The dependence of the glass transition temperature of poly(N-vinylcarbazole) upon steric microstructure and molecular weight

Poly(N-vinylcarbazole) (PVK) samples were found to exhibit up to three glass transition temperatures T_g, corresponding to the whole chain and the syndiotactic and isotactic stereoblocks. An increasing tendency to multiple T_gs, and hence to phase separation, was observed with increasing isotacticity. Limiting values at infinite molecular weight for syndiotactic and isotactic PVK were obtained from correlations of the T_gs corresponding to the syndiotactic and isotactic stereoblocks with their respective average stereoblock lengths derived from ¹³C NMR measurements. They were found to be 549 and 399 K, respectively. The conventional T_g for PVK was found to exhibit the following dependence upon the syndiotactic dyad mole fraction X_s: The molecular weight dependences of the conventional T_gs for several fractionated PVK samples obeyed a Fox–Flory-type relation with values of ?dT_g/d(1/M) varying between 7.6 × 10³ for isotactic PVK and 2.7 × 10⁵ for Luvican M 170.     

Thermal and dynamic mechanical relaxation behavior of stereoregular poly(2-hydroxyethyl methacrylate)

Thermal, dynamic mechanical, and dielectric relaxation techniques were used to determine the relaxation behavior of isotactic and syndiotactic poly(2-hydroxyethyl methacrylate) (pHEMA). Activation energies E_a were determined for the dielectric γ relaxation and compared with those of poly(2-methoxyethyl methacrylate) (pMEMA) to determine the influence of hydrogen bonding on side-chain relaxation processes. No difference in E_a was observed between syndiotactic pHEMA and atactic (predominantly syndiotactic) pMEMA. Isotactic pHEMA, however, had E_a + 1 kcal/mole higher than that of syndiotactic pHEMA. This was attributed to improved side-chain packing in the isotactic polymer.     

Dielectric properties of stereoregular poly(methyl methacrylates)

To obtain more useful information about the effect of the degree of stereoregularity on the motion of the polymer chain, the dielectric and dilatometric measurements were made for a series of stereoregular poly(methyl methacrylates) (PMMA). The α- and β-absorptions were observed in each sample, of which the dielectric behaviors of the α-process are discussed. The temperature dependence of the relaxation time of the α-process was sufficiently represented by the WLF equation and the resulting values of the parameters f_g and B in the modified WLF equation were found smaller for isotactic-rich PMMA than those values for syndiotactic PMMA. It may be deduced from these results that the chain mobility of the isotactic PMMA is larger than that of the syndiotactic. The dielectric increment of the α-process in the isotactic PMMA is much larger than that in the syndiotactic PMMA, increasing rapidly with temperature, and taking its maximum in the temperature range of 55 to 60°C. The dielectric transition was clearly observed in the case of isotactic-rich PMMA.     

Physical aging of poly(ether sulfone)-modified epoxy resin

The physical aging process of 4,4′-diaminodiphenylsulfone (DDS) cured diglycidyl ether bisphenol-A (DGEBA) blended with poly(ether sulfone) (PES) was studied by differential scanning calorimetry (DSC) at four aging temperatures between T_g-50°C and T_g-10°C. At aging temperatures between T_g-50 and T_g-30°C, the experimental results of epoxy resin blended with 20 wt% of PES showed two enthalpy relaxation processes. One relaxation process was due to the physical aging of PES, the other relaxation process was due to the physical aging of epoxy resin. The distribution of enthalpy relaxation process due to physical aging of epoxy resin in the blend was broader and the characteristic relaxation time shorter than those of pure epoxy resin at the above aging temperatures (between T_g-50 and T_g-30°C). At an aging temperature between T_g-30 and T_g-10°C, only one enthalpy relaxation process was found for the epoxy resin blended with PES, the relaxation process was similar to that of pure epoxy resin. The enthalpy relaxation process due to the physical aging of PES in the epoxy matrix was similar to that of pure PES at aging temperatures between T_g-50 and T_g-10°C. © 1997 John Wiley & Sons, Inc.     

Observation of pentads in deuterated polyacrylonitrile by NMR spectroscopy

The deuterium-decoupled methine proton spectra of polyacrylonitrile-β,β-d₂ were measured at 156°C in dimethylsulfoxide-d₆ solution. Splittings of triad peaks caused by pentad sequences were observed. The isotactic triad resonance was resolved into three peaks and the heterotactic resonance into two peaks, while the syndiotactic resonance was unresolved or resolved into three peaks. The splittings were assigned by comparing the probability of each pentad sequence with observed intensities. The pentad signal shifted to the higher magnetic field with increasing number of meso configurations as neighbors of the central triad. It was observed that the pentad of atactic polyacrylonitrile-β,β-d₂ obeyed Bernoullian statistics but that of isotactic polymer obtained by γ-ray irradiation of the canal complex seemingly obeyed first-order Markov statistics.     

Glass transition temperatures of stereoblock,isotactic and atactic polypropylenes of various chain lengths

The effect of sample molecular weight on the glass transition temperature has been examined for isotactic, stereoblock and atactic polypropylene samples. Asymptotic values of T₉ (∞) (isotactic) = 272°K, T₉ (∞) (atactic) = 266°K, and T_g (∞) (stereoblock) = 266°K were found. Deviation from T_g (∞) was observed when M?_n was below 10⁴; the dependence of T_g on M?_n has been discussed in relation to the Gibbs-DiMarzio treatment of the glass transition. The possible effects of both tacticity and crystallinity on T_g were examined; comparison of the data obtained with those of other workers was made. It was concluded that molecular order in polypropylene samples could affect T_g significantly and that this was particularly obvious in short chain stereoblock fractions.     

Comments on “some evidence against the existence of the liquid-liquid transition. IV. The temperature dependence of shear viscosity”

A formal definition of T_LL as a function of M?ⁿ for polystyrene was prepared with literature T_LL values from torsional braid analysis (TBA), differential scanning calorimetry (DSC), and zero-shear melt viscosity η₀. Data from six authors using anionically prepared PS and blends thereof were involved. The resultant linear least-squares regression line, T_LL(°C) = 148.5 ? 11.487 × 10⁴M? [standard error in T_LL (calculated) 4.056 K, correlation coefficient R² = 0.9534] is considered valid from M?_n = 2000 to the entanglement molecular weight M_c = 35,000. The “best” T_LL values reported by Orbon and Plazek from double Arrhenius plots are well below this line for M?_v = 47,000, 16,400, 3400, and above it for M?_v = 1100. These best T_LL values are artifacts arising from no or insufficient data points above or below T_LL and/or too many data points near T_g. The associated high enthalpies of activation which they report confirm this diagnosis. The fact that these artificial T_LL values tend to disappear when checked by the three-parameter Vogel equation, logη = logA + B exp[(T ? T_∞)^?1], has no relevance to the controversy concerning the existence and meaning of T_LL. The claim by Orbon and Plazek that T_LL values obtained by TBA, DSC, and melt viscosity are all artifacts of the individual methods by which they were obtained is inconsistent with the excellent master plot which they generate. Alternative plotting devices which reveal T_LL > T_g from η₀ vs. T^?1 data, as developed by van Krevelen and Hoftyzer and by Utracki and Simha (not previously considered by either party), are reviewed. A statistical examination of the nature of the Vogel–Fulcher–Tammann–Hesse equation, based on synthetic data, is presented. Evidence for T_LL in atactic polypropylene is offered based on published data by Plazek and Plazek. T_LL is considered to possess both relaxational and quasiequilibrium attributes, just as T_g does.     

Conformations produced by interactions of the side chains in poly(silylenemethylene) with the repeating sequence [Si(CH3)R?CH2]x [R = ?O(CH2)3OC6H4C6H5]

A coarse-grained model has been developed for asymmetrically substituted poly(silylenemethylene)s in which the side chain is a flexible spacer terminated by a biphenyl unit. Each monomer unit is represented by four coarse-grained beads that interact via a Lennard–Jones potential and are subject to the first- and second-order interactions deduced from the atomistically detailed model. Metropolis Monte Carlo simulations were performed for isolated syndiotactic, isotactic, and atactic chains. Snapshots from the equilibrated coarse-grained chain on the discrete space of a high coordination lattice were reverse-mapped to atomistically detailed structures in continuous space. At 373 K, the chains were disordered independent of the stereochemical composition. The occupancy of bond pairs depended on the stereochemical composition, with the trans-gauche (tg) sequence being favored by the isotactic chain. When the simulation was performed with the backbone constrained to specific periodic structures, the g helix was the lowest energy structure for either the atactic or isotactic chains. For the syndiotactic chain, the g and gt helices were favored. The appearance of the g helix as the favored periodic structure of the isolated chain was consistent with the chain conformation reported previously for the smectic phase of this polymer in the bulk state. The g helix was disrupted when the backbone was allowed to access nonhelical conformations, even though these conformations may have been slightly higher in energy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 886–896, 2005     

A–B–A stereoblock copolymers of N‐isopropylacrylamide

A–B–A stereoblock polymers with atactic poly(N‐isopropylacrylamide) (PNIPAM) as a hydrophilic block (either A or B) and a non‐water‐soluble block consisting of isotactic PNIPAM were synthesized using reversible addition fragmentation chain transfer (RAFT) polymerizations. Yttrium trifluoromethanesulfonate was used in the tacticity control, and bifunctional S,S′‐bis(α,α′‐dimethyl‐α″‐acetic acid)‐trithiocarbonate (BDAT) was utilized as a RAFT agent. Chain structures of the A–B–A stereoblock copolymers were determined using ¹H NMR, SEC, and MALDI‐TOF mass spectrometry. BDAT proved to be an efficient RAFT agent in the controlled synthesis of stereoregular PNIPAM, and both atactic and isotactic PNIPAM were successfully used as macro RAFT agents. The glass transition temperatures (T_g) of the resulting polymers were measured by differential scanning calorimetry. We found that the T_g of isotactic PNIPAM is molecular weight dependent and varies in the present case between 115 and 158 °C. Stereoblock copolymers show only one T_g, indicating the miscibility of the blocks. Correspondingly, the T_g may be varied by varying the mutual lengths of the A and B blocks. The phase separation of aqueous solutions upon increasing temperature is strongly affected by the isotactic blocks. At a fixed concentration (5 mg/mL), an increase of the isotacticity of the stereoblock copolymers decreases the demixing temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 38–46, 2008     

Dependence of the glass transition temperature of poly(methyl methacrylate) on tacticity and molecular weight

The preparation of five samples of poly(methyl methacrylate) covering a wide range of tacticity and their electron irradiation to produce series of varying molecular weight are described. The glass transition temperature T_g of each polymer was determined by DTA techniques. Plots of T_g and the reciprocal of the molecular weight are well fitted in every case by a straight line. The data are also fitted to the Gibbs-DiMarzio theory and the values of the energy and free-volume parameters obtained are discussed. A method of estimating T_g of pure syndiotactic poly(methyl methacrylate) by extrapolation is presented, the value obtained being 160°C.     

Cooperative motions in PVC studied by thermally stimulated currents: Comparison with A.C. dielectric derivative analysis

The thermally stimulated current–thermal sampling (TSC–TS) technique was used to study the broadened glass transition in conventional “atactic” poly(vinyl chloride), PVC. The activated parameters obtained from the TSC–TS data, mainly the apparent activation energy (E_a), characterize the breadth of glass transitions in a very sensitive way. These results are compared with those values of E_a obtained from the literature, using a recently proposed method of analyzing a.c. dielectric constants and their derivatives, over the temperature range of −100–130°C. Both techniques detect weak cooperative glass transition-like relaxations well below the main glass transition of ca. 80°C. As is the case with “atactic” PMMA, the data suggest that compositional heterogeneity related to a small fraction of predominantly isotactic sequences contribute to the broad glass transition extending ca. 60°C below the main glass transition in atactic PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 913–918, 1998     

Dependence of the glass transition temperature of poly (methyl methacrylates) on their tacticity

The specific isobaric heat capacities of poly (methylmethacrylates) (PMMA) having various tacticities were measured by the DSC method within a broad range of temperatures including the glass transition. Glasses with uniform thermal history were used in the measurements and the data were treated by employing a procedure which provided the thermodynamic T_g independent of the experimental conditions. The semiquantitative validity of Boyer's empirical relationT _g ×c_p=const. was confirmed; also it was found that within the limits of experimental accuracy the c_p,g values at 298 K andC _p,l values at 400 K are independent of the tacticity of the sample.Using the data thus measured and linearized equations representing the dependence ofT _g on the content of iso-, syndio- and heterotriads, the T_g values of pure isotactic PMMA and pure syndiotactic PMMA were found to be respectively 315 K and 397 K.Dedicated to Professor Dr. F. H. Müller.     

Synthesis of isotactic,syndiotactic, and heterotactic poly(tributyltin methacrylate) and poly(tributyltin methacrylate-co-styrene)

Pure isotactic and enriched syndiotactic poly(tributyltin methacrylate) were synthesized by the reaction of the respective poly(methacrylic acid) with tributyltin oxide. The heterotactic polymer was prepared in a similar manner and from free radical initiated (AIBN or BPO) polymerization of tributyltin methacrylate. In each case, polymer configuration was confirmed by ¹H-NMR of the hydrolyzed/esterfied product. The relatively large ¹¹⁹Sn-NMR linewidth of the isotactic tributyltin containing polymer suggests an intra-molecular exchange of the pendant tin groups. T_g, T_d, and M _v data are also reported. Poly(tributyltinmethacrylate-co-styrene) was prepared by free radical polymerization and reactivity ratios [r(styrene) = 0.51, r(TBTM) = 0.49] and Q-e values for TBTM (0.78, 0.38) were determined.     

Thermally stimulated current studies of thermotropic polyesters with polymethylene spacers (I): The glass transition and relaxation behavior of anisotropic and isotropic glasses

Thermally stimulated current (TSC) and relaxation map analysis (RMA) were used to study the glass transitions and relaxation phenomena of the anisotropic and isotropic glasses for the semiflexible polyesters with various polymethylene spacers (n = 7 ˜ 10). TSC analysis indicated that the glass transition temperatures (T_g) of polymers at around 40 ˜ 50°C exhibited an apparent even-odd behavior not only for the anisotropic glasses but also for the isotropic glasses. The T_g of the isotropic glass for the polymer with even n value was observed to be higher than those for the two neighboring polymers with odd n values. The anisotropic glass for the polymer with even n value had a lower T_g than those for the two neighboring polymers with odd n values. The lower value was attributed to the configuration and orientation effects on the behavior of polarization. RMA revealed that the relaxation modes of the investigated polymers were also influenced by the configuration and orientation effects. The dipolar relaxation of the anisotropic glass for the polymer with odd n value occurred at a higher temperature and had a lower entropy (enthalpy) of activation than that of the isotropic glass for the same polymer due to the orientation effect. However, an inverse relation was found to occur for the polymer with even n value, which came from the trans configuration of the even polymethylene spacers. Finally, the thermokinetic properties evaluated by RMA (e.g., the final state after depolarization) correlated quite well with the results obtained by TSC. © 1995 John Wiley & Sons, Inc.     

Carbon-13 NMR spin-lattice relaxation times of isotactic and syndiotactic sequences in amorphous polypropylene

Spin-lattice relaxation times (T₁) for methyl, methylene, and methine carbons in an amorphous polypropylene have been measured as a function of temperature from 46 to 138°C. The carbons from isotactic sequences characteristically exhibited the longest T₁'s of those observed. The T₁ differences increased with temperature with the largest difference occuring for methine carbons where a 32% difference was observed. Activation energies were determined for the motional processes affecting T₁'s for isotactic and syndiotactic sequences with essentially no dependence upon configuration noted.     

Solid matrix polymerization and stereoisomeric complexes of poly(methyl methacrylate)

The polymerization of methyl methacrylate within solid matrices of stereoregular poly(methyl methacrylate) has been studied by proton NMR and wide angle X-ray diffraction. The semi-crystalline isotactic (i-) PMMA matrix was synthesized in the laboratory by anionic polymerization initiated by phenylmagnesium bromide, and the syndiotactic (s-) PMMA matrix was synthesized through a Ziegler–Natta reaction. Matrix polymerization of the monomer was initiated through the redox activation of benzoyl peroxide with N,N-dimethyl-p-toluidine. NMR measurements of triad distributions in matrix-polymerized chains suggest that the well-known stereospecific replica polymerization in PMMA (syndiotactic sequences promote isotactic sequences and vice versa) plays only a limited role in the systems studied. Experimental results indicate that chains grown within the i-PMMA or s-PMMA solid matrices have greater degrees of configurational disorder. The greater concentration of atactic triads in these chains could be the result of limited free volume or steric effects during polymerization in a highly condensed environment. X-ray diffraction studies of solution cast blends of isotactic PMMA and PMMA with conventional tacticity reveal some crystallinity with a structure characteristic of the stereocomplex formed by isotactic and syndiotactic PMMA from suitable solvents. Evidence was obtained for the presence of this complex in solidified mixtures of the i-PMMA solid matrix and liquid monomer. This observation is an example of special intermolecular structures that can form under conditions of in situ growth of chains within a pre-polymerized matrix.     

Thermally stimulated current (TSC) study of the Tg and Tll transitions in anionic polystyrenes

The thermally stimulated current (TSC) technique has been used to investigate three anionic polystyrenes of M?_n 17,000, 71,700, and 1.55 × 10⁶, i.e., M < M_c, M > M_c, and M ? M_c, where M_c is the entanglement molecular weight. A current maximum near T_g designated T_Mg, has relaxation times which follow an Arrhenius equation. A second current maximum at T > T_g appears to be the T_ll process and is designated T_Mll. Relaxation times for it follow a Vogel equation. T_Mg and T_Mll vary with molecular weight, increasing below M_c and leveling off above M_c at a temperature of about 170°C. Values of T_Mg and T_Mll are compared with values of T_g and T_ll obtained from torsional braid analysis, which involves melt flow; and with differential-scanning-calorimetric values on fused films, where there is no transport of polymer. It is concluded from such cross-comparisons that TSC, at least for polystyrene, is a quasistatic test which may involve microscopic viscosity. Macroscopic viscosity does not play a role. The ratio T_Mll/T_Mg is in the range 1.10–1.16, similar to T_ll/T_g values by other methods. A few comments about T_ll in atactic poly(methyl methacrylate) by the TSC method are given.     

Influence of tacticity on orientation and relaxation in uniaxially stretched polymethylmethacrylates

Orientation and relaxation behavior in uniaxially stretched stereoregular polymethyl-methacrylate (PMMA) was investigated. When compared at a reference temperature T = T_g + constant, isotactic PMMA orients more readily and relaxes slightly faster than the conventional or syndiotactic polymers. Orientation relaxation of the different PMMAs can be reduced to a unique master curve, whatever the tacticity, when the results are compared at same monomeric friction coefficient. © 1996 John Wiley & Sons, Inc.     

Hydrogen‐bond‐assisted stereocontrol in the radical polymerization of N‐isopropylacrylamide with secondary alkyl phosphate: The effect of the bulkiness of the ester group

The radical polymerization of N‐isopropylacrylamide (NIPAAm) in toluene at low temperatures was investigated in the presence of triisopropyl phosphate (TiPP). The addition of TiPP induced a syndiotactic specificity that was enhanced by the polymerization temperature being lowered, whereas atactic polymers were obtained in the absence of TiPP, regardless of the temperature. Syndiotactic‐rich poly(NIPAAm) with a racemo dyad content of 65% was obtained at ?60 °C with a fourfold amount of TiPP, but almost atactic poly(NIPAAm)s were obtained by the temperature being lowered to ?80 °C. This result contrasted with the result in the presence of primary alkyl phosphates, such as tri‐n‐propyl phosphate: the stereospecificity varied from syndiotactic to isotactic as the polymerization temperature was lowered. NMR analysis at ?80 °C revealed that TiPP predominantly formed a 1:1 complex with NIPAAm, although primary alkyl phosphates preferentially formed a 1:2 complex with NIPAAm. Thus, it was concluded that a slight increase in the bulkiness of the added phosphates influenced the stoichiometry of the NIPAAm–phosphate complex at lower temperatures, and consequently a drastic change in the effect on the stereospecificity of NIPAAm polymerization was observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3899–3908, 2005     

Structure and properties of poly(methyl methacrylate) particles prepared by a modified microemulsion polymerization

Nanoscale poly(methyl methacrylate) (PMMA) particles were prepared by modified microemulsion polymerization. Different from particles made by traditional microemulsion polymerization, the particles prepared by modified microemulsion polymerization were multichain systems. PMMA samples, whether prepared by the traditional procedure or the modified procedure, had glass-transition temperatures (T_g's) greater than 120 °C and were rich in syndiotactic content (55–61% rr). After the samples were dissolved in CHCl₃, there were decreases in the T_g values for the polymers prepared by the traditional procedure and those prepared by the modified process. However, a more evident T_g decrease was observed in the former than in the latter; still, for both, T_g was greater than 120 °C. Polarizing optical microscopy and wide-angle X-ray diffraction indicated that some ordered regions formed in the particles prepared by modified microemulsion polymerization. The addition of a chain-transfer agent resulted in a decrease in both the syndiotacticity and T_g through decreasing polymer molecular weight. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 733–741, 2004