPTPT ), and poly[2,5‐(3‐octylthiophene)‐alt‐5,5'‐(1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole)] ( PTTPT ) were synthesized and characterized. The new polymers were readily soluble in common organic solvents and the thermogravimetric analysis showed that the three polymers are thermally stable with the 5% degradation temperature >379 °C. The absorption maxima of the polymers were 478, 483, and 485 nm in thin film and the optical band gaps calculated from the onset wavelength of the optical absorption were 2.15, 2.20, and 2.13 eV, respectively. Each of the polymers was investigated as an electron donor blending with PC₇₀BM as an electron acceptor in bulk heterojunction (BHJ) solar cells. BHJ solar cells were fabricated in ITO/PEDOT:PSS/polymer:PC₇₀BM/TiO_x/Al configurations. The BHJ solar cell with PPTPT :PC₇₀BM (1:5 wt %) showed the power conversion efficiency (PCE) of 1.35% (J_sc = 7.41 mA/cm², V_oc = 0.56 V, FF = 33%), measured using AM 1.5G solar simulator at 100 mW/cm² light illumination. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Modular synthesis of polymers containing 2,5‐di(thiophenyl)‐N‐arylpyrrole

A modular and facile route has been developed to synthesize functionalized 2,5‐di(thiophen‐2‐yl)‐1‐H‐arylpyrroles from readily available starting materials. These units are compatible with various polymerization conditions and are versatile building blocks for conjugated polymers. The polymers show high thermal stability and solubility in a number of solvents. Characterization of the polymers reveals a correlation between molecular packing, controllable by polymer design, and charge carrier mobility. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1133–1139     

Synthesis and characterization of a thermotropic liquid‐crystalline poly[2,5‐bis(4′‐alkoxycarbonylphenyl) styrene]

We report the synthesis and characterization of a series of novel mesogen‐jacketed liquid‐crystalline polymers, poly[2,5‐bis(4′‐alkoxycarbonylphenyl)styrene]s ( 1‐m , where m is the number of carbon atoms in the alkyl tails), along with the corresponding monomers, 2,5‐bis(4′‐alkoxycarbonylphenyl)styrenes ( 2‐m ), and their precursors, 2,5‐bis(4′‐alkoxycarbonylphenyl)toluenes ( 3‐m ). The influence of the tail length on the thermotropic properties of the two types of low‐molecular‐mass compounds and macromolecules was investigated with a combination of differential scanning calorimetry, polarized optical microscopy, and wide‐angle X‐ray diffraction techniques. Except for compound 3‐3 , which exhibited a monotropic nematic phase, all members of the low‐molar‐mass molecules developed no mesophase during both heating and cooling processes. The glass‐transition temperatures of the polymers decreased as the tail lengths increased. The 5% weight loss temperatures of all the polymers under a nitrogen atmosphere were above 360 °C, indicating quite high thermal stability. Although polymers 1‐1 and 1‐2 were non‐liquid‐crystalline, columnar nematic phases were observed for the remaining homopolymers with longer alkyl tails. The mesophases of 1‐3 to 1‐9 that developed at high temperatures remained upon cooling to room temperature, whereas those of 1‐10 to 1‐12 disappeared during the cooling process. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 830–847, 2007.     

Morphology and mechanical properties of blown films of a low‐density polyethylene/linear low‐density polyethylene blend

The morphologies of films blown from a low‐density polyethylene (LDPE), a linear low‐density polyethylene (LLDPE), and their blend have been characterized and compared using transmission electron microscopy, small‐angle X‐ray scattering, infrared dichroism, and thermal shrinkage techniques. The blending has a significant effect on film morphology. Under similar processing conditions, the LLDPE film has a relatively random crystal orientation. The film made from the LDPE/LLDPE blend possesses the highest degree of crystal orientation. However, the LDPE film has the greatest amorphous phase orientation. A mechanism is proposed to account for this unusual phenomenon. Cocrystallization between LDPE and LLDPE occurs in the blowing process of the LDPE and LLDPE blend. The structure–property relationship is also discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 507–518, 2002; DOI 10.1002/polb.10115     

Tuning h‐bond capability of hydroxylated‐poly(2,3,4,5,6‐pentafluorostyrene) grafted copolymers prepared by chemoselective and versatile thiol‐para‐fluoro “click‐type” coupling with mercaptoalcohols

Novel H‐bond donor copolymers were designed by a versatile “click type” grafting reaction of unprotected mercaptoalcohols onto poly(2,3,4,5,6‐pentafluorostyrene) (PPFS). As demonstrated by ¹⁹F NMR and Fourier transform infrared spectroscopy (FTIR) analyses, the reaction appears to be chemoselective as the SH groups solely react onto the para‐fluoro position of the PFS units. The nucleophilic substitution was successfully performed with two mercaptoalcohols bearing either one or two hydroxyl groups. By carefully selecting the experimental conditions, a library of copolymers with various degree of substitution up to 95% was obtained in a reasonable timescale through kinetic control. By turbidity analysis, the ability of these functional polymers to form in solution interpolymer complexes with poly(4‐vinyl pyridine) was shown to be tunable by adjusting the molecular characteristics. FTIR, X‐ray photoelectron spectroscopy, and Differential scanning calorimetry evidence that different types of blends (immiscible, partially or totally miscible, and complex) can be achieved, and that the driving force of the interaction originates from H‐bond. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of conducting poly(aniline‐co‐o‐aminophenethyl alcohol)s

Poly(o‐aminophenethyl alcohol) and its copolymers containing the aniline unit were synthesized in aqueous hydrochloric acid medium by chemical oxidative polymerization. The chemical composition of these novel polymers was determined spectroscopically, and their viscosities were measured. These polymers exhibit good solubility in organic solvents that is attributed mainly to the polar hydroxyethyl side groups. Their structures (chain conformation and morphological structure) and properties (conductivity, electrochemical characteristics, glass transition, and degradation behavior) were characterized and then interpreted on the basis of the chemical composition along with the electronic and steric hindrance effects associated with the hydroxyethyl side group. Overall, the side group has a significant effect on the polymerization and influences the structure, chain conformation, and properties of the resultant polymer. The poly(aniline‐co‐o‐aminophenethyl alcohol)s containing 20–40 mol % o‐aminophenethyl alcohol units are potential conducting materials for microelectronic and electromagnetic shielding applications because they are easier to process than polyaniline but retain its beneficial properties. These polymers can also be used as a functional conducting polymer intermediate owing to the reactivity of the side group. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 983–994, 2002     

Homopolymerizations and random copolymerizations of olefins with amino‐substituted cyclopentadienylchromium complexes

1‐(2‐N,N‐Dimethylaminoethyl)‐2,3,4,5‐tetramethylcyclopentadienyl‐chromium dichloride ( 1 ), (2‐N,N‐dimethylaminoethyl)cyclopentadienylchromium dichloride ( 6 ), and (2‐N,N‐dimethylaminoethyl)indenylchromium dichloride ( 7 ) in the presence of modified methylaluminoxane exhibit high catalytic activities for the polymerization of ethylene with random copolymerizations of ethylene with propylene, ethylene with 1‐hexene, and propylene with 1‐hexene. These initiators conduct polymerizations to give high molecular weight polymers with low polydispersities. However, the stereoregularities are very poor in these reactions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2759–2771, 2002     

Microwave‐assisted synthesis of star‐shaped poly(ε‐caprolactone)‐block‐poly(L‐lactide) copolymers and the crystalline morphologies

A monomode microwave reactor was used for the synthesis of designed star‐shaped polymers, which were based on dipentaerythritol with six crystallizable arms of poly(ε‐caprolactone)‐b‐poly(L ‐lactide) (PCL‐b‐PLLA) copolymer via a two‐step ring‐opening polymerization (ROP). The effects of irradiation conditions on the molecular weight were studied. Microwave heating accelerated the ROP of CL and LLA, compared with the conventional heating method. The resultant hexa‐armed polymers were fully characterized by means of FTIR, ¹H NMR spectrum, and GPC. The investigation of thermal properties and crystalline behaviors indicated that the crystalline behaviors of polymers were largely depended on the macromolecular architecture and the length of the block chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of novel π‐conjugated polymers with phosphole ring derivatives

Novel π‐conjugated polymers ( 8 – 10 ) were prepared by the palladium‐catalyzed Sonogashira coupling reaction of three kinds of phosphole‐ring‐containing monomers with 2,5‐dihexyloxyl‐1,4‐diethynylbenzene. The obtained polymers ( 8 – 10 ) were regioregulated with the 2,5‐substituted phosphole ring in the polymer main chain and characterized with ¹H, ¹³C, and ³¹P NMR and FTIR. Polymers 8 – 10 were found to have an extended π‐conjugated system according to the results of UV–vis absorption spectra. In the fluorescence emission spectra of 8 – 10 , moderate emission peaks were observed in the visible blue‐to‐green region. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2867–2875, 2007     

Proton‐conducting polymers based on benzimidazoles and sulfonated benzimidazoles

A sulfonated derivative of polybenzimidazole is reported, and its properties are analyzed in comparison with related polybenzimidazole proton‐conducting materials. Poly(2,5‐benzimidazole), poly(m‐phenylenebenzobisimidazole), and poly[m‐(5‐sulfo)‐phenylenebenzobisimidazole] were prepared by condensation of the corresponding monomers in polyphosphoric acid. Several adducts of these polymers with phosphoric acid were prepared. The resulting materials were characterized by chemical analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis; also, the dc conductivity of doped and undoped derivatives was measured. Similar to what has been observed for the commercial polybenzimidazole polymer (also examined here for comparison), the title polymers exhibit high thermal stability. Furthermore, their doping with phosphoric acid leads to a significant increase in conductivity from less than 10^?11 Scm^?1 for the undoped polymers to 10^?4 Scm^?1 (both at room temperature) for their acid‐loaded derivatives. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3703–3710, 2002     

Biobased poly(2,5‐furandimethylene succinate‐co‐butylene succinate) crosslinked by reversible Diels–Alder reaction

We synthesized biobased poly(2,5‐furandimethylene succinate‐co‐butylene succinate) [P(FS‐co‐BS)] copolymers by polycondensation of 2,5‐bis(hydroxymethyl)furan, 1,4‐butanediol, and succinic acid. These copolymers could be crosslinked to form network polymers by means of a reversible Diels–Alder reaction with bis‐maleimide. The thermal properties, mechanical properties, and healing abilities of the P(FS‐co‐BS)s and the network polymers were investigated. The mechanical properties of the network polymers depended on the comonomer composition of the P(FS‐co‐BS)s and the maleimide/furan ratio in the network polymers. Some of the copolymers exhibited healing ability at room temperature, and their healing efficiency was enhanced by solvent or heat. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 216–222     

Polyimides based on 2,5‐bis(4‐aminophenoxy)biphenyl

A diamine monomer II , 2,5‐bis(4‐aminophenoxy)biphenyl, was prepared through a nucleophilic substitution reaction of phenylhydroquinone and p‐chloronitrobenzene in the presence of potassium carbonate in N,N‐dimethylformamide, followed by catalytic reduction with hydrazine and Pd/C. A series of all‐aromatic, organosoluble polyimides bearing pendent phenyl groups were synthesized from the diamine with six kinds of commercial dianhydrides via a conventional two‐stage process. For improving solubility of polypyromellitimide, copolypyromellitimides with arbitrary solubilities were prepared from II and a pair of dianhydrides, which were mixed at certain molar ratios. These polymers showed good solubilities in N‐methyl‐2‐pyrrolidone and m‐cresol. The softening temperatures of these polyimides were recorded between 206 and 269 °C. Polymers had glass‐transition temperatures at 230–286 °C and 10% weight‐loss temperatures above 521 °C in air or nitrogen atmospheres. Their films had high tensile moduli and strengths. Excellent properties of these polyimides are attributed to the incorporation of the pendent phenyl group in diamine II . © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 429–438, 2002; DOI 10.1002/pola.10116     

Morphology,structure, and properties of in situ compatibilized linear low‐density polyethylene/polystyrene and linear low‐density polyethylene/high‐impact polystyrene blends

Blends of linear low‐density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high‐impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl₃), was adopted to initiate the Friedel–Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl₃ blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel–Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE‐g‐PS and LLDPE‐g‐HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m². Scanning electron microscopy micrographs showed that the size of the domains decreased from 4–5 to less than 1 μm, depending on the content of added AlCl₃. The crystallization behavior of the LLDPE/PS blend was investigated with differential scanning calorimetry. Fractionated crystallization phenomena were noticed because of the reduction in the size of the LLDPE droplets. The melt‐flow rate of the blending system depended on the competition of the grafting reaction of LLDPE with PS and the degradation of the blending components. The degradation of PS only happened during the alkylation reaction between LLDPE and PS. Gel permeation chromatography showed that the alkylation reaction increased the molecular weight of the blend polymer. The low molecular weight part disappeared with reactive blending. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1837–1849, 2003     

The suzuki–heck polymerization as a tool for the straightforward obtainment of poly(fluorenylene‐vinylene) sensitizers for dye‐sensitized solar cells

This article describes the synthesis and properties of the first poly(arylene‐vinylene)‐based sensitizers for application in dye‐sensitized solar cells (DSSC). The polymers were prepared by the Suzuki–Heck copolymerization of potassium vinyltrifluoroborate (PVTB) with a mixture of dibromoaryl comonomers designed to obtain macromolecules able to bind onto the photoelectrode by means of carboxyphenylene units. The copolymerization reactions were carried out in the presence of an excess of PVTB to lower the molecular weights of the polymers, which were obtained as soluble materials. The polymers poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene] ( P1 ), poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene‐co‐(4,7‐benzothiadiazolylene)‐vinylene] ( P2 ), and poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene‐co‐2,5‐thienylene‐vinylene] ( P3 ) were used in DSSC devices, obtaining conversion efficiencies up to 0.88% ( P3 ). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Field‐effect transistors based on PPV derivatives as a semiconducting layer

A series of modified thiophene groups containing PPV‐based semiconducting materials, poly[(2,5‐bis(octyloxy)‐1,4‐phenylenevinylene)‐alt‐(2,2′bithienylenevinylene)] ( PPBT ), poly[(2,5‐bis(octyloxy)‐1,4‐phenylenevinylene)‐alt‐(5,5‐thiostilylenevinylene)] ( PPTVT ), have been synthesized through a Horner coupling reaction. From the FTIR and ¹H NMR spectroscopy, the configuration of the vinylene groups in the polymers was all trans (E) geometry. The weight‐average molecular weights (M_w) of PPBT and PPTVT were found to be 11,700 and 11,800, with polydispersity indices of 2.51 and 2.53, respectively. PPBT and PPTVT thin films exhibit UV–visible absorption maxima at 538 and 558 nm, respectively, and the strong absorption shoulder peaks at 578 and 602 nm, respectively. Solution processed field‐effect transistors (FET) fabricated using all the polymers showed p‐type OTFT characteristics. The field‐effect mobility of the PPTVT was obtained up to 2.3 × 10^?3 cm² V^?1 s^?1, an on/off ratio of 1.0 × 10⁵ with ambient air stability. Studies of the atomic force microscopy (AFM) and X‐ray diffraction (XRD) analysis of the polymer thin films revealed that all the polymers were amorphous structure. The greater planarity and rigidity of PPTVT compared to PPBT results in elongation of conjugation length and better π–π stacking of polymer chains in amorphous region, which leads to improved FET performance. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 111–120, 2009