Unexpected Molecular Weight Dependence to the Physical Aging of Thin Polystyrene Films Present at Ultra‐High Molecular Weights

The physical aging behavior, time‐dependent densification, of thin polystyrene (PS) films supported on silicon are investigated using ellipsometry for a large range of molecular weights (MWs) from M_w = 97 to 10,100 kg mol^?1. We report an unexpected MW dependence to the physical aging rate of h < 80‐nm thick films not present in bulk films, where samples made from ultra‐high MWs ≥ 6500 kg mol^?1 exhibit on average a 45% faster aging response at an aging temperature of 40 °C compared with equivalent films made from (merely) high MWs ≤ 3500 kg mol^?1. This MW‐dependent difference in physical aging response indicates that the breadth of the gradient in dynamics originating from the free surface in these thin films is diminished for films of ultra‐high MW PS. In contrast, measures of the film‐average glass transition temperature T _g(h) and effective average film density (molecular packing) show no corresponding change for the same range of film thicknesses, suggesting physical aging may be more sensitive to differences in dynamical gradients. These results contribute to growing literature reports signaling that chain connectivity and entropy play a subtle, but important role in how glassy dynamics are propagated from interfaces. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1224–1238     

Kinetics,polymer molecular weights,and microstructure in zirconocene‐catalyzed 1‐hexene polymerization

1‐Hexene was polymerized by rac‐(dimethylsilyl)bis(4,5,6,7‐tetrahydro‐1‐indenyl)zirconium dichloride catalyst and methylaluminoxane cocatalyst over the temperature range 0–100 °C. The polymerization rate, polymer molecular weight, and polymer microstructure (stereospecificity and regiospecificity) were studied as a function of the temperature and the concentrations of monomer, catalyst, and cocatalyst. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3802–3811, 2000     

Structural relaxation of stacked ultrathin polystyrene films

The T_g depression and kinetic behavior of stacked polystyrene ultrathin films is investigated by differential scanning calorimetry (DSC) and compared with the behavior of bulk polystyrene. The fictive temperature (T_f) was measured as a function of cooling rate and as a function of aging time for aging temperatures below the nominal glass transition temperature (T_g). The stacked ultrathin films show enthalpy overshoots in DSC heating scans which are reduced in height but occur over a broader temperature range relative to the bulk response for a given change in fictive temperature. The cooling rate dependence of the limiting fictive temperature, T_f′, is also found to be higher for the stacked ultrathin film samples; the result is that the magnitude of the T_g depression between the ultrathin film sample and the bulk is inversely related to the cooling rate. We also find that the rate of physical aging of the stacked ultrathin films is comparable with the bulk when aging is performed at the same distance from T_g; however, when conducted at the same aging temperature, the ultrathin film samples show accelerated physical aging, that is, a shorter time is required to reach equilibrium for the thin films due to their depressed T_g values. The smaller distance from T_g also results in a reduced logarithmic aging rate for the thin films compared with the bulk, although this is not indicative of longer relaxation times. The DSC heating curves obtained as a function of cooling rate and aging history are modeled using the Tool-Narayanaswamy-Moynihan model of structural recovery; the stacked ultrathin film samples show lower β values than the bulk, consistent with a broader distribution of relaxation times. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2741–2753, 2008     

Synthesis of poly(4‐vinylpyridine) by reverse atom transfer radical polymerization

Controlled radical polymerization of 4‐vinylpyridine (4VP) was achieved in a 50 vol % 1‐methyl‐2‐pyrrolidone/water solvent mixture using a 2,2′‐azobis(2,4‐dimethylpentanitrile) initiator and a CuCl₂/2,2′‐bipyridine catalyst–ligand complex, for an initial monomer concentration of [M]₀ = 2.32–3.24 M and a temperature range of 70–80 °C. Radical polymerization control was achieved at catalyst to initiator molar ratios in the range of 1.3:1 to 1.6:1. First‐order kinetics of the rate of polymerization (with respect to the monomer), linear increase of the number–average degree of polymerization with monomer conversion, and a polydispersity index in the range of 1.29–1.35 were indicative of controlled radical polymerization. The highest number–average degree of polymerization of 247 (number–average molecular weight = 26,000 g/mol) was achieved at a temperature of 70 °C, [M]₀ = 3.24 M and a catalyst to initiator molar ratio of 1.6:1. Over the temperature range studied (70–80 °C), the initiator efficiency increased from 50 to 64% whereas the apparent polymerization rate constant increased by about 60%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5748–5758, 2007     

Effects of the oriented mesophase on the cold crystallization of syndiotactic polystyrene and its blend with poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The effects of molecular orientation on the crystallization and polymorphic behaviors of syndiotactic polystyrene (sPS) and sPS/poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) blends were studied with wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry. The oriented amorphous films of sPS and sPS/PPO blends were crystallized under constraint at crystallization temperatures ranging from 140 to 240°C. The degree of crystallinity was lower in the cold‐crystallized oriented film than in the cold‐crystallized isotropic film. This was in contrast to the case of the cold crystallization of other polymers such as poly(ethylene terephthalate) and isotactic polystyrene, in which the molecular orientation induced crystallization and accelerated crystal growth. It was thought that the oriented mesophase was obtained in drawn films of sPS and that the crystallization of sPS was suppressed in that phase. The WAXD measurements showed that the crystal phase was more ordered in an sPS/PPO blend than in pure sPS under the same annealing conditions. The crystalline order recovered in the cold‐crystallized sPS/PPO blends in comparison with the cold‐crystallized pure sPS because of the decrease in the mesophase content. The crystal forms depended on the crystallization temperature, blend composition, and molecular orientation. Only the α′‐crystalline form was obtained in cold‐crystallized pure sPS, regardless of molecular orientation, whereas α′, α″, and β′ forms coexisted in the cold‐crystallized sPS/PPO blends prepared at higher crystallization temperatures (200–240°C). The β′‐form content was much lower in the oriented sPS/PPO blend than in the isotropic blend sample at the same temperature and composition. It was concluded that the oriented mesophase suppressed the crystallization of the stable β′ form more than that of the metastable α′ and α″ forms during the cold crystallization of sPS/PPO blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1665–1675, 2003     

Copolymerization of methyl methacrylate with lauryl methacrylate using group transfer polymerization

The syntheses of random and block copolymers (using sequential monomer addition) of methyl methacrylate (MMA) and lauryl methacrylate (LMA) have been investigated by group transfer polymerization (GTP) over a wide composition range using tetrabutylammonium bibenzoate (TBABB) as catalyst and 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene (MTS) as initiator in tetrahydrofuran (THF) at room temperature. The absolute molecular weight of the copolymers were determined by SEC-MALLS. The observed molecular weights were generally higher than the calculated molecular weights. However, the molecular weight distributions were very narrow (1.02–1.1). Use of trimethylsilyl benzoate as a “livingness enhancer” improved the livingness of the first block (PLMA) and block copolymers with no detectable contamination of homopolymer. Statistical copolymers of MMA and LMA were prepared, and the reactivity ratios of the two monomers under the defined conditions were determined. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1999–2007, 1997     

Thermosensitive sol–gel transition behaviors of poly(ethylene oxide)/aliphatic polyester/poly(ethylene oxide) aqueous solutions

The thermoreversible gelation of Pluronic [poly(ethylene oxide) (PEO)–polypropylene oxide (PPO)–PEO] aqueous solutions originates from micelle formation and micelle volume changes due to PEO–water and PPO–water lower critical solution temperature behavior. The micelle volume fraction is known to dominate the sol–gel transition behavior of Pluronic aqueous solutions. Triblock copolymers of PEO and aliphatic polyesters, instead of PPO, were prepared by hexamethylene diisocyanate coupling and dicyclohexyl carbodiimide coupling. Through changes in the molecular weight and hydrophobicity of the polyester middle block, the hydrophobic–hydrophilic balance of each block was systematically controlled. The following aliphatic polyesters were used: poly(hexamethylene adipate) (PHA), poly(ethylene adipate) (PEA), and poly(ethylene succinate) (PESc). With the hydrophobicity and molecular weight of the middle block increasing, the critical micelle concentration at the same critical micelle temperature decreased, and the absolute value of the micellization free energy increased. The micelle size was rather insensitive to temperature but slightly decreased with increasing temperature. PEO–PHA–PEO and PEO–PEA–PEO triblock copolymers needed high polymer concentrations to form gels. This was ascribed to the tight aggregation of PHA and PEA chains in the micelle core due to strong hydrophobic interactions, which induced the contraction of the micelle core. However, because of the relatively hydrophilic core, a PEO–PESc–PEO aqueous solution showed gelation at a low polymer concentration. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 772–784, 2004     

Stereocomplex formation between enantiomeric poly(α‐methyl‐α‐ethyl‐β‐propiolactones): Effect of molecular weight

Optically pure S(?) and R(+)‐poly(α‐methyl‐α‐ethyl‐β‐propiolactones) (PMEPLs) of controlled low molecular weights were synthesized by anionic polymerization of the corresponding optically active monomers, and characterized using gel permeation chromatography, Maldi‐TOF mass spectrometry, and NMR spectroscopy. Blends of PMEPLs of opposite configurations and different molecular weights were investigated. All blends lead to the formation of a stereocomplex and its crystallization prevails over a wide range of mixing ratios. The stereocomplex melts 30–40 °C above that of the corresponding pure polymers, depending on the molecular weight; pairs of polymers having similar molecular weights exhibit the highest melting temperatures and enthalpies of fusion. Finally, when the stereocomplex is dispersed in a PMEPL matrix, it acts as a very effective nucleation agent for the crystallization of the polymer in excess. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2380–2389, 2007     

Molecular weight dependency of crystallization and melting behavior of β‐nucleated isotactic polypropylene

Compounds of isotactic polypropylene (iPP) and β‐nucleating agent were used to investigate the relationship between the development of β phase and molecular weight in iPP under quiescent crystallization conditions by using wide angle X‐ray diffraction and differential scanning calorimetry techniques. In all cases, the dependency of the formation of β phase in iPP on molecular weight of iPP at a defined crystallization temperature range was found. The iPP with high molecular weight possessed a wide range of crystallization temperature in inducing rich β phase. However, poor or even no β phase was obtained for the samples with low molecular weight in the same range. In addition, an upper critical crystallization temperature of producing dominant β phase was found at 125 °C. Beyond this temperature, a phenomenon of prevailing α phase became obvious. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1301–1308     

Well‐controlled polymerization of 2‐azidoethyl methacrylate at near room temperature and click functionalization

A functional monomer with a pendant azide moiety, 2‐azidoethyl methacrylate (AzMA), was polymerized via reversible addition‐fragmentation chain transfer (RAFT) polymerization with excellent control over the molecular weight distribution (PDI = 1.05–1.15). The subsequent copper‐catalyzed Huisgen 1,3‐dipolar cycloadditions of phenyl acetylene with polyAzMA was achieved at room temperature with high conversion. The resulting functional polymer exhibited identical ¹H NMR and IR spectra with the polymer of the same molecular structure but prepared by a prefunctionalization approach, confirming the retention of the azide side chains during the RAFT polymerization of AzMA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4300–4308, 2007     

Isothermal and nonisothermal crystallization kinetics of poly(propylene terephthalate)

The kinetics of crystallization of poly(propylene terephthalate) (PPT) samples of different molecular weights were studied under both isothermal and nonisothermal conditions. The Avrami and Lauritzen–Hoffmann treatments were applied to evaluate kinetic parameters of PPT isothermal crystallization. It was found that crystallization is faster for low‐molecular‐weight samples. The modified Avrami equation, and the combined Avrami–Ozawa method were found to successfully describe the nonisothermal crystallization process. Also, the analysis of Lauritzen–Hoffmmann was tested and it resulted in values close to those obtained with isothermal crystallization data. The nonisothermal kinetic data were corrected for the effect of the temperature lag and shifted alone with the isothermal kinetic data to obtain a single master curve, according to the method of Chan and Isayev, testifying to the consistency between the isothermal and corrected nonisothermal data. A new method for ranking of polymers, referring to the crystallization rates, was also introduced. This involved a new index that combines the maximum crystallization rate observed during cooling with the average crystallization rates over the temperature range of the crystallization peak. Furthermore, the effective energy barrier of the dynamic process was evaluated with the isoconversional methods of Flynn and Friedmann. It was found that the energy barrier is lower for the low‐molecular‐weight PPT. The effect of the catalyst remnants on the crystallization kinetics was also investigated and it was found that this is significant only for low‐molecular‐weight samples. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3775–3796, 2004     

Synthesis of fluorene‐based high performance polymers. I. Poly(arylene thioether)s with excellent solubility and high refractive index

Several poly(arylene thioether)s ( PTEs ) containing a fluorene moiety were synthesized by the polycondensation of masked dithiols such as 9,9‐bis(4‐(N,N‐dimethyl‐S‐carbamoyl)phenyl)fluorene and various difluoroarenes. All PTEs were obtained in quantitative yields. The PTEs showed good thermal stability: the 10% weight loss temperature was over 480 °C under both nitrogen and air atmosphere by TGA, and glass temperature was within a range of 204–275 °C by DSC. Most PTEs exhibited remarkably high refractive index values in a range of 1.66–1.72 at 589 nm, whereas they had a very low degree of birefringence properties. Furthermore, the PTEs showed high solubility in ordinary organic solvents such as chloroform, N‐methylpyrrolidone, and tetrahydrofuran. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3073–3082, 2007     

Poly(L‐lysine) and clay nanocomposite with desired matrix secondary structure: Effects of polypeptide molecular weight

Nanocomposites (NC) were formed using cationic poly(L ‐lysine) (PLL), a semicrystalline polypeptide, that was reinforced by sodium montmorillonite (MMT) clay via solution intercalation technique. By varying solution conditions such as pH, temperature, and polypeptide concentration in the presence of clay platelets, the secondary structure of PLL was controllably altered into α‐helical, β‐sheet, and random coil. The high molecular weight polypeptide shows a strong propensity to fold into the β‐sheet structure when cast as films, irrespective of the initial secondary structure in solution. Nanocomposite local morphology confirms intercalated MMT platelets with PLL over a wide range of compositions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 239–252, 2007.     

Molecular modeling of cellulose in amorphous state. III. An innovative elastomeric crosslink system

The flexibility of molecular structures of rubber materials was evaluated using molecular modeling techniques to develop new crosslink agents which improve deformation recovery of cellulose without significant loss of the mechanical strength. Among the studied structures Poly(propylene oxide) (PPO) pentamer appears to be the most flexible and coiled one. Our calculation results showed that, cellulose crosslinked with PPO pentamers had similar deformation recovery to that crosslinked with DMDHEU. No conformation transitions were observed in these crosslinks when cellulose models were extended to 15% strain, which is consistent with the previous result that conformation transitions in crosslinks should be avoided upon extension to achieve a good recovery on crosslinked cellulose. In addition, PPO crosslinks did not significantly affect the breaking strain of cellulose based upon the cavity volume calculations, and they helped to remove the stress concentration among cellulose chains as suggested by the results of hydrogen bonding analysis. Thus, breaking strength of cellulose might not be significantly affected by PPO crosslinks as well. The preliminary experimental results confirmed above observations. Therefore, PPO pentamer appears to be a promising elastomeric backbone structure of crosslinking agents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1821–1833, 2007     

Properties and morphology of poly(L-lactide). II. Hydrolysis in alkaline solution

Hydrolysis of poly(L -lactide) (PLLA) films in 0.01N NaOH at 37°C was investigated by gel permeation chromatography, differential scanning calorimetry, scanning electron microscopy, and polarizing optical microscopy. The change in molecular weight distribution and surface morphology of PLLA films during hydrolysis revealed that PLLA film hydrolysis in dilute alkaline solution proceeded mainly via the surface erosion mechanism. An insignificant dependence of the rate of weight loss per unit surface area on the PLLA film thickness also supported this conclusion. Etching of the outside of PLLA spherulites resulted in preferred hydrolysis of PLLA chains in the amorphous region. The disorientation of lamella and inhomogeneous erosion in the spherulites implied that hydrolysis of PLLA chains occurred predominantly in the amorphous region between the crystalline regions in the spherulites. The rate of weight loss per unit surface area decreased linearly with the increase in the initial crystallinity of PLLA film, while the radius of spherulites had practically no significant effect on the hydrolysis of PLLA film. The specific low molecular weight of PLLA chains produced by hydrolysis increased with the rise in annealing temperature of the PLLA film, suggesting that the PLLA chains released were the component of one fold in the crystalline region. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 59–66, 1998     

Synthesis of novel branched ethylene/cyclopentene copolymers with only cis‐1,3‐enchained cyclopentene units using α‐diimine nickel(II) complexes in the presence of methylaluminoxane

The copolymerization of ethylene with cyclopentene catalyzed by three α‐diimine nickel(II) complexes in the presence of methylaluminoxane (MAO) was investigated. High‐molecular‐weight branched ethylene/cyclopentene copolymers with only cis‐1,3‐enchained cyclopentene units, which has not been reported previously, were obtained. The catalytic activity, cyclopentene incorporation, copolymer molecular weight, and molecular‐weight distribution could be controlled over a wide range through the variation of the catalyst structure and polymerization conditions, including cyclopentene concentration in the feed and polymerization temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2186–2192, 2008     

Synthesis and characterization of a fluorinated polyanhydride

A fluorinated aromatic polyanhydride ( B ) was synthesized from the melt condensation of mixed anhydrides of 4,4′‐(hexafluoroisopropylidene)bis benzoic acid. Although the mixed anhydride from acetic anhydride yielded only a mixture of oligomers (weight‐average molecular weight < 2000), higher weight‐average molecular weight materials in the range of 15,000–18,000 were obtained with trifluoroacetic anhydride. Polymer B was soluble in chloroform and tetrahydrofuran, had a relatively high glass‐transition temperature of 176 °C with no melting point detected to 310 °C, and showed excellent thermal stability (5% weight loss observed at 380 °C by thermogravimetric analysis). The hydrolytic degradation of the fluorinated polyanhydride in a 0.1 M phosphate buffer of pH 7.4 at 37 °C was initially zero‐order, with 35% degradation occurring in 10 days. Loss of film integrity following that led to accelerated degradation, and almost complete dissolution was observed by the 16th day. The stability of the fluorinated polyanhydride in the solid state and in the solvent tetrahydrofuran was also evaluated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3027–3036, 2002     

Nonisothermal crystallization and melting behavior of a luminescent conjugated polymer,poly(9,9‐dihexylfluorene‐alt‐co‐2,5‐didecyloxy‐1,4‐phenylene)

The nonisothermal crystallization kinetics of a luminescent conjugated polymer, poly(9,9‐dihexylfluorene‐alt‐co‐2,5‐didecyloxy‐1,4‐phenylene) (PF6OC10) with three different molecular weights was investigated by differential scanning calorimetry under different cooling rates from the melt. With increasing molecular weight of PF6OC10, the temperature range of crystallization peak steadily became narrower and shifted to higher temperature region and the crystallization rate increased. It was found that the Ozawa method failed to describe the nonisothermal crystallization behavior of PF6OC10. Although the Avrami method did not effectively describe the nonisothermal crystallization kinetics of PF6OC10 for overall process, it was valid for describing the early stage of crystallization with an Avrami exponent n of about 3. The combined method proposed in our previous report was able to satisfactorily describe the nonisothermal crystallization behavior of PF6OC10. The crystallization activation energies determined by Kissinger, Takhor, and Augis‐Bennett models were comparable. The melting temperature of PF6OC10 increased with increasing molecular weight. For low‐molecular‐weight sample, PF6OC10 showed the characteristic of double melting phenomenon. The interval between the two melting peaks decreased with increasing molecular weight, and only one melting peak was observed for the high‐molecular‐weight sample. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 976–987, 2007     

Viscometric properties of dilute polystyrene/dioctyl phthalate solutions

We report viscometric data collected in a Couette rheometry on dilute, single‐solvent polystyrene (PS)/dioctyl phthalate (DOP) solutions over a variety of polymer molecular weights (5.5 × 10⁵ ≤ M_w ≤ 3.0 × 10⁶ Da) and system temperatures (288 K ≤ T ≤ 318 K). In view of the essential viscometric features, the current data may be classified into three categories: The first concerns all the investigated solutions at low shear rates, where the solution properties are found to agree excellently with the Zimm model predictions. The second includes all sample solutions, except for high‐molecular‐weight PS samples (M_w ≥ 2.0 × 10⁶ Da), where excellent time–temperature superposition is observed for the steady‐state polymer viscosity at constant polymer molecular weights. No similar superposition applies at a constant temperature but varied polymer molecular weights, however. The third appears to be characteristic of dilute high‐molecular‐weight polymer solutions, for which the effects of temperature on the viscosity curve are further complicated at high shear rates. The implications concerning the relative importance of hydrodynamic interactions, segmental interactions, and chain extensibility with increasing polymer molecular weight, system temperature, and shear rate are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 787–794, 2006     

Vesicular and tubular structures prepared from self‐assembly of novel amphiphilic ABA triblock copolymers in aqueous solutions

A kind of novel soft amphiphilic ABA triblock copolymers, poly(L ‐lysine)‐b‐poly(tetrahydrofuran)‐b‐poly(L ‐lysine), was synthesized by the anionic ring‐opening polymerization of ε‐benzyloxycarbonyl‐L ‐lysine N‐carboxyanhydride using amine‐terminated poly(tetrahydrofuran) as a macroinitiator and subsequent removal of the protecting group. The resulting copolymers possessing a nearly symmetrical and narrow molecular weight distribution were dissolved in water at an appropriate concentration range at room temperature to yield vesicles as confirmed by using negative stain TEM and DLS. Meanwhile, nanotubes were obtained as the result of the conjunction of vesicles by reducing the medium temperature as evidenced by TEM. The effect of pH and salt concentration variations on the self‐assembly behavior was also examined. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1042–1050, 2008