Polymeric nanocomposite comprising gold nanoparticles and bilaterally sulfur‐functionalized polystyrene

Anionic polymerization technique has been utilized to synthesize a bilaterally sulfur‐functionalized polystyrene, SCH3‐polystyrene‐SH. The synthesis scheme consists of (1) initiation of 4‐vinylbenzylmethyl sulfide with sec‐butyllithium to form a living sulfur‐containing initiator, (2) polymerization of styrene, and (3) termination of growing polystyrene chain with ethylene sulfide. The resulting bilaterally sulfur‐functionalized polystyrene is used to make polystyrene/gold nanoparticles (AuNPs) nanocomposite with AuNPs formed in situ in polymer solution through reduction of AuClO₄. The effects of the polymer/Au molar ratio as well as the molecular weight of polymer on the size and dispersion of formed AuNPs have been studied, and the superiority of bilaterally functionalized polymer to unilaterally functionalized polymer has been demonstrated. The polystyrene/AuNPs composite has been characterized by GPC, ¹H‐NMR, ¹³C‐NMR, EDS, TEM, UV‐Vis, and DSC. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1268–1277     

Donor–acceptor rod–coil block copolymers comprising poly[2,7‐(9,9‐dihexylfluorene)‐alt‐bithiophene] and fullerene as compatibilizers for organic photovoltaic devices

The successful synthesis is described for a donor–acceptor rod–coil block copolymer comprising blocks of poly[2,7‐(9,9‐dihexylfluorene)‐alt‐bithiophene] (F6T2) and polystyrene functionalized with fullerene (PS(C₆₀)) (F6T2‐b‐PS(C₆₀)). This new material was obtained by combining Suzuki polycondensation with radical addition fragmentation chain transfer. The block copolymer was characterized by nuclear magnetic resonance, gel permeation chromatography, and optical spectroscopy methods. Photophysical data for (F6T2‐b‐PS(C₆₀)) and a related block copolymer (F6T2‐b‐PS(PCBM)) (PCBM, phenyl‐C61‐butyric acid methyl ester) are reported and their performance as compatibilizers in bulk heterojunction organic solar cells is assessed. It is demonstrated that the addition of the rod–coil block copolymers to the active layer extends the operational stability of organic photovoltaic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 888–903     

Star‐shaped polystyrenes with glycoconjugated periphery and interior: Synthesis and entrapment of hydrophilic molecule

Star‐shaped polystyrenes with acetyl glucose in the periphery and interior were synthesized via two‐steps, 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO)‐mediated living radical polymerizations. In the first step, styrene (St) was polymerized with 4‐[1′‐(2″,2″,6″,6″‐tetramethyl‐1″‐piperidinyloxy)ethyl]phenyl 2,3,4,6‐tetra‐O‐acetyl‐β‐D ‐glucopyranoside, 1 , at 120 °C to afford a TEMPO‐terminated polystyrene with acetyl glucose in the chain‐end, arm‐polymer 2 . Similarly, St was polymerized with 1‐phenyl‐1‐(2′,2′,6′,6′‐tetramethyl‐1′‐piperidinyloxy)ethane, 3 , to obtain a TEMPO‐terminated polystyrene, arm‐polymer 4 . In the second step, the coupling reaction of arm‐polymer 2 was performed using divinylbenzene (DVB) as a linking agent in m‐xylene at 138 °C, giving a star‐shaped polystyrene with acetyl glucose in the periphery, 5 . The coupling reaction of arm‐polymer 4 with DVB was carried out in the presence of 1 , which produced a star‐shaped polystyrene with acetyl glucose in the interior, 6 . Dynamic laser light scattering (DLS) measurements indicated that 5 and 6 existed as the particles in toluene with the average diameters ranging from 12–40 nm. The numbers of the arm (N_arm) were 12–23 and 6–64 for 5 and 6 , respectively, which were determined by their isolated yields and static laser light scattering (SLS) measurements. The numbers of the acetyl glucose units (N₁) were 12–23 and 9–104 for 5 and 6 , respectively, which were determined from specific rotation ([α]₃₆₅). Finally, 5 and 6 were modified by deacetylation using sodium methoxide, producing star‐shaped polystyrenes with glucose in the periphery and interior, 7 and 8 , respectively. The final architectures were found to entrap a hydrophilic molecule at their glycoconjugated periphery or interior in good solvents for polystyrene such as chloroform. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4373–4381, 2005     

Preparation of polymer optical fibers doped with nonlinear optical active organic chromophores

We synthesized two novel organic nonlinear optical chromophores—chiral S(+)‐N‐[p‐(4‐nitrostyryl) phenyl] prolinol and non‐chiral [p‐(4‐nitrostyryl) phenyl] piperdine—as potential laser‐active dyes for photonic applications. Both materials show good optical transmittance in the telecommunication frequency region, desirable solubility in acrylic polymer optical fiber matrices, and attractive fluorescence properties that are advantageous for laser‐gain materials and devices. Subsequently, these two chromophores were incorporated into poly(methyl methacrylate) and poly(ethyl methacrylate) and drawn into polymer optical fibers. The relevant properties of these organic dye‐doped fibers have been studied, revealing essential attributes of laser‐active characteristics. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1794–1801, 2001     

RAFT polymerization in supercritical carbon dioxide based on an induced precipitation approach: Synthesis of 2‐ethoxyethyl methacrylate/acrylamide block copolymers

A new controlled/living heterogeneous polymerization technique using RAFT in benign supercritical CO₂ is described involving the formation of monomer‐swollen seed particles by precipitation of macroRAFT agent prior to polymerization. Controlled/living character of the induced precipitation is compared with the equivalent solution polymerization. The large scale synthesis of poly(2‐ethoxyethyl methacrylate)‐b‐poly(acrylamides) useful for biomedical applications is made possible with the polymer isolated as powders at high conversions, thus circumventing the requirement for volatile organic solvents. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2351–2356     

Multiblock poly(4‐vinylpyridine) and its copolymer prepared with cyclic trithiocarbonate as a reversible addition–fragmentation transfer agent

The polymerization of 4‐vinylpyridine was conducted in the presence of a cyclic trithiocarbonate (4,7‐diphenyl‐[1,3]dithiepane‐2‐thione) as a reversible addition–fragmentation transfer (RAFT) polymerization agent, and a multiblock polymer with narrow‐polydispersity blocks was prepared. Two kinds of multiblock copolymers of styrene and 4‐vinylpyridine, that is, (ABA)_n multi‐triblock copolymers with polystyrene or poly(4‐vinylpyridine) as the outer blocks, were prepared with multiblock polystyrene or poly(4‐vinylpyridine) as a macro‐RAFT agent, respectively. GPC data for the original polymers and polymers cleaved by amine demonstrated the successful synthesis of amphiphilic multiblock copolymers of styrene and 4‐vinylpyridine via two‐step polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2617–2623, 2007     

Surface modification of multiwalled carbon nanotubes via nitroxide‐mediated radical polymerization

The nitroxide‐mediated radical polymerization of styrene was carried out on the surfaces of multiwalled carbon nanotubes (MWNTs) initiated by an MWNT‐supported initiator multiwalled carbon nanotube–2″,2″,6″,6″‐tetramethylpiperidinyloxy (MWNT–Tempo). The content of polystyrene grafted from the surface was controlled by changes in the polymerization conditions, such as the reaction times or the ratios of monomers to initiators. The obtained polystyrene‐grafted multiwalled carbon nanotubes (MWNT–PSs) were further used to initiate the polymerization of 4‐vinylpyridine to get polystyrene‐b‐poly(4‐vinylpyridine)‐grafted multiwalled carbon nanotubes (MWNT–PS‐b‐P4VPs). In contrast to unmodified MWNTs, MWNT–PSs had relatively good dispersibility in various organic solvents, such as tetrahydrofuran, CHCL₃, and o‐dichlorobenzene. The structures and properties of MWNT–PSs and MWNT–PS‐b‐P4VPs were characterized and studied with several methods, including thermogravimetric analysis, Fourier transform infrared, ultraviolet–visible, and transmission electron microscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4656–4667, 2006     

Synthesis of poly(ethylene‐co‐vinyl alcohol)‐g‐polystyrene graft copolymer and their applications for ordered porous film and compatibilizer

A series of new functional poly(ethylene‐co‐vinyl alcohol)‐g‐polystyrene graft copolymers (EVAL‐g‐PS) with controlled molecular weight (M_n = 38,000–94,000 g mol^?1) and molecular weight distribution (M_w/M_n = 2.31–3.49) were synthesized via a grafting from methodology. The molecular structure and component of EVAL‐g‐PS graft copolymers were confirmed by the analysis of their ¹H NMR spectra and GPC curves. The porous films of such copolymers were fabricated via a static breath‐figure (BF) process. The influencing factors on the morphology of such porous films, such as solvent, temperature, polymer concentration, and molecular weight of polymer were investigated. Ordered porous film and better regularity was fabricated through a static BF process using EVAL‐g‐PS solution in CHCl₃. Scanning electron microscopy observation reveals that the EVAL‐g‐PS graft copolymer is an efficient compatibilizer for the blend system of low‐density polyethylene/polystyrene. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 516–524     

Low thresholds for a nonconventional polymer blend—Amplified spontaneous emission and lasing in F81−x:SYx system

A mixture of two polymer materials, poly (9,9‐dioctylfluorene) (F8), and one of the poly(para‐phenylenevinylene) derivatives, superyellow (SY) have been used to make F8_1?x:SY_x polymer blend system. Under a 3–5 ns pulsed‐laser excitation, this system showed excellent optical properties with low threshold values of ≈14 µJ/cm² and ≈8 µJ/cm² for amplified spontaneous emission and optically pumped lasing, respectively. The proposed system was also electroluminescent and an interesting candidate for future research on polymer injection lasers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 15–21     

Synthesis of well‐defined AB20‐type star polymers with cyclodextrin‐core by combination of NMP and ATRP

The synthesis of an AB₂₀‐type heteroarm star polymer consisting of a polystyrene arm and 20‐arms of poly(methyl methacrylate) or poly(tert‐butyl acrylate) was carried out using the combination of nitroxide‐mediated polymerization (NMP) and atom transfer radical polymerization (ATRP). The NMP of styrene was carried out using mono‐6‐[4‐(1′‐(2″,2″,6″,6″‐tetramethyl‐1″‐piperidinyloxy)‐ethyl)benzamido]‐β‐cyclodextrin peracetate ( 1 ) to afford end‐functionalized polystyrene with an acetylated β‐cyclodextrin (β‐CyD) unit (prepolymer 2 ) with a number‐average molecular weight (M_n) of 11700 and a polydispersity (M_w/M_n) of 1.17. After deacetylation of prepolymer 2 , the resulting polymer was reacted with 2‐bromoisobutyric anhydride to give end‐functionalized polystyrene with 20(2‐bromoisobutyrol)s β‐CyD, macroinitiator 4 . The copper (I)‐mediated ATRP of methyl methacrylate (MMA) and tert‐butyl acrylate (tBA) was carried out using macroinitiator 4 . The resulting polymers were isolated by SEC fractionation to produce AB₂₀‐type star polymers with a β‐CyD‐core, 5 . The well‐defined structure of 5 with weight‐average molecular weight (M_w)s of 13,500–65,300 and M_w/M_n's of 1.26–1.28 was demonstrated by SEC and light scattering measurements. The arm polymers were separated from 5 by destruction with 28 wt % sodium methoxide in order to analyze the details of their characteristic structure. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4271–4279, 2005     

Synthesis and solvent‐dependent micellization of the amphiphilic block copolymer poly(styreneboronic acid)‐block‐polystyrene

The amphiphilic organoboron block copolymer poly (styreneboronic acid)‐block‐polystyrene ( PSBA‐b‐PS ) has been prepared through a postpolymerization modification route from the silicon‐functionalized block copolymer poly(4‐trimethylsilylstyrene)‐block‐polystyrene ( PSSi‐b‐PS ). PSBA‐b‐PS is obtained through highly selective reaction of PSSi‐b‐PS with BBr₃ at room temperature and subsequent hydrolysis of the BBr₂‐functionalized intermediate. Transmission electron microscopy studies demonstrate that PSBA‐b‐PS undergoes pH dependent micellization in aqueous solution. Different morphologies could be realized by using different mixtures of water and organic solvents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2438–2445, 2010     

Thermoresponsive poly(ionic liquid): Controllable RAFT synthesis,thermoresponse, and application in dispersion RAFT polymerization

The thermoresponsive poly(ionic liquid) of poly[1‐(4‐vinylbenzyl)‐3‐methylimidozolium tetrafluoroborate] trithiocarbonate (P[VBMI][BF₄]‐TTC) showing the soluble‐to‐insoluble phase transition in the methanol/water mixture at the upper critical solution temperature (UCST) was synthesized by solution RAFT polymerization and the synthesized P[VBMI][BF₄]‐TTC was employed as macro‐RAFT agent to mediate the RAFT polymerization under dispersion condition to afford the thermoresponsive diblock copolymer nanoparticles of poly[1‐(4‐vinylbenzyl)‐3‐methylimidozolium tetrafluoroborate]‐b‐polystyrene (P[VBMI][BF₄]‐b‐PS). The controllable solution RAFT polymerization was achieved as indicated by the linearly increasing polymer molecular weight with the monomer conversion and the narrow molecular weight distribution. The P[VBMI][BF₄]‐TTC macro‐RAFT agent mediated dispersion polymerization afforded the P[VBMI][BF₄]‐b‐PS nanoparticles, the size of which was uncorrelated with the polymerization degree of the P[VBMI][BF₄] block. Several parameters including the polymerization degree, the polymer concentration and the water content in the solvent of the methanol/water mixture were found to be correlated with the UCST of the poly(ionic liquid). The synthesized poly(ionic liquid) is believed to be a new thermos‐responsive polymer and will be useful in material science. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 945–954     

Attapulgite grafted with polystyrene via a simultaneous reverse and normal initiation atom transfer radical polymerization

The surface grafting of attapulgite (ATP) with polystyrene (PS) was established via a simultaneous reverse and normal initiation atom transfer radical polymerization (SR&NIATRP). 4‐(chloromethyl)phenyltrimethoxysilane (CMPTMS) chemical bounded on the surface of ATP (ATP‐Cl, Cl‐I) was prepared via one‐step self‐assembly. SR&NI ATRP of styrene was conducted using CuCl₂ complex tris(2‐(dimethylamino)ethyl)amine (Me₆‐TREN) as the catalytic system, initiated by 2,2‐azobis(isobutyronitrile) (AIBN) and ATP‐Cl. FT‐IR, XRD, XPS, TGA and TEM data were consistent with the grafting of benzyl chloride groups and PS chains on ATP surface. The controllability of polymerization was investigated by the kinetics behavior under different molar ratio of AIBN and CuCl₂. The obtained polymer possessed a uniform distribution of molecular weights with a lower polydispersity index of 1.2～1.4. The relationship between polymerization on the surface of ATP and in solution was discussed in detail based on TGA data of hybrid particles and GPC trace of free polymer in solution. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1508–1516     

Breaking embedded electrospun fibers (BEEF): Fabrication of polymer spheres encapsulated in polymer films

In this work, a novel method to fabricate polymer spheres encapsulated in polymer films by breaking embedded electrospun fibers (BEEF) was developed. Polymer fibers were first prepared by electrospinning and embedded in other polymer films using a three‐layer deposition method. After thermal annealing, the electrospun fibers transform into individual spheres with regular spacing and sizes. Poly(methyl methacrylate) (PMMA) and polystyrene (PS) are both used as the fiber or film materials. The transformation process can be observed in‐situ by optical microscope (OM) and is similar to the Plateau–Rayleigh instability. The growth rates of the surface undulation of the fibers are calculated, and higher growth rates are observed at higher annealing temperatures. The sizes of the encapsulated polymer spheres agree well with the theoretical predictions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2463–2470     

Fluorous solvent‐soluble imaging materials containing anthracene moieties

Highly fluorinated photoresist polymers that can undergo photodimerization reactions were designed using an anthracene‐based monomer. Through the random radical copolymerizations of 6‐(anthracen‐9‐yl)hexyl methacrylate ( AHMA ) and semiperfluorodecyl methacrylate ( FDMA ) with four different compositions, polymers with M_n = 20,000–27,000 (M_w/M_n = 2.0–2.9) were prepared in benzotrifluoride. The polymers, in particular fluorous solvent‐soluble imaging material‐2 ( FSIM‐2 ), showed sufficient solubility in fluorous solvents, including hydrofluoroethers, but were rendered insoluble by UV exposure (365 nm). This photochemical solubility change was evaluated quantitatively by a quartz crystal microbalance technique, along with tracing the chemical reaction by UV–vis spectroscopy. Finally, FSIM‐2 and fluorous solvents were applied to the photolithographic patterning of organic light‐emitting diode pixels. In the patterning protocol involving the lift‐off of resist films in fluorous solvents, FSIM‐2 was recognized as a promising photoreactive material when compared with a reference polymer P(FDMA‐MAMA) , which necessitates acidolysis reactions for lithographic imaging. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1252–1259     

Light‐emitting diodes and lasers based on polymer films doped with small organic molecules and rare‐earth complexes

We investigated the lasing properties of optically pumped polymer films. Amplified spontaneous emission (ASE) around 400 nm was observed in polymer films of polystyrene (PS) and poly(N‐vinylcarbazole) (PVK) doped up to 20% with the hole‐transporting organic molecule N,N′‐bis(3‐methylphenyl)‐N,N′‐diphenylbenzidine (TPD). Thus, TPD‐based films are candidates for blue‐emitting organic diode lasers. Films containing several semiconducting organic molecules and polymers and rare‐earth complexes were also investigated. Energy transfer was observed in PVK films doped with various europium and samarium complexes. PS films containing the electron‐transporting organic molecule 2‐(4‐biphenylyl)‐5‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazole and small amounts of TPD also showed energy transfer to the europium complexes, but not to the samarium ones. None of these films demonstrated ASE; therefore, they are not appropriate for lasing purposes. However, because rare‐earth ions have very sharp emission spectra, these materials are candidates for very monochromatic light‐emitting diodes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2706–2714, 2003     

Synthesis,characterization, and solar cell and transistor applications of phenanthro[1,2‐b:8,7‐b′]dithiophene–Diketopyrrolopyrrole semiconducting polymers

Synthesis, characterization, and polymer solar cell and transistor application of a series of phenanthro[1,2‐b:8,7‐b′]dithiophene‐based donor–acceptor (D–A)‐type semiconducting polymers combined with a diketopyrrolopyrrole unit are reported. The present polymers showed some unique features such as strong aggregation behavior, high thermal stability, and short π–π stacking distance (3.5–3.6 Å), which are suitable for high performance organic materials. In addition, they have a significantly extended absorption up to 1000 nm with a band gap of ca. 1.2 eV. However, such strong intermolecular interaction reduced their solubility and molecular weights, which resulted in low crystalline nature and moderate field‐effect mobility of 0.01 cm² V^?1 s^?1. Furthermore, such strong aggregation behavior led to the large‐scale phase separation in the blend films, which may prevent the effective photocurrent generation, limiting J_sc and power conversion efficiency of 2.0%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 709–718     

New series of highly phenyl‐substituted polyfluorene derivatives for polymer light‐emitting diodes

A new series of highly phenyl‐substituted polyfluorene derivatives were synthesized and characterized. The resulting polymers were amorphous and showed excellent solubility in common organic solvents, such as chloroform, tetrahydrofuran, xylene, toluene, chlorobenzene, and so forth. All possessed satisfied thermal stability with glass‐transition temperatures (T_g's) in the range of 79–115 °C. They emitted blue light with photoluminescent (PL) maximum peaks at about 408–412 nm in thin films. The PL efficiencies of the polymer films were measured around 30–33%. The highly phenylated pendants improved the T_g of polyfluorene without forming defects in the polymers and reduced their tendency to form aggregate/excimers. Polymer light‐emitting diodes were fabricated from these polymers with the configuration of indium tin oxide/polyethylenedioxythiophene:polystyrene sulfonic acid/polymer/Ba/Al, which emitted bright blue light with maximum peaks at 418–420 nm. The maximum external quantum efficiencies of these devices were 0.41–0.6%. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2985–2993, 2004     

Synthesis and thermal properties of hybrid copolymers of syndiotactic polystyrene and polyhedral oligomeric silsesquioxane

Copolymerizations of styrene and the polyhedral oligomeric silsesquioxane (POSS)–styryl macromonomer 1‐(4‐vinylphenyl)‐3,5,7,9,11,13,15‐heptacyclopentylpentacyclo [9.5.1.1^3,9.1^5,15.1^7,13] octasiloxane have been performed with CpTiCl₃ in conjunction with methylaluminoxane. Random copolymers of syndiotactic polystyrene (sPS) and POSS have been formed and fully characterized with ¹H and ¹³C NMR, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. NMR data reveal a moderately high syndiotacticity of the polystyrene backbone consistent with this use of CpTiCl₃ as a catalyst and POSS loadings as high as 24 wt % and 3.2 mol %. Thermogravimetric analysis of the sPS–POSS copolymers under both nitrogen and air shows improved thermal stability with higher degradation temperatures and char yields, demonstrating that the inclusion of the inorganic POSS nanoparticles makes the organic polymer matrix more thermally robust. The polymerization activity and thermal stability are also compared with those of reported atactic polystyrene–POSS copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 885–891, 2002; DOI 10.1002/pola.10175     

Ultrafine hydrogel fibers with dual temperature‐ and pH‐responsive swelling behaviors

Ultrafine hydrogel fibers that were responsive to both temperature and pH signals were prepared through the electrospinning of poly(N‐isopropylacrylamide) (PNIPAAm) and poly(acrylic acid) mixtures in dimethylformamide. Both the diameters (700 nm to 1.2 μm) and packing of the fibers could be controlled through changes in the polymer compositions and PNIPAAm molecular weights. These fibers were rendered water‐insoluble by the addition of either Na₂HPO₄ or poly(vinyl alcohol) (PVA) to the solution, followed by the heat curing of the fibers. The fibers crosslinked with Na₂HPO₄ swelled to 30–120 times in water; this was significantly higher than the swelling of those crosslinked with PVA. The PVA‐crosslinked hydrogel fibers, however, exhibited faster swelling kinetics; that is, they reached equilibrium swelling in less than 5 min at 25 °C. They were also more stable after 1 week of water exposure; that is, they lost less mass and retained their fibrous form better. All the hydrogel fibers showed a drastic increase in the swelling between pH 4 and 5. The PVA‐crosslinked hydrogel fibers exhibited distinct temperature‐responsive phase‐transition behavior of PNIPAAm, whereas the Na₂HPO₄‐crosslinked hydrogel fibers showed altered two‐stage phase transitions that reflected side‐chain modification of PNIPAAm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6331–6339, 2004