Synthetic thermally reversible gel systems. III

Polyacrylylglycinamide (PAG) and its thermally reversible aqueous gels have been investigated and comparisons made with gelatin. For unfractionated PAG homopolymers in 2M NaCNS at 25°C, the Mark-Houwink-Sakurada equation is [η] = 1.16 × 10^?3 M?_n^0.52. The Huggins k′ value is found to be about 0.9 and the Flory-Huggins polymer-solvent interaction parameter, 0.49. A theoretically calculated value of K_θ is very close to the experimental one and it is for this reason and the observed μ and M?_n exponent values that 2M NaCNS at 25°C approaches being a θ solvent for PAG. A thermodynamic approach based on equilibrium swelling and modulus measurements indicates that a single thermally reversible crosslink in a gelatin gel involves numerous peptide backbone units, whereas in PAG gels a crosslink perhaps involves only one residue from each of two chains. These results complement the very high exothermic heat of gelation crosslinking, δH_c, for gelatin compared to PAG. ΔH_c has been measured on PAG samples of different DP and found to be independent of chain length. Similar measurements on acrylylglycinamide copolymers and terpolymers containing basic and acidic groups produce no change in δH_c so that coulombic forces do not appear to be significant. Data are also included relating to the density of PAG, its glass transition and thermal decomposition temperature, the tensile modulus of equilibrium-swelled PAG films in water and the chain-transfer constant of methanol with the acrylylglycinamide free radical.     

Synthesis of transition‐metal‐ion‐selective poly(N‐isopropylacrylamide) hydrogels by the incorporation of an Aza crown ether

A functionalized cyclam was synthesized by the attachment of a polymerizable acryloyl group to one of the four nitrogens on the cyclam molecule. The polymerization of the functionalized cyclam was performed with N‐isopropylacrylamide and N,N′‐methylene bisacrylamide, and the gels obtained were studied in the presence of different transition‐metal‐ion solutions. There was a drastic difference in the phase‐transition temperature (T_c) of the poly(N‐isopropylacrylamide) (PNIPAAm)/cyclam gel in comparison with the pure PNIPAAm gel. For the described system, a T_c shift of 15 °C was obtained. The presence of functionalized cyclam increased the hydrophilicity and T_c of the aforementioned polymer gels in deionized water (at pH 6) because of the presence of protonated amino moieties. The PNIPAAm/cyclam gels showed a dependence of the swelling behavior on pH. T_c of the pure PNIPAAm gel was weakly influenced by the presence of any transition‐metal ions, such as Cu²⁺, Ni²⁺, Zn²⁺, and Mn²⁺. The addition of Cu²⁺ or Ni²⁺ to the PNIPAAm/cyclam gel reduced T_c of the polymer gel, and a shift of approximately 12 °C was observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1594–1602, 2003     

Synthetic thermally reversible gel systems. VII

Polymethacrylylglycinamides (PMG), like polyacrylylglycinamides (PAG), form thermally reversible aqueous gels, but higher molecular weights and/or concentrations are required and the melting points of the gels are lower. The heats of crosslinking for aqueous PMG gels fall in the range of ?5 to ?10 kcal/mole of crosslinks, the same as for aqueous PAG gels, implying that the crosslinks are chemically similar. PMG and PAG are incompatible with each other but both are individually compatible with some types of gelatin. The solubilities of PMG and PAG are similar. Various reagents, however, affect PMG and PAG gels in quite different manners. Aqueous PMG solutions, just outside conditions required for gelation, are rheopectic. Intrinsic viscosities [η] of PMG in 2M NaCNS are about 2.5 times those in water. The Huggins' k′ value for PMG in 2M NaCNS has a value of 0.39–0.40, and both it and [η] are essentially temperature-independent over the range 25–45°C. In water at 25°C for PMG, k′ has an average value of about 1.4. With increasing temperature, for H₂O, there is a considerable increase in [η] which is accompanied by a decrease in the value of k′. Osmotic molecular weight measurements on unfractionated PMG in H₂O at 40°C yield π/c versus c plots having essentially zero slope, implying a value of close to zero for the second virial coefficient, a value of about 0.5 for the polymer–solvent interaction parameter, and a condition close to a θ condition. An approximate viscosity–M _n relationship for polydisperse PMG is [η]_{2M NaCNS, 25deg;C} = 1.7 × 10^?8 M _n^1.5. The low value of K and high value of the exponent do not result from large differences in polydispersity but rather from a stiff, rodlike configuration in solution. This steric hindrance to rotation also manifests itself in the extreme brittleness of PMG films and in a ΔH_p for homopolymerization of only ?6 kcal/-mole. The infrared spectra of MG monomer and PMG are recorded as well as the density and refractive index for PMG. PMG has a glass transition at 226°C by DTA and by TGA, thermal decomposition sets in at about 300°C. From copolymerization with acrylic acid, values of 1.66 and +0.06, respectively, were obtained for the resonance factor Q and the electrical factor e for MG monomer.     

Effects of hydroxy compounds on gel formation of gelatin

 Network formation of gelatin gel is known to consist of three-dimensionally cross-linked triple helices among polypeptide chains. The effects of added low molecular weight mono-ols, diols and polyols on the higher-order structure formation of gelatin chains were investigated using the following measurements: melting temperature, viscoelasticity and spin-lattice relaxation time (T ₁) of H¹⁷ ₂O of gels, and circular dichroism spectra of diluted gelatin solutions. Furthermore, hydration behaviors of these hydroxy compounds were evaluated from the dynamic hydration numbers (n _DHN) derived from T ₁ of H¹⁷ ₂O in the solutions. It was found that network structures of gelatin gels containing hydoxy compounds were influenced by the number and position of hydroxyl groups as well as the number of carbon atoms of these coexisting compounds. The effect of hydroxyl groups of hydroxy compounds was considered to stabilize the helices among gelatin chains. Especially, the addition of polyols with large number of hydroxyl groups increased the number of cross-linking junctions in the gel networks, which consist of the aggregation among the helices. On the contrary, the effect of carbon atoms of hydroxy compounds is to disturb the formation of the helices and the aggregation among the helices. Received: 18 April 1996/Accepted: 23 July 1996     

Effects of phenolic compounds on gelation behavior of gelatin gels

The effects of phenolic additives on the gelation behavior of gelatin gels were investigated using thermomechanical analysis (TMA) for study of gel‐melting temperature, dynamic mechanical analysis (DMA) for study of gel‐storage modulus and gel‐aging stability, viscometry for study of gelation time, and texture analyzer for study of gel strength and gel melting. Thermodynamically, the addition of 1,3‐benzenediol, 1,4‐benzenediol or 1,3,5‐benzenetriol favored the gelation process of gelatin solutions (increases in T_m and aging stability) due to the introduction of extra physical crosslinks among gelatin chains through hydrogen bonding, while the addition of 1,2‐benzenediol had a negative effect (decreases in T_m and aging stability) possibly due to intra‐hydrogen bonding of the additive molecule itself. All the phenolic compounds had little effect on gel moduli. Kinetically, the introduction of 1,2‐benzenediol or 1,4‐benzenediol slowed the gelation process, while introduction of catechin, a polyphenol, accelerated the first stage of the gelation process. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 224–231, 2001     

Temperature response of aqueous solutions of pyrene end‐labeled poly(N‐isopropylacrylamide)s probed by steady‐state and time‐resolved fluorescence

Aqueous solutions of a series of monodisperse poly(N‐isopropylacrylamide)s end‐labeled with n‐butyl‐1‐pyrene at one or both chain ends (Py_n‐PNIPAMs with n = 1 or 2) were studied by turbidimetry, light scattering, and fluorescence. For a given polymer concentration and heating rate, the cloud point (T_c) of an aqueous Py_n‐PNIPAM solution, determined by turbidimetry, was found to increase with the number‐average molecular weight (M_n) of the polymer. The steady‐state fluorescence spectra and time‐resolved fluorescence decays of Py_n‐PNIPAM aqueous solutions were analyzed and all parameters retrieved from these analyses were found to be affected as the solution temperature passed through T_c, the solution cloud point, and T_m, the temperature where dehydration of PNIPAM occurred. The trends obtained by fluorescence to characterize the aqueous Py_n‐PNIPAM solutions as a function of temperature were found to be consistent with the model proposed for telechelic PNIPAM by Koga et al. in 2006. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 308–318     

CURRENT TERTIARY OIL RECOVERY IN CHINA

We investigated the relationship between the macroscopic viscosity lpar;η_N ), determined by creep measurement, and the microscopic viscosity, estimated by rotational correlation time (τ_c) of spin label determined by ESR method, for wheat and potato starch gels. Both η_Nand τ_c. Of wheat starch gel increased linearly with an increase of starch concentration. Both η_N and τ_c of potato starch gel increased exponentially with an increase of starch concentration. The τ_c of wheat starch gel related linearly to the η_N of the gel at 30, 40 and 50°C. For potato starch gels, the τ_c.also related significantly to the η_N at 30, 40 and 50°C. The τ_c of free BrAcTEMPO was much smaller than that of spin-labeled AcTEMPO in wheat starch gel. It is concluded that the change in microscopic viscosity of starch gels agrees with their change in macroscopic viscosity.     

Novel Method of Producing Polymer Gels in Aqueous Solution Using UV Irradiation

Summary: We developed a novel method of producing polymer gels in aqueous solution using UV irradiation. Persulfates were effective photosensitive initiators of polymerization and/or gelation of acryloyl‐type monomers/polymers. The gelation was confirmed by an abrupt increase in light scattering intensity, 〈I(q)〉_T, at the gelation point. The gelation method entails significant advantages: it does not need any cross‐linkers, temperature control (heating), and additives except the persulfate.

The UV irradiation time dependence of light scattering intensity, 〈I(q)〉_T, for pre‐gel solutions containing N‐isopropylacrylamide (NIPAm) and/or ammonium persulfate (APS).     

Building Block approach to SiO2–ZrO2 porous materials†

(2‐Hydroxyethyl)trimethylammonium silicate, Si₈O₂₀[N(CH₃)₃(C₂H₄OH)]₈·nH₂O, was allowed to react with zirconium tetrakis(2,4‐pentanedionate) in methanol, resulting in gel formation. The gels were heat‐treated at 650–1000 °C in air. The product at 650 °C showed a specific surface area of 500 m² g⁻¹, and the average pore diameter was ca 4.3 nm, indicating the formation of a thermally stable mesoporous body. Gels with the same composition were also prepared by sol–gel processing using tetraethoxysilane as a silica source. The specific surface area of the product yielded by heating the gels at 650 °C was 425 m² g⁻¹ and the average pore diameter was ca 2.8 nm, which were lower than those of the product from the gels prepared with (2‐hydroxyethyl)trimethylammonium silicate. These differences have been attributed to the difference in nanostructure of the gels, caused by the structure of the silica sources and their polymerization behaviour. Copyright © 1999 John Wiley & Sons, Ltd.     

X-ray Photon Correlation Spectroscopy of Dynamics in Thermosensitive Gels

Summary : Temperature-sensitive hydrogels undergo a volume phase transition (VPT) when heated above a critical temperature T_c. For the poly(N-isopropyl acrylamide) (PNIPA)-water system, T_c. = 34 °C. Below T_c the gels are transparent and highly swollen. On warming above T_c they promptly turn white and start to deswell. The rate of deswelling, however, can be orders of magnitude slower than that of swelling below T_c. The unstable intermediate structure above T_c, can retain the solvent and conserve the sample volume for may days, even with millimetre-sized samples. Light scattering observations of the internal structure of these gels above T_c are precluded by their strong turbidity. Small angle X-ray scattering measurements (SAXS), on the other hand, are less subject to multiple scattering as X-rays penetrate more easily into the bulk material. Conventional (incoherent) SAXS observations reveal intense scattering from smooth internal water-polymer interfaces with an estimated surface area of about 7 m²/g in the swollen gel. The dynamics in the off-equilibrium high temperature state, investigated by X-ray photon correlation spectroscopy (XPCS), displays a relaxation rate that is linearly proportional to the wavevector q, rather than to q² as in diffusion processes. The physical origin of this relaxation is consistent with jamming, a phenomenon that is common in other disordered systems.     

Thermodynamic Studies of Bi-Univalent Electrolytes. VI. Thermodynamics of Cadmium Acetate from E. M. F. and Calorimetric Measurements

E. M. F. of the Cell, Cd-Hg (2-phase)/CdAc₂(m), Hg₂Ac₂(s)/Hg was measured at 20°, 25°, 30° and 40°C. The standard e. m. f. of the cell, Cd/CdAc₃(m), Hg₂Ac₂(c)/Hg was evaluated as E°=1.1500?11.09×10^?4T+1.06×10^?8T² The thermodynamic data of the reaction, Cd(c) + Hg₂Ac₂(c)=2Hg(l)+Cd⁺⁺(aq)+2Ac^?(aq) at 25°C were estimated as ΔF°=?42,139, ΔH°=?48,698 cal mole^?1 and ΔS°=?22.0 cal deg^?1 mole^?1 at 25°C. The thermodynamic data for the formation of Hg₂Ac₂(s) were evaluated as ΔF_f°=?202.3, ΔH_f°=?154.5 Kcal mole^?1 and S°=72.9 cal deg^?1 mole^?1. From measurements of the heats of solution of CdAc₂·2H₂O in aqueous solution, the relative partial molal enthalpies of cadmium acetate in aqueous solution were estimated.     

Behavior of a Metastable Gel of Sodium N‐Stearoyl‐l‐Glutamate/Water System

Gel formation was observed at 25°C in a mono sodium N‐stearoylglutamate (C18GS)/water system by quick cooling (quenching, 15°C/minute), whereas coagel was formed by slow cooling (annealing, 1°C/minute). Two kinds of phase transition temperatures, T_gel (coagel‐gel) and T_c (gel‐liquid crystal or micelle), were detected in the annealing system using a differential scanning calorimeter (DSC). On the other hand, only T_c was observed in the quenching system. Since the phase transition entropies at T_c in both the quenching and annealing systems are similar, both gels are considered to be in the same structure, and the gel observed in the quenching system at low temperature is in the metastable, supercooled state. Judging from the ¹H‐NMR data and microscopic observation, a homogenous gel is formed above 7 wt% of C18GS. With an increase in surfactant concentration, the thixotropic tendency of the gel increases due to the decrease in free‐water. Since it was difficult to show gel formation with the shorter chain homologs, C14GS and C12GS, the hydrocarbon chain length of the surfactant appears to be very important in the formation of a metastable, supercooled gel.     

Synthetic thermally reversible gel systems. V

Differential thermal analysis has been used to study the fusion of aqueous thermally reversible gels of gelatin and polyacrylylglycinamide (PAG). In the case of gelatin gels, endotherms close to the melting point are readily observed and these are sometimes preceeded by a small exothermic heat of gel reorganization. Calculations are presented to show that breaking of the gelatin gel network requires only a small fraction of the observed endothermic heat of fusion and that most of the heat is required for melting larger crystallites within gelatin aggregates and for perhaps a helix → coil transition. Failure to observe endotherms by DTA over the known temperature range of fusion of PAG gels is consistent with prior measurements and conclusions. The noncrystallinity of PAG gels and soluble aggregates together with a heat of crosslinking of only ?5 to ?10 kcal/mole of crosslinks places the heat of fusion of PAG gels outside the lower limits of DTA sensitivity.     

Multiple melting behavior of poly(butylene succinate). II. Thermal analysis of isothermal crystallization and melting process

The multiple melting behavior of poly(butylene succinate) (PBSu) was studied with differential scanning calorimetry (DSC). Three different PBSu resins, with molecular weights (MWs) of 1.1 × 10⁵, 1.8 × 10⁵, and 2.5 × 10⁵, were isothermally crystallized at various crystallization temperatures (T_c) ranging from 70 to 97.5 °C. The T_c dependence of crystallization half‐time (τ) was obtained. DSC melting curves for the isothermally crystallized samples were obtained at a heating rate of 10 K min⁻¹. Three endothermic peaks, an annealing peak, a low‐temperature peak L, and a high‐temperature peak H, and an exothermic peak located between peaks L and H clearly appeared in the DSC curve. In addition, an endothermic small peak S appeared at a lower temperature of peak H. Peak L increased with increasing T_c, whereas peak H decreased. The T_c dependence of the peak melting temperatures [T_m(L) and T_m(H)], recrystallization temperature (T_re), and heat of fusion (ΔH) was obtained. Their fitting curves were obtained as functions of T_c. T_m(L), T_re, and ΔH increased almost linearly with T_c, whereas T_m(H) was almost constant. The maximum rate of recrystallization occurred immediately after the melting. The mechanism of the multiple melting behavior is explained by the melt‐recrystallization model. The high MW samples showed similar T_c dependence of τ, and τ for the lowest MW sample was longer than that for the others. Peak L increased with MW, whereas peak H decreased. In spite of the difference of MW, T_m(L), T_m(H), and T_re almost coincided with each other at the same T_c. The ΔH values, that is crystallinity, for the highest MW sample were smaller than those for the other samples at the same T_c. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2039–2047, 2005     

Hydrogels from diacylphosphatidylcholine

The formation of hydrogels from diacylphosphatidylcholine (PC) and water/glycerol mixtures and the properties of the gels are reported. The gels are formed when L_α phases from the PC in the solvent mixtures are cooled from T >55 °C below the Krafft temperature of the PC (T _m ∼52 °C). The glycerol can also be replaced by other co-solvents like butylenglycol. Above T _m, the PC spontaneously forms L_α phases with multilamellar vesicles that show a strong stationary birefringence. On cooling below T_m, the L_α phases jellify to transparent gels. DSC measurements of the gels show that the PC molecules undergo a phase transition into the crystalline state. This transition does not seem to be accompanied by a change of the morphological structure of the liquid L_α phase. The hydrogels also have a stationary birefringence. The vesicles in the gels have been imaged by the CryoTEM method. The hydrogels are already formed with as little as 1% of PC in the mixed solvent. The rheological properties of the gels were determined from oscillating rheological measurements. Samples with 10% of PC have a storage modulus of >10,000 Pa.     

The effects of solvent type on the concentration dependence of the compression modulus of thermoreversible isotactic polystyrene gels

Solutions of isotactic polystyrene in either trans-decalin or 1-chlorodecane were transformed into gels by quenching from a high temperature (ca. 180°C) to ?20°C. The relaxation modulus in compression of these gels was measured over a range of concentrations of from 0.04 g/g to 0.40 g/g. At 22°C, the gels show a double logarithmic stress relaxation rate, m, which is higher than for PVC and gelatin gel systems. 120 s isochronal modulus concentration diagrams exhibit non-power law behavior, i.e., not only is the general trend such that the double logarithmic slope decreases with increasing concentration, but there are also regions in which abrupt changes in modulus occur over narrow ranges in concentrations. These features in the concentration dependence of the modulus are less pronounced than those found previously¹ in isotactic polystyrene/cis-decalin gels. The behavior is interpreted to be inconsistent with a fringed micelle picture of the gel structure. Preliminary results are reported indicating that polymer fraction and temperature of gel formation can significantly affect the modulus of the gels.     

DENSITY, EQUILIBRIUM HEAT OF FUSION AND EQUILIBRIUM MELTING TEMPERATURE OF NYLON 1010

The density, equilibrium heat of fusion and equilibrium melting temperature of Nylon 1010 were determined by means of infrared spectrum, differential scanning calorimetry, wide angle X-ray diffraction and density measurement techniques. According to Starkweatber' s method crystalline density ρ_c and amorphous density ρ_a were estimated to be 1.098 and 1.003 g/cm~3 respectively by extrapolating the straight lines of the IR absorbanee against density to zero intensity. Owing to the less intense in absorbance and less sensitive to the change in crystallinity of the amorphors band the thus obtained ρ_c was too low in value. Thereby the value of the ratio ρ_c /ρ_a is far less than generally accepted mean value for most crystalline polymers. Accordingly, traditional X-ray diffraction method was used through determining thc crystalline dimension(a=4.9, b=5.4, c=27.8, α=49°β=77.0°, γ=63.5°), and a rather correct value of ρ_c or the crystal density 1.13 g/cm~3 was obtained. The equilibrium heat of fusion △H_m~0 was estimated to be 244.0 J/g piotting △H_m 's of specimens with different crystallinity against their corre sponding specific volumes _(sp), and extrapolating to completely crystalline condition (_(sp)~c= 1/ρ_c) As to the equilibrium melting temperature T_m~0, because of the easiness of recrystallization of melt crystallized Nylon 1010 specimen, the well-known Hoffman's T_m-T_c method failed in determining this value and an usually rarely used Kamide double extrapolation method was adopted. The so obtained value of T_m~0 487 seems to be fairly reasonable.     

Which Polyesters Can Mimic Polyethylene?

Self‐metathesis of erucic acid by [(PCy₃)(η‐C‐C₃H₄N₂Mes₂)Cl₂Ru = CHPh] (Grubbs second‐ generation catalyst) followed by catalytic hydrogenation and purification via the ester yields 1,26‐hexacosanedioate (>99% purity). Polyesterification with 1,26‐hexacosanediol, generated from the diester, affords polyester‐26,26, which features a T_m of 114 °C (T_c = 92 °C, ΔH_m = 160 J g⁻¹). Ultralong‐chain model polyesters‐38,23 (T_m = 109 °C) and −44,23 (T_m = 111 °C), generated via multistep procedures including acyclic diene metathesis polymerization, underline that melting points of such aliphatic polyesters do not gradually increase with methylene sequence chain length. Available data suggest that to mimic linear polyethylenes thermal properties, even longer sequences, amounting to at least four times a fatty acid chain, fully incorporated in a linear fashion are required.     

Synthesis,swelling properties,and network structure of new stimuli‐responsive poly(N‐acryloyl‐N′‐ethyl piperazine‐co‐N‐isopropylacrylamide) hydrogels

Poly(N‐acryloyl‐N′‐ethyl piperazine‐co‐N‐isopropylacrylamide) hydrogels were prepared by thermal free‐radical copolymerization of N‐acryloyl‐N′‐ethyl piperazine (AcrNEP) and N‐isopropylacrylamide (NIPAM) in solution using N, N′‐methylene bisacrylamide as the crosslinking agent. The gels were responsive to changes in external stimuli such as pH and temperature. The pH and temperature responsive character of the gels was greatly dependent on the monomer content, namely AcrNEP and NIPAM, respectively. The gels swelled in acidic (pH 2) and de‐swelled in basic (pH 10) solutions with a response time of 60 min. With increase in temperature from 23 to 80 °C the swelling of the gels decreased continuously and this effect was different in acidic and basic solutions. The temperature dependence of equilibrium water content of the gels was evaluated by the Gibbs–Helmholtz equation. Detailed analysis of the swelling properties of these new gels in relation to molecular heterogeneity in acidic (pH 2) and basic (pH 10) solutions were performed. Water transport property of the gels was studied gravimetrically. In acidic solution, the diffusion process was non‐Fickian (anomalous) while in basic solution, the diffusion was quasi‐Fickian. The effect was more evident in solution of pH 2 than in pH 10. Various structural parameters of the gels such as number‐average molar mass between crosslink (M_c), the crosslink density (ρ_c), and the mesh size (ξ) were evaluated. The mesh sizes of the hydrogels were between 64 and 783 Å in the swollen state in acidic solution and 20 and 195 Å in the collapsed state in basic solution. The mesh size increased between three to four times during the pH‐dependent swelling process. The amount of unbound water (free water) and bound water of the gels was also evaluated using differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Effect of chain architecture on the phase transition of star and cyclic poly(N‐isopropylacrylamide) in water

The heat‐induced phase transition of aqueous solutions of Poly(N‐isopropylacrylamide) (PNIPAM) in water is examined for a four‐arm PNIPAM star (s‐PNIPAM), a cyclic PNIPAM (c‐PNIPAM), and their linear counterparts (l‐PNIPAM) in the case of polymers (1.0 g L^?1) of 12,700 g mol^?1 < M_n < 14,700 g mol^?1. Investigations by turbidity, high‐sensitivity differential scanning calorimetry (HS‐DSC), and light scattering (LS) indicate that the polymer architecture has a strong effect on the cloud point (T_c: decrease for s‐PNIPAM; increase for c‐PNIPAM), the phase transition enthalpy change (ΔH decrease for s‐PNIPAM and c‐PNIPAM), and the hydrodynamic radius of the aggregates formed above T_c (R_H: c‐PNIPAM < s‐PNIPAM < l‐PNIPAM). The properties of s‐PNIPAM are compared with those of previously reported PNIPAM star polymers (3 to 52 arms). The overall observations are described in terms of the arm molecular weight and the local chain density in the vicinity of the core of the star, by analogy with the model developed for PNIPAM brushes on nanoparticles or planar surfaces. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2059–2068.