Thermo‐ and pH‐responsive behaviors of graft copolymer and blend based on chitosan and N‐isopropylacrylamide

Thermo‐ and pH‐sensitive polymers were prepared by graft polymerization or blending of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm). The graft copolymer and blend were characterized by Fourier transform‐infrared, thermogravimetric analysis, X‐ray diffraction measurements, and solubility test. The maximum grafting (%) of chitosan‐g‐(N‐isopropylacrylamide) (NIPAAm) was obtained at the 0.5 M NIPAAm monomer concentration, 2 × 10⁻³ M of ceric ammonium nitrate initiator and 2 h of reaction time at 25°C. The percentage of grafting (%) and the efficiency of grafting (%) gradually increased with the concentration of NIPAAm up to 0.5 M, and then decreased at above 0.5 M NIPAAm concentration due to the increase in the homopolymerization of NIPAAm. Both crosslinked chitosan‐g‐NIPAAm and chitosan/PNIPAAm blend reached an equilibrium state within 30 min. The equilibrium water content of all IPN samples dropped sharply at pH > 6 and temperature > 30°C. In the buffer solutions of various pH and temperature, the chitosan/PNIPAAm blend IPN has a somewhat higher swelling than that of the chitosan‐g‐NIPAAm IPN. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1381–1391, 2000     

Preparation of composite‐crosslinked poly(N‐isopropylacrylamide) gel layer and characteristics of reverse hydrophilic–hydrophobic surface

The composite‐crosslinked poly(N‐isopropylacrylamide) (PNIPAAm) gels were prepared by grafting N‐isopropylacrylamide on the surface of glass plates modified by organosilanes. The glass plates as the substrate increase the mechanical strength of composite PNIPAAm gel layers. We investigated the effects of a series of organosilanes and the reaction time of organosilanes on surface characteristics, such as the static contact angle and the layer thickness. We discuss the equilibrium swelling ratio and the water release behavior of the gel layers in terms of the crosslinking density of the composite gels. The composite gels exhibit not only the characteristics of remarkable water release but also the reversed hydrophilic–hydrophobic surface properties. The gel layers are hydrophilic under 25°C and change to hydrophobic above 40°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1–11, 1999     

“Smart” membrane materials: Preparation and characterization of PVDF‐g‐PNIPAAm graft copolymer

In this research, a smart membrane material of graft copolymer of poly(vinylidene fluoride) with poly(N‐isopropylacrylamide) (PVDF‐g‐PNIPAAm) was synthesized by atom transfer radical polymerization (ATRP) using poly(vinylidene fluoride) (PVDF) as a macroinitiator and direct initiation of the secondary fluorinated site PVDF facilitates grafting the N‐isopropylacrylamide comonomer. The copolymers were characterized by Fourier transform infrared (FTIR), ¹H NMR, gel‐permeation chromatography (GPC), and X‐ray photoelectron spectroscopy (XPS). The temperature‐sensitive membrane was prepared from the PVDF‐g‐PNIPAAm graft copolymers by the phase inversion method. The effects of temperature on the flux of pure water of membrane was investigated. The results showed that alkyl fluorides were successfully applied as ATRP initiators in the synthetic condition and the flux of pure water through the PVDF‐g‐PNIPAAm membrane depended on the temperature change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1482–1486, 2007     

A novel dual stimuli‐responsive thiol‐end‐capped ABC triblock copolymer: synthesis via reversible addition–fragmentation chain transfer technique,and investigation of its self‐assembly behavior

A novel thermo‐ and pH‐responsive thiol‐end‐capped ABC triblock copolymer, namely poly(acrylic acid)‐block ‐poly(N ‐isopropylacrylamide)‐block ‐poly(? ‐caprolactone)–SH (PAA‐b ‐PNIPAAm‐b ‐PCL‐SH), was synthesized using a combination of ring‐opening polymerization and reversible addition–fragmentation chain transfer polymerization techniques. The chemical structures of all samples were characterized by means of Fourier transform infrared and ¹H NMR spectroscopies. The molecular weight of each segment was investigated using both ¹H NMR spectroscopy and gel permeation chromatography. The self‐assembly behavior of the PAA‐b ‐PNIPAAm‐b ‐PCL‐SH triblock copolymer under thermal and pH stimuli was fully investigated by means of fluorescence and UV–visible spectroscopies as well as dynamic light scattering measurements. The critical micelle concentration for the synthesized triblock copolymer was determined to be 0.0178 g L^?1 using the fluorescence probe technique. The average size of PAA‐b ‐PNIPAAm‐b ‐PCL‐SH micelles was determined to be 25 nm using transmission electron microscopy observations, and its lower critical solution temperature was determined to be 41–43 °C using UV–visible spectroscopy. © 2017 Society of Chemical Industry     

Thermoresponsive sodium alginate‐g‐poly(N‐isopropylacrylamide) copolymers III. Solution properties

Stimuli‐responsive biocompatible and biodegradable materials can be obtained by combining polysaccharides with polymers exhibiting lower critical solution temperature (LCST) phase behavior, such as poly(N‐isopropylacrylamide) (PNIPAAm). The behavior of aqueous solutions of sodium alginate (NaAl) grafted with PNIPAAm (NaAl‐g‐PNIPAAm) copolymers as a function of composition and temperature is presented. The products obtained exhibit a remarkable thermothickening behavior in aqueous solutions if the degree of grafting, the concentration, and the temperature are higher than some critical values. The sol–gel‐phase transition temperatures have been determined. It was found that at temperatures below LCST the systems behave like a solution, whereas at temperatures above LCST, the solutions behave like a stiff gel, because of PNIPAAm segregation. This behavior is reversible and could find applications in tissue engineering and drug delivery systems. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Highly transparent thermoresponsive surfaces based on tea‐stain‐inspired chemistry

A highly transparent thermoresponsive surface that could switch its wettability at different temperatures was constructed via tea‐stain‐inspired chemistry. The pristine tannic acid was modified by alkyl bromide with a substitution degree of 1.7 alkyl bromide units per tannic acid molecule. A coating of the alkyl bromine modified tannic acid with a thickness of 22 ± 3 nm was deposited onto the surface of glass via auto‐oxidation. A poly(N‐isopropylacrylamide) (PNIPAAm) brush was grafted from the alkyl bromide initiator via surface initiation atom transfer radical polymerization with a polymer grafting density of 8.6 × 10^?3 mg/cm². Due to the low thickness of the tannic acid and PNIPAAm coating, the transparency of this thermoresponsive surface remained constant at 94.3% even when the temperature was changed from 20 to 40 °C, but the water contact angle of this surface increased rapidly when the temperature was elevated from 25 to 35 °C. Due to the inevitable hydrolysis and deprotonation, this tea‐stain‐inspired chemistry‐based coating was stable in aqueous solution with a pH of 7 or isopropanol for soaking times of up to 24 h. The coating reported here may have various potential applications such as surfaces for cell culture media, food storage, or self‐cleaning materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46694.     

Preparation and characterization of a temperature‐sensitive nonwoven poly(propylene) with increased affinity for guest molecules

A temperature‐sensitive hydrogel with the capability of inclusion complex formation with guest molecules was successfully grafted onto the surface of nonwoven polypropylene (nonwoven PP). This was carried out by the use of N‐isopropylacrylamide monomer and a modified cyclodextrin (acrylamidomethyl‐β‐cyclodextrin (β‐CD‐NMA)). Fourier‐transform infra red (FT‐IR) and elemental analyses confirmed the presence of poly(N‐isopropylacrylamide) (PNIPAAm) and β‐CD‐NMA components on the surface of the textile. Equilibrium swelling ratio measurements showed that the grafted hydrogel maintained its temperature‐sensitive property compared to a nongrafted hydrogel. The effect of β‐CD‐NMA and crosslink agent concentrations on the grafting yield was studied. The β‐CD‐NMA content into the PNIPPAM‐ β‐CD‐NMA grafted nonwoven PP (PNIPAAm‐β‐CD‐NMA‐PP) was estimated by FT‐IR through a new procedure. The estimated amounts of β‐CD‐NMA in PNIPAAm‐β‐CD‐NMA‐PP were determined to be 0.9, 1.9 mg g^?1 for 0.019M and 0.049M concentrations of β‐CD‐NMA in monomer solution, respectively. The PNIPAAm‐β‐CD‐NMA‐PP showed a remarkable increase in absorbance affinity of 8‐anilino‐1‐naphthalenesulfonic acid ammonium salt at 20°C from 0.93 to 3.33 µmol g^?1 compared to PNIPAAm‐PP. Furthermore, the results showed a temperature‐sensitive loading affinity for PNIPAAm‐β‐CD‐NMA‐PP in absorbance of guest molecules due to the presence of β‐CD‐NMA. The use of hydrophobic guest molecules such as fragrance oils and antibiotics in modified fabrics can provide new applications in textile and pharmaceutical industry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40497.     

Novel PDMS‐based membranes: Sodium chloride and glucose permeability

Permeation of sodium chloride and glucose through polydimethylsiloxane‐poly(N‐isopropylacrylamide) (PDMS‐PNIPAAm) interpenetrating polymer networks (IPNs) of two different microstructures was investigated. We have successfully developed small‐molecule permeable IPNs, by modifying PDMS film structure. A group of PDMS films was prepared using conventional solvent casting (SC) method and another group produced by introducing oil, followed by SC and leaching the oil out (SCOL method). Scanning electron microscopy (SEM) and attenuated total reflection fourier transformer infrared (ATR‐FTIR) spectroscopy results confirmed the presence of PNIPAAm in the SC and SCOL IPNs. Results obtained from spectra of differential scanning calorimetry (DSC) showed that these IPNs had a phase transition temperature at about 32°C. Permeation measurements showed that the presence of PNIPAAm as the second phase in the IPN, improved the permeability of PDMS film. According to the results, maximum permeation coefficient was related to SCOL IPN containing 15.8% ± 0.3%PNIPAAm, at 23°C (5.98 × 10^?7 ± 7.93 × 10^?9 cm²/s for sodium chloride and 3.6 × 10^?7 ± 7 × 10^?9 cm²/s for glucose). These results suggested that these PDMS‐PNIPAAm IPNs with sodium chloride and glucose permeability may be further developed as ophthalmic biomaterials or corneal replacements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly(2‐alkyloyloxyethylacrylate) and poly(2‐alkyloyloxyethylacrylate‐co‐methylacrylate) comblike polymers as novel phase‐change materials for thermal energy storage

A series of poly(2‐alkyloyloxyethylacrylate) and poly(2‐alkyloyloxyethylacrylate‐co‐methylacrylate) polymers as novel polymeric phase‐change materials (PCMs) were synthesized starting from 2‐hydroxyethylacrylate and fatty acids. The chemical structure and crystalline morphology of the synthesized copolymers were characterized with Fourier transform infrared and ¹H‐NMR spectroscopy and polarized optical microscopy, respectively, and their thermal energy storage properties and thermal stability were investigated with differential scanning calorimetry and thermogravimetric analysis, respectively. The thermal conductivities of the PCMs were also measured with a thermal property analyzer. Moreover, thermal cycling testing showed that the copolymers had good thermal reliability and chemical stability after they were subjected to 1000 heating/cooling cycles. The synthesized poly(2‐alkyloyloxyethylacrylate) polymers and poly(2‐alkyloyloxyethylacrylate‐co‐methylacrylate) copolymers as novel PCMs have considerable potential for thermal energy storage and temperature‐control applications. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Switchable Wettability of Thermo‐Responsive Biocompatible Nanofibrous Films Created by Electrospinning

Thermo‐responsive PNIPAAm/PLLA nanofibrous films with tunable surface morphologies and better biocompatibility were prepared by electrospinning technique. The electrospun composite films possessed a “bead‐on‐string” structure. The wettability of nanofibrous films was observed by water CA measurements. The results showed that the electrospinning process and addition of PLLA did not change the thermo‐sensitivity of PNIPAAm. The wettability of electrospun PNIPAAm/PLLA composite films could switch from superhydrophilic to superhydrophobic when the temperature increased from 20 to 50 °C. Electrospinning is a promising way to create stimuli‐responsive surfaces with potential application in the design and tactics of controllable drug delivery system.

     

Temperature/pH‐sensitive comb‐type graft hydrogels composed of chitosan and poly(N‐isopropylacrylamide)

Comb‐type graft hydrogels, composed of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm), were prepared to manifest rapid temperature and pH sensitivity. Instead of directly grafting the NIPAAm monomer onto the chitosan chain, semitelechelic PNIPAAm with carboxyl end group was synthesized by radical polymerization using 3‐mercaptopropionic acid as the chain‐transfer agent, and was grafted onto chitosan having amino groups. The comb‐type hydrogels were prepared with two different graft yields and grafting regions, such as surface‐ and bulk‐grafting, and then compared with a chitosan hydrogel. The synthesis of telechelic PNIPAAm and the formation of amide group were confirmed by using FTIR spectroscopy and gel permeation chromatography. Results from the water state and thermal stability revealed that the introduction of the PNIPAAm side chain disturbed the ordered arrangement of the chitosan molecule, resulting in an increase in the equilibrium water content. Comb‐type graft hydrogels showed rapid temperature and pH sensitivity because of the free‐ended PNIPAAm attached to the chitosan main chain and the chitosan amino group itself, respectively. In particular, the surface graft hydrogel maintained its dimension at low pH, although the chitosan main chain was not crosslinked, whereas chitosan and bulk graft hydrogel were dissolved as a result of the coating effect of pH‐independent PNIPAAm. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2612–2620, 2004     

Thermally and magnetically dual‐responsive mesoporous silica nanospheres: preparation,characterization, and properties for the controlled release of sophoridine

Novel thermally and magnetically dual‐responsive mesoporous silica nanoparticles [magnetic mesoporous silica nanospheres (M‐MSNs)–poly(N‐isopropyl acrylamide) (PNIPAAm)] were developed with magnetic iron oxide (Fe₃O₄) nanoparticles as the core, mesoporous silica nanoparticles as the sandwiched layer, and thermally responsive polymers (PNIPAAm) as the outer shell. M‐MSN–PNIPAAm was initially used to control the release of sophoridine. The characteristics of M‐MSN–PNIPAAm were investigated by transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetry, N₂ adsorption–desorption isotherms, and vibrating specimen magnetometry analyses. The results indicate that the Fe₃O₄ nanoparticles were incorporated into the M‐MSNs, and PNIPAAm was grafted onto the surface of the M‐MSNs via precipitation polymerization. The obtained M‐MSN–PNIPAAm possessed superparamagnetic characteristics with a high surface area (292.44 m²/g), large pore volume (0.246 mL/g), and large mesoporous pore size (2.18 nm). Sophoridine was used as a drug model to investigate the loading and release properties at different temperatures. The results demonstrate that the PNIPAAm layers on the surface of M‐MSN–PNIPAAm effectively regulated the uptake and release of sophoridine. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40477.     

Preparation,characterization, and drug‐release properties of pH/temperature‐responsive poly(N‐isopropylacrylamide)/chitosan semi‐IPN hydrogel particles

Novel poly(N‐isopropylacrylamide) (PNIPAAm)/chitosan (CS) semi‐interpenetrating polymer network hydrogel particles were prepared by inverse suspension polymerization. The prepared particles were sensitive to both temperature and pH, and they had good reversibility in solution at different temperatures and pH values. The swelling ratios of PNIPAAm/CS hydrogel particles decreased slightly with the addition of CS, which did not shift the lower critical solution temperature. The drug‐release behavior of the particles was investigated using cyclic adenosine 3′,5′‐monophosphate (cAMP) as a model drug. The release of cAMP from the hydrogel particles was affected by temperature, pH, and the CS content in the particles. These results showed that semi‐IPN hydrogel particles appeared to be of great promise in pH‐ and temperature‐sensitive oral drug release. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of thermal‐responsive poly(propylene) membranes grafted with n‐isopropylacrylamide by plasma‐induced polymerization and their water permeation

Poly(propylene) (PP) membrane grafted with poly(N‐isopropylacrylamide) (PNIPAAm), which is known to have a lower critical solution temperature (LCST) at around 32°C, was prepared by the plasma‐induced graft polymerization technique. Graft polymerization of PNIPAAm onto a PP membrane was confirmed by microscopic attenuated total reflection/Fourier transform IR spectroscopy. The grafting yield of PNIPAAm increased with the concentration of N‐isopropylacrylamide monomer and the reaction time of graft polymerization. The average pore size of the PP membrane also affected the grafting yield. From the field emission scanning electron microscopy (FE‐SEM) measurement, we observed a morphological change in the PP‐g‐PNIPAAm membrane under wet conditions at 25°C below LCST. The permeability of water through the PP‐g‐PNIPAAm membrane was controlled by temperature. The PP‐g‐PNIPAAm membrane (PN05 and PN10) exhibited higher water permeability (L_p) than the original PP substrate membrane below LCST. As the temperature increased to above LCST, L_p gradually decreased. In addition, the graft yield of PNIPAAm and the average pore size of the PP substrate influenced water permeability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1168–1177, 2002; DOI 10.1002/app.10410     

Synthesis,curing behavior and thermal properties of silicon‐containing hybrid polymers with Si−C≡C units

Three novel kinds of linear silicon‐containing hybrid polymers with Si?C≡C units were synthesized by polycondensation reactions using the Grignard reagent method. All the polymers were thermosetting, highly heat‐resistant, moldable and easily soluble in common organic solvents. The structure, curing behavior, thermal and oxidative properties were characterized using Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. The results obtained can provide theoretical guidance for determining the curing of the resin system. In addition, the cured polymers exhibit excellent thermal and oxidative stabilities with temperatures of 5% weight loss (T_d5) above 480 °C and 450 °C in nitrogen and air respectively; the residues at 1000 °C were above 70.0% and 45.0% respectively. The thermal and oxidative stabilities of the polymers are attributed to a crosslinking reaction between the Si?H and C≡C bonds or C≡C bonds. These polymers have the potential for use as high‐temperature‐resistant resins and ceramic precursors. © 2013 Society of Chemical Industry     

Actual air separation through poly(aniline‐co‐toluidine)/ethylcellulose blend thin‐film composite membranes

Several multilayer thin‐film composite membranes were fabricated of ethylcellulose (EC) and poly(aniline‐co‐ortho‐toluidine) or poly(ortho‐toluidine) blend as selective thin films and three ultrafiltration membranes with a 10‐ to 45‐nm pore size and 100‐ to 200‐μm thickness as porous supports. The relationships between the actual air‐separation performance through the composite membranes and layer number, composition, casting solution concentration of the thin selective film are discussed. The oxygen‐enriched air (OEA) flux through the composite membranes increases steadily with increasing operational temperature and pressure. The oxygen concentration enriched by the composite membranes appears to decrease with operating temperature, but increases with operating pressure. The actual air‐separation property through the composite membranes seems to remain nearly constant for at least 320 days. The respective highest OEA flux, oxygen flux, and oxygen concentration, respectively, were found to be 4.78 × 10⁻⁵ cm³ (STP)/s · cm², 2.2 × 10⁻⁵ cm³ (STP)/s · cm², and 46% across EC/poly(o‐toluidine) (80/20) blend monolayer thin‐film composite membranes in a single step at 20°C and 650 kPa operating pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 458–463, 2000     

Emulsion‐electrospinning n‐octadecane/silk composite fiber as environmental‐friendly form‐stable phase change materials

The ultrafine n‐octadecane/silk composite fibers as form‐stable phase change materials were successfully developed by the emulsion‐electrospinning method. The effect of n‐octadecane content in the emulsion on the morphology and thermal energy storage capacity of the composite fibers were scientifically investigated. Scanning electron microscopy images show that the composite fibers display cylindrical shape with smooth surface and uniform diameter. Differential scanning calorimetry results demonstrate that the composite fibers exhibit reversible phase transition behavior, high thermal energy storage capacity, and good thermal reliability. Meanwhile, the composite fibers exhibit the capability to regulate their interior temperature as the ambient temperature alters according to the thermo‐infrared images. In addition, the composite fibers are friendly to the environment due to the biodegradability of silk. Therefore, the n‐octadecane /silk composite fibers have the great potential application of serving as form‐stable phase change materials for thermal energy storage and thermal regulation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45538.     

Thermally Resistive Electrospun Composite Membranes for Low‐Grade Thermal Energy Harvesting

In this work, thermally insulating composite mats of poly(vinylidene fluoride) (PVDF) and polyacrylonitrile (PAN) blends are used as the separator membranes. The membranes improve the thermal‐to‐electrical energy conversion efficiency of a thermally driven electrochemical cell (i.e., thermocell) up to 95%. The justification of the improved performance is an intricate relationship between the porosity, electrolyte uptake, electrolyte uptake rate of the electrospun fibrous mat, and the actual temperature gradient at the electrode surface. When the porosity is too high (87%) in PAN membranes, the electrolyte uptake and electrolyte uptake rate are significantly high as 950% and 0.53 µL s^?1, respectively. In such a case, the convective heat flow within the cell is high and the power density is limited to 32.7 mW m^?2. When the porosity is lesser (up to 81%) in PVDF membranes, the electrolyte uptake and uptake rate are relatively low as 434% and 0.13 µL s^?1, respectively. In this case, the convective flow shall be low, however, the maximum power density of 63.5 mW m^?2 is obtained with PVDF/PAN composites as the aforementioned parameters are optimized. Furthermore, multilayered membrane structures are also investigated for which a bilayered architecture produces highest power density of 102.7 mW m^?2.     

Thermal properties of blends of poly(hydroxybutyrate‐co‐hydroxyvalerate) and poly(styrene‐co‐acrylonitrile)

Thermal properties of blends of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) and poly(styrene‐co‐acrylonitrile) (SAN) prepared by solution casting were investigated by differential scanning calorimetry. In the study of PHBV‐SAN blends by differential scanning calorimetry, glass transition temperature and melting point of PHBV in the PHBV‐SAN blends were almost unchanged compared with those of the pure PHBV. This result indicates that the blends of PHBV and SAN are immiscible. However, crystallization temperature of the PHBV in the blends decreased approximately 9–15°. From the results of the Avrami analysis of PHBV in the PHBV‐SAN blends, crystallization rate constant of PHBV in the PHBV‐SAN blends decreased compared with that of the pure PHBV. From the above results, it is suggested that the nucleation of PHBV in the blends is suppressed by the addition of SAN. From the measured crystallization half time and degree of supercooling, interfacial free energy for the formation of heterogeneous nuclei of PHBV in the PHBV‐SAN blends was calculated and found to be 2360 (mN/m)³ for the pure PHBV and 2920–3120 (mN/m)³ for the blends. The values of interfacial free energy indicate that heterogeneity of PHBV in the PHBV‐SAN blends is deactivated by the SAN. This result is consistent with the results of crystallization temperature and crystallization rate constant of PHBV in the PHBV‐SAN blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 673–679, 2000     

Effect of multiwall carbon nanotube and au nanoparticle on the structure–property relationship of poly(N‐isopropyl acrylamide)

Temperature‐sensitive poly(N‐isopropyl acrylamide) (PNIPAAm) was synthesized both in the presence and absence of nanomaterials like allyl mercaptan decorated gold nanoparticle and allyalcohol‐conjugated multiwall carbon nanotube. The influence of the nanomaterials on the structure–property relationship of PNIPAAm was analyzed and critically compared to the pristine PNIPAAm. During the in situ polymerization, the nanosphere shape of Au nanoparticle was converted into Au nanorod shape, which was confirmed through UV–vis spectroscopy. The glass transition temperature (T_g) of polymer/nanocomposites was greater than that of the pristine polymer. Thermogravimetric analysis declared that the polymer/nanocomposites exhibited higher thermal stability than the homopolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012