Dielectric study of low-temperature relaxations in poly(isobutyl methacrylate), poly(n-butyl methacrylate), poly(isopropyl methacrylate), and poly(4-methylpentene-1)

Isochronal measurements of dielectric constant and loss are made for poly(isobutyl methacrylate) (PiBMA), poly(n-butyl methacrylate) (PnBMA), poly(isopropyl methacrylate) (PiBMA), and poly(4-methylpentene-1) (P4MP1) at temperatures ranging from 4°K to 250°K. Loss peaks are found around 120°K (10–100 Hz) for PiBMA, PnBMA, and P4MP1. By comparing the activation energy with the calculated potential barrier for the internal rotation of alkyl group in the side chain, the motion responsible for the 120°K peak is concluded to be essentially the rotation of the isopropyl group as a whole for PiBMA and P4MP1 but, for PnBMA, the rotation of n-propyl group accompanied by the rotation of the end ethyl group. Multiple paths of internal rotation are involved with the 120°K peaks of PiBMA and, in particular, PnBMA, which explain differences between PiBMA and PnBMA in the broadness and the temperature location of the 120°K peak. The 120°K peak is in general assigned to a side chain including a sequence? O? C? C? C or ? C? C? C? C. PiPMA without this sequence in the side chain does not show the 120°K peak, but it exhibits the 50°K peak (1 kHz) like poly(ethyl methacrylate). The 50°K peak is assigned to the rotation of ethyl or isopropyl group attached to COO group. Poly-L-valine in which the isopropyl group is directly attached to carbon does not have the 50°K peak. An additional loss peak at 20°K (1 kHz) for P4MP1 is also discussed on the basis of the calculated potential.     

Higher aliphatic polyaldehydes. IV. Transitions in poly(n-valeraldehyde), poly(n-hexaldehyde), poly(n-heptaldehyde), and poly(n-octaldehyde)

Crystalline polymers of n-valeraldehyde, n-hexaldehyde, n-heptaldehyde, and n-octaldehyde were prepared by anionic polymerization with lithium tertiary butoxide as the initiator at low temperatures. The polymers were end-capped with acetic anhydride, and their thermal stability was studied primarily by DTG. It was found that all polymers degrade rapidly above 150°C. All polymers show a dual melting-point behavior. The first melting region, which is associated with the melting of the side chain, is 80–85°C for poly(n-valeraldehyde); 87–90°C for poly(n-hexaldehyde); 78–101°C for poly(n-heptaldehyde); and 41–69°C for poly(n-octaldehyde). Annealing and quenching of the samples showed that this melting-point region consisted of several endotherm peaks whose intensity changed according to the thermal history of the sample. Although the samples are apparently highly crystalline, the side-chain crystallinity is apparently only in the 20% range.     

The dielectric β-relaxation of poly(bis-benzimidazobenzisoquinolinones)

The dielectric relaxation of poly(bis-benzimidazobenzisoquinolinones) has been studied in the frequency range from 10¹ to 10⁵ Hz and at temperatures from ?150 to +80°C. The data show that the relaxation is due mainly to diffusion of water in the polymer with simultaneous reorientation of water dipoles.     

Effects of thermal history,crystallinity, and solvent on the transitions and relaxations in poly(bisphenol-A carbonate)

The following system of nomenclature for the transitions and relaxations in polycarbonate has been proposed: α = T_g = 150, β = 70, γ = ?100, and δ = ?220°C (frequency range of 10–50 Hz). The three component peaks of the γ relaxation are denoted by γ₁, γ₂, and γ₃ relaxations correspond to phenylene, coupled phenylene-carbonate, and carbonate motions, respectively. Dynamic mechanical analysis of poly(bisphenol-A carbonate) using the DuPont 981–990 DMA system shows that the magnitude of the β relaxation depends upon the thermal history of the polycarbonate; annealing greatly reduces the intensity of the β relaxation. A relaxation map constructed for the β relaxation gives an activation energy of 46 kcal/mol. Exposure of polycarbonate to methylene chloride vapor for various times shows that after an induction period of about 5 min the intensity of the γ₃ relaxation at ?78°C decreases whereas the intensity of the γ₁ relaxation of ?30°C is unaffected and the ratio E″(γ₁)/E″(γ₃) increases linearly with the square root of time. This has been ascribed to the interaction of methylene chloride on the carbonate group in polycarbonate. Thermal crystallization of polycarbonate does not affect the positions of the γ relaxation and the glass transition peaks, but merely reduces their intensity. The glass transition peak intensity falls off sharply in comparison to the γ relaxation intensity. Both the γ₃ and γ₁ peaks in polycarbonate have been observed simultaneously for the first time by dynamic mechanical analysis. Impact strength measurements show that methylene chloride treatment of polycarbonate results in a change in mode of failure from ductile to brittle with a resultant 40-fold reduction in impact energy for fracture. Thermally crystallized polycarbonate exhibits brittle fracture with very low force and energy at break.     

Solvation of polymeric organolithium compounds. Stoichiometry and heats of interaction of N,N,N′,N′-tetramethylethylenediamine (TMEDA) with poly(styryl)lithium and poly(isoprenyl)lithium

The enthalpies of interaction of N,N,N′,N′-tetramethylethylenediamine (TMEDA) with poly-(isoprenyl)lithium and poly(styryl)lithium were measured as a function of R ([base]/[Li]) by using high-dilution solution calorimetry at 25°C. Both polymeric organolithiums exhibit initial exothermic enthalpies of interaction with TMEDA (R ? 0.1) of ca. ?13 kcal/mole. The concentration dependencies show a break (decrease) in the plot of ΔH vs. R at ca. R = 0.5 for poly(isoprenyl)lithium and at ca. R = 1.0 for poly(styryl)lithium.     

Synthesis and properties of nitrogen‐linked poly(2,7‐carbazole)s as hole‐transport material for organic light emitting diodes

A novel class of carbazole polymers, nitrogen‐linked poly(2,7‐carbazole)s, was synthesized by polycondensation between two bifunctional monomers using the palladium‐catalyzed amination reaction. The polymers were characterized by ¹H NMR, Infrared, Gel permeation chromatography, and MALDI‐TOF MS and it was revealed that the combination of the monomer structures is important for producing high molecular weight polymers. Thermal analysis indicated a good thermal stability with high glass transition temperatures, e.g., 138 °C for the higher molecular weight polymer P2 . To pursue the application possibilities of these polymers, their optical properties and energy levels were investigated by UV‐Vis absorption and fluorescence spectra as well as their electrochemical characteristics. Although the blue light emission was indeed observed for all polymers in solution, the quantum yields were very low and the solid films were not fluorescent. On the other hand, the HOMO levels of the polymers estimated from the onset potentials for the first oxidation in the solid thin films were relatively high in the range of ?5.12 to ?5.20 eV. Therefore, light emitting diodes employing these polymers as a hole‐transport layer and iridium(III) complex as a triplet emitter were fabricated. The device of the nitrogen‐linked poly(2,7‐carbazole) P3 with p,p′‐biphenyl spacer, which has a higher HOMO level and a higher molecular weight, showed a much better performance than the device of P2 with m‐phenylene spacer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3880–3891, 2009     

Crystal structure of poly(γ-methyl L-glutamate) at high temperature

A unique crystal structure of the α-helical form of poly(γ-methyl L -glutamate) appearing above 170°C is analyzed by x-ray diffraction. At room temperature, the unit cell determined for a well-annealed sample is hexagonal with dimension a = 11.8₂ Å and contains one α helix with pitch P = 5.42 Å and unit height p = 1.493 Å. This form is reversibly transformed at about 170°C into a modification characterized by a trigonal unit cell (a = 21.2₇ Å) having three times the cross section of the single-chain unit cell and containing three α helices with P = 5.50 Å and p = 1.504 Å. In a narrow temperature range below 180°C, the three chains in the unit cell are not interrelated by any crystallographic symmetry element, but they are reasonably associated with one another so that all helices are surrounded by other helices in the same way. The axial and azimuthal displacements between neighboring chains are expressed by z = ±4p/3 and ? = ± (2π/3)(4p/P ? 1), respectively. The segmental main-chain motion, which becomes appreciable above 150°C, is composed of screw-type motion along the α-helix fold and correlated P/3 axial jumps. The relation between the structural transition and thermal motion is discussed.     

Synthesis and characterization of poly (2-vinylpridine)-b-poly (t-butyl methacrylate)

The synthesis of well defined and monodisperse (M_w/M_n ≤ 1.2) narrow molecular weight distribution poly (2-vinylpyridine)-poly (t-butyl methacrylate) (P2VP-PTBMA) AB block copolymers is carried out by initiation of 2-vinylpyridine polymerization by 1,1-diphenylhexyllithium in THF at-78°C, followed by addition of TBMA and termination at ?78°C using MeOH. The formation of the BAB block copolymer is carried out in a similar fashion except that 1,4-dilithio-1,1,4,4-tetraphenylbutane is used as initiator. The corresponding synthesis of P2VP-PMMA block copolymers is carried in a similar manner, except that 1-2 equivalents of TBMA is used to end-functionalize the living P2VP before the addition of MMA. Without the addition of TBMA, trimodal molecular weight distributions in P2VP-b-PMMA are obtained. All the block copolymers are characterized by Size Exclusion Chromatography (SEC), Nuclear Magnetic Resonance (NMR), and Differential Scanning Calorimetry (DSC). © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of new poly(aryl ether)s with isolated fluorophores

Four novel poly(aryl ether)s ( P1 – P4 ) consisting of alternate isolated electron‐transporting (3,3″′‐bis‐trifluoromethyl‐p‐quaterphenyl for P1 , P3 or 3,3″′‐dicyano‐p‐quaterphenyl for P2 , P4 ) and hole‐transporting fluorophores [N‐(2‐ethylhexyl)‐3,6‐bis(styryl)carbazole for P1 , P2 or 9,9‐dihexyl‐2,7‐bis(styryl)fluorene for P3 , P4 ] were synthesized and characterized. These poly(aryl ether)s can be dissolved in organic solvents and exhibited good thermal stability with 5% weight‐loss temperature above 500 °C in nitrogen atmosphere. The photoluminescent (PL) spectra of the films of these polymers showed maximum peaks at around 442–452 nm. The PL spectral results revealed that the emission of polymers was dominated by the fluorophores with longer emissive wavelength via the energy transfer from p‐quaterphenyl to 3,6‐bis(styryl)carbazole or 2,7‐bis(styryl)fluorene segments. Therefore, the p‐quaterphenyl segments function only as the electron‐transporting/hole‐blocking units in these polymers, and the other segments are the emissive centers and hole‐transporting units. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital energy levels of these polymers were measured by cyclic voltammetry. The electron‐donating nitrogen atom on carbazole resulted in the higher HOMO energy levels of P1 and P2 than those of P3 and P4 . The single‐layer light‐emitting diodes (LED) of Al/poly(aryl ether)s ( P1 – P4 )/ITO glass were fabricated. P1 , P2 , and P4 revealed blue electroluminescence, but P3 emitted yellow light as a result of the excimer emission. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2215–2224, 2002     

Complex formation of poly(4-vinyl-N-alkylpyridinium) salts or polymer containing flavin mononucleotide with indole derivatives

A charge-transfer-type complex formation between poly(4-vinyl-N-propylpyridinium bromide) (C3PVP), poly(4-vinyl-N-butylpyridinium bromide) (C4PVP) or poly(4-vinyl-N-benzylpyridinium chloride) (BzPVP), and indole derivatives or between polymer containing flavin mononucleotide residues and indole derivatives was studied in the presence of simple and polyelectrolytes. The association constant (K) of the complex formation with indole acetate increased in the order BzPVP > C4PVP > C3PVP, which indicated an important contribution by hydrophobic interaction. The addition of simple and polyelectrolytes decreased the association constants. This was explained by the “secondary salt effect” of the salts. The importance of the electrostatic interactions in the complexation systems was obvious. The influence of simple electrolytes on the K values was discussed theoretically according to Manning's theory.     

Polyisobutylene-containing block polymers by sequential monomer addition. X. Synthesis of poly(α-methylstyrene-b-isobutylene-b-α-methylstyrene) thermoplastic elastomers

Preparatory to triblock synthesis experiments, the cationic polymerization of α-methylstyrene (αMeSt) was investigated using the 2-chloro-2,4,4-trimethylpentane (TMPCI)/TiCl₄ initiating system in the presence of triethylamine (Et₃N) as electron donor (ED) and CH₃Cl/n-hexane mixed solvent in the ?80 to ?40°C range. Conversions are influenced by temperature, [TiCl₄], [Et₃N], and [αMeSt]. The polymerization of αMeSt is living at ?80°C: Both termination and chain transfer to monomer are frozen out, however, initiation is slow relative to propagation. Highly syndiotactic (>94%) Pα Mest was obtained. At?60deg;C initiator efficiency is ca. 100%, but termination becomes evident. Et₃N may act both as Ed and as proton scavenger. Novel poly(α-methystyrene-b-isobutylene-b-α-methylstyrene) (PαMeSt-PIB-PαMeSt) triblocks have been synthesized by adding αMeSt to biliving polyisobutylene carbocations (⊕PIB⊕) in the ?80 to ?40°C range. The effects of temperature, solvent polarity, and [Et₃N] on the block copolymerization have been investigated. At ?80°C, the rate of crossover from ⊕PIB⊕ to αMeSt is lower than that of propagation of PαMeSt⊕, so that the triblock is contaminated by PIB and PIB-b-PαMeSt. At ?60°C, crossover occurs preferentially. The rate of propagation relative to that of crossover is also reduced by lowering the solvent polarity and increasing the [Et₃N]. High crossover efficiency and blocking efficiency can be obtained under optimum blocking conditions. The triblocks are novel thermoplastic elastomers (TPEs). © 1994 John Wiley & Sons, Inc.     

Synthesis and functionalities of poly(N-vinylalkylamide). V. Control of a lower critical solution temperature of poly(N-vinylalkylamide)

N-vinyl-n-butyramide (NVBA), N-vinylisovaleramide (NVIVA), and N-vinyl-n-valeramide (NVVA), which are N-vinylalkylamides with different alkyl groups were synthesized and their solution behavior in a polymeric form was examined. Copolymers of N-vinylisobutyramide (NVIBA) with N-vinylacetamide (NVA), NVIBA with NVVA, and NVVA with NVA were prepared by the solution polymerization to control the LCSTs. The resultant polyNVBA showed a lower critical solution temperature (LCST) sharply at 32°C, but polyN-vinylisovaleramide (polyNVIVA) and polyN-vinyl-n-valeramide(polyNVVA) that have n-butyl and isobutyl groups, respectively, on their side chains were insoluble even in cold water. The water solubility of the resulting polymers was found to vary, depending on the molecular shapes as well as the side chain length of the alkyl groups in question. The copolymers consisting of NVVA, NVIBA, and NVA in water showed LCSTs sharply between 10 and 90°C, depending on changes in their comonomer content. It was found that the changes in LCST that are caused by the incorporation of comonomers are due to changes in the overall hydrophilicity of the polymer. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3087–3094, 1997     

Dynamic mechanical relaxation effects in some poly(arylene sulfones)

Poly-4,4′-oxydiphenylenesulfonyl and poly-4,4′-methylenediphenylenesulfonyl were synthesized by an electrophilic substitution polymerization of the arylene monosulfonyl chloride monomers. The glass-transition temperatures T_g of these polymers were determined by calorimetric and dynamic mechanical measurements, and the number-average molecular weights were determined by vapor-pressure osmometry. Both polymers were found to have the same T_g at equivalent molecular weight; the limiting value at high molecular weight is 238°C. Both polymers have two dynamic mechanical relaxation peaks at temperatures far below T_g. One is in the neighborhood of 0°C, and the other is at ?110°C. Plausible origins for these relaxations, and the absence of any near 0°C in poly(4,4′-isopropylidenediphenylene-co-4,4′-sulfonyldiphenylene dioxide), are discussed.     

Physical characterization of poly(ω‐pentadecalactone) synthesized by lipase‐catalyzed ring‐opening polymerization

The Candida antarctica lipase B (Novozyme‐435)‐catalyzed ring‐opening polymerization of ω‐pentadecalactone in toluene was performed. Poly(ω‐pentadecalactone) [poly(PDL)] was obtained in a 93% isolated yield in 4 h with a number‐average molecular weight of 64.5 × 10³ g/mol and a polydispersity index of 2.0. The solid‐state properties of poly(PDL) were investigated by thermogravimetric analysis (TGA) coupled with mass spectrometry, differential scanning calorimetry (DSC), stress–strain measurements, wide‐angle X‐ray diffraction, and dynamic mechanical and dielectric spectroscopies. Poly(PDL) is a crystalline polymer that melts around 100 °C. The polyester shows good thermal stability, with a main TGA weight loss centered at 425 °C. Because of the high degree of poly(PDL) crystallinity, the glass transition (?27 °C) is revealed by relaxation techniques such as dynamic mechanical and dielectric spectroscopies, rather than by DSC. In addition to the glass transition, the viscoelastic spectrum of poly(PDL) also shows two low‐temperature secondary relaxations centered at ?130 (γ) and ?90 °C (β). They are attributed to local motions of the long methylene sequence (γ) and complex units involving water associated with the ester groups (β). The mechanical properties of poly(PDL) are typical of a hard, tough material, with an elastic modulus and yield parameters comparable to those of low‐density polyethylene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1721–1729, 2001     

Synthesis and Properties of Carbazole-containing Copolymers from Bis[3-(4-fluorobenzoyl)carbazole] Methane

A novel difluoride containing carbazole groups was designed. Two series of polycarbazoles based on the novel monomer were synthesized via C-N coupling reactions with either 4,4′-biphenol or bisphenol A. Copolymers were obtained with 4,4′-difluorobenzophenone or bis(4-fluorophenyl) sulfone as comonomer. The solubilities of the poly(carbazole ketones)s were poor, but the poly(carbazaole sulfones)s all dissolved in NMP, DMSO and DMAC. Tough films of poly(carbazole sulfones)s could be easily cast from NMP solutions. The viscosities of poly(carbazole sulfones)s were 0.72 ～ 0.90 dL/g. The T_gs of polymers ranged from 162.4°C to 258.9°C. The temperatures of 5% wt loss ranged from 460°C to 509°C. UV-Vis absorptions and blue light emissions properties are also presented.     

Synthesis of ABA‐triblock and star‐diblock copolymers with poly(2‐adamantyl vinyl ether) and poly(n‐butyl vinyl ether) segments: New thermoplastic elastomers composed solely of poly(vinyl ether) backbones

ABA‐type triblock copolymers and AB‐type star diblock copolymers with poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] hard outer segments and poly(n‐butyl vinyl ether) [poly(NBVE)] soft inner segments were synthesized by sequential living cationic copolymerization. Although both the two polymer segments were composed solely of poly(vinyl ether) backbones and hydrocarbon side chains, they were segregated into microphase‐separated structure, so that the block copolymers formed thermoplastic elastomers. Both the ABA‐type triblock copolymers and the AB‐type star diblock copolymers exhibited rubber elasticity over wide temperature range. For example, the ABA‐type triblock copolymers showed rubber elasticity from about ?53 °C to about 165 °C and the AB‐type star diblock copolymer did from about ?47 °C to 183 °C with a similar composition of poly(2‐AdVE) and poly(NBVE) segments in the dynamic mechanical analysis. The AB‐type star diblock copolymers exhibited higher tensile strength and elongation at break than the ABA‐type triblock copolymers. The thermal decomposition temperatures of both the block copolymers were as high as 321–331 °C, indicating their high thermal stability. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Temperature-rise fractionation of poly(3-alkyl thiophenes)

In this article, we have investigated a temperature-rise fractionation procedure for poly(3-hexyl thophene) (P3HT) and poly(3-octyl thophene) (P3OT) that provides well-defined molecular weight (MW) fractions with improved molecular weight distributions (MWD) when compared with Soxhlet extraction. This process involves dispersing the material over C18-boned silica stationary phase in a jacketed column and using incremental rises in column temperature (T_col) to gradually improve solvent quality and selectively dissolve higher molecular weight samples with a narrow polydispersity (PDI). Fractionation of P3HT with ΔT_col = 5 °C in methylene chloride (MC) yielded 7 fractions ranging from M_p of 20 to 53 kg/mol with an average PDI of 1.80 compared with a mother sample of 3.10. Predominant recovery of P3HT was acquired for fractions with T_col > 20 °C (30 wt %). Subsequent separation of P3OT in methylene chloride, with a reduced ΔT_col of 3 °C per fraction, due to increased solubility from the longer alkyl chain, generated 8 fractions with a weight range of M_n = 22 to 57 kg/mol with an mean PDI of 1.23 with the mother sample having PDI = 2.34, demonstrating the tunability of this method. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2547–2555, 2009     

Dielectric γ relaxation in poly(2-hydroxyethyl methacrylate)

The dielectric constant and loss were measured for poly(2-hydroxyethyl methacrylate) from ?90 to 34°C over the frequency range 30 to 3 × 10⁵ Hz in the γ relaxation region. The relaxation was also characterized using activation energies.     

ESR spectra of poly(methacrylic acid) and poly(methyl methacrylate): Reinterpretation of the 9-line spectrum

The temperature dependence of the ESR spectra of poly(methacrylic acid) and poly-(methyl methacrylate) γ-irradiated at room temperature was studied between ?196°C and +25°C. The conventional 9-line spectrum was observed throughout this range with no significant spectral change, in contrast to the propagating radical ··· CH₂? °C(CH₃)COOR found in methacrylic acid monomer or barium methacrylate dihydrate irradiated at ?196°C. In addition, the irradiation of methacrylic acid monomer with a low dose at 0°C gave the same 13-line spectrum as that of the propagating radical obtained by the irradiation at ?196°C, while prolonged irradiation at 0°C gave the same conventional 9-line spectrum as that of poly(methacrylic acid) or poly(methyl methacrylate). The conventional 9-line spectrum has a much weaker 4-line component than that of the propagating radical. The difference comes from the surrounding matrix, and the conventional 9-line spectrum is well interpreted by introducing the concept of the distribution of the conformational angle in the irregular polymer matrix. From simulation of the ESR spectrum, it was found that the intensity of the 4-line component is very sensitive to the distribution, and that the observed 9-line spectrum is well reproduced assuming a Gaussian distribution (half-height width of 5–6°) around the most probable conformation which is nearly the same as that of the propagating radical, where the conformational angles of the two C? H_β bonds to the half-filled p-orbital are 55° and 65°.     

Synthesis of some aliphatic poly(ester-β-sulfone)s by a novel method

A new synthetic method of preparing poly(ester-β-sulfone)s from sodium formaldehyde sulfoxylate (SFS) and a diacrylate monomer (1,6-hexanediol diacrylate or 1,9-nonanediol diacrylate) in aqueous solution was studied. The structures of poly(ester-β-sulfone)s were identified and their crystal morphology analyzed. It turned out that the poly(ester-β-sulfone)s crystals were ring-shaped spherulites. The melting point of both poly(ester-β-sulfone)s was 97°C and 116°C, respectively. The thermal degradation temperature in both cases was close to 281°C.