Relaxational behavior of poly(4‐tetrahydropyranyl) methacrylate

Complex permittivity of poly(4‐tetrahydropyranyl methacrylate) (P4THPMA) was measured by dielectric spectroscopy. The spectra obtained show several relaxation processes labeled as δ, γ, β, and α in increasing order of temperature. These processes have been characterized and assigned to specific molecular motions. Comparison of the dielectric activity obtained for P4THPMA with those reported for poly(1,3‐dioxan‐5‐yl‐methacrylate) (PDMA) and poly(cyclohexyl methacrylate) (PCHMA) was performed. In fact, these three polymers have similar chemical structures with aliphatic rings in the ester residue. However, significant differences between the dielectric behavior of these polymers have been observed. In addition, complementary molecular mechanic (MM) calculations have been carried out. The energy barriers obtained by these calculations lead to energy barriers which are in relatively good agreement with those derived from the dielectric measurement by means Arrhenius plots. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3135–3147, 2006     

Thermal degradation of bromine-containing polymers: Part 11—Blends of poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) with poly(methyl methacrylate) and poly(methyl acrylate)

The products of degradation of blends of poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) with poly(methyl methacrylate) and poly(methyl acrylate) are predominantly those to be expected from the degradation of the individual polymers. However, the appearance of methyl bromide and methanol from all four blends indicates that some interaction does occur across the phase boundary between the two constituent polymers. This is presumed to consist of the reaction of hydrogen bromide, formed by decomposition of the brominated polymers with the methyl groups of the acrylate and methacrylate polymers.     

Dielectric relaxation studies of some linear crosslinked and branched polymers

Dielectric loss measurements are reported for polystyrene, crosslinked polystyrene, polyacrylamide, branched polyacrylamide, and poly(methyl methacrylate) at 1 and 10 kHz f over the temperature range ?85 to +100°C. Crosslinking and branching have a pronounced effect on the dielectric relaxation spectra of polymers. The methods of preparation of these polymers and their viscosity molecular weight data are also reported.     

Comparative study of the mechanical relaxation behavior of polymethacrylates containing different bulky side groups

The syntheses of poly(1,3‐dioxan‐5‐yl methacrylate), poly(cis‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate), poly(trans‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate), poly(cis‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate), and poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) are reported. The mechanical relaxation spectrum of the simplest polymer, poly(1,3‐dioxan‐5‐yl methacrylate), exhibits a prominent β relaxation centered at ?98 °C, at 1 Hz, followed in increasing order of temperature by an ostensible glass–rubber relaxation process. In addition to the β relaxation, the loss curves of poly(trans‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate) and poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) display in the glassy state a high activation energy relaxation, named the β* process, that seems to be a precursor of the glass–rubber relaxation of these polymers. The mechanical spectra of poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) and poly(cis‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) exhibit a low activation energy process in the low‐temperature side of the spectra, which is absent in the other polymers. The molecular origin of the mechanical activity of these polymers in the glassy state is discussed in qualitative terms. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1154–1162, 2002     

Water sorption by poly(tetrahydrofurfuril methacrylate)'s

Polymers consisting of poly(heterocyclic methacrylate)s are considered as potential materials for clinical applications such as drug delivery and cartilage repair. Much of the success of these systems has been attributed to the complex nature of their water sorption properties. Dielectric permittivity is very sensitive to water sorption. Dielectric relaxation spectroscopy studies have been carried out on two heterocyclic poly(methacrylate)s: poly(tetrahydrofurfuryl methacrylate) (PTHFMA) and poly(3‐methyl tetrahydrofurfuryl methacrylate) (P3MTHFMA). The isochrones representing the dielectric losses show in both cases high conductivity at low frequencies and high temperatures. In PTHFMA two conductive processes are observed, which can be associated to the existence of two types of water sorption. These effects have been analyzed and were removed from the dielectric spectra by using classical empirical equations. Both polymers show ostensible α‐relaxation centered in the vicinity of 350 K at 10⁰ Hz. This relaxation was analyzed by means of the empirical Havriliak‐Negami equation. Reminiscent β‐relaxation could also exist. Both polymers present well defined γ and δ subglass absorptions at approximately 120 K, 160 K for PTHFMA and 125 K, 163 K for P3MTHFMA, at 10⁰ Hz, associated to local intramolecular relaxations in side groups. These relaxations were analyzed using semiempirical symmetric model. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 109–120, 2008     

Precise Synthesis of New Triblock Co- and Terpolymers by a Methodology Combining Living Anionic Polymers with a Specially Designed Linking Reaction

Five A-B-A′, A-C-A′, B-A-B′, C-A-C′, and C-B-C′ triblock terpolymers with block orders difficult to synthesize by sequential polymerization have been successfully synthesized by a new methodology combining living anionic polymers with a specially designed linking reaction using α-phenylacrylate as the reaction site. Here, A(A′), B(B′), and C(C′) represent groups of polymers (having chain-end anions with different nucleophilicities), which are only polymerizable from A(A′) to B(B′) to C(C′) via sequential polymerization. The corresponding polymers are polystyrene (A) and poly(α-methylstyrene) (A′), poly(2-vinylpyridine) (B) and poly(4-vinylpyridine) (B′) and polymers from methacrylate type monomers like poly(methyl methacrylate) (C), poly(tert-butyl methacrylate) (C′), poly(2-hydroxyethyl methacrylate) (C′), poly(2,3-dihydroxypropyl methacrylate) (C′), and poly(ferrocenylmethyl methacrylate) (C′). Furthermore, three synthetically difficult B-A-B, C-A-C, and C-B-C triblock copolymers with molecular asymmetry in both side blocks have also been synthesized by the developed methodology. All of the polymers thus synthesized are quite new triblock terpolymers and copolymers with well-defined structures, i.e., precisely controlled molecular weights, compositions and narrow molecular weight distributions (M_w/M_n ≤ 1.05).     

General properties of secondary relaxations in polymers as determined by the thermally stimulated current method

The method of thermally stimulated current (TSC) has been used to study the low-temperature dielectric β relaxations of several polymers including especially poly(vinyl chloride), poly(vinyl acetate), polyamide 6, 6,6,poly(t-butyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(phenyl methacrylate), and poly(t-butyl methacrylate). The distribution characteristics of the relaxation processes have been determined from the corresponding TSC peaks by a fractional polarization technique which consists of applying the electric field in several discrete steps during a slow cooling. Several common features have been found in all the polymers investigated: the β peaks are characterized by a distribution of relaxation times resulting from a distribution in activation energy and this distribution is quasisymmetrical and continuous. These facts are in agreement with the hypothesis of a relaxation involving local motions of small polar groups undergoing various interactions with the environment. Some discrepancy remains, however, between our calculated values of the mean activation energy and those obtained from the dielectric loss.     

Dynamic mechanical and dielectric relaxations of poly(difluorobenzyl methacrylates)

This work reports the mechanical and dielectric relaxation spectra of three difluorinated phenyl isomers of poly(benzyl methacrylate), specifically, poly(2,4‐difluorobenzyl methacrylate), poly(2,5‐difluorobenzyl methacrylate) and poly(2,6‐difluorobenzyl methacrylate). The strength of the dielectric glass–rubber relaxation of the 2,6 difluorinated phenyl isomer is, respectively, nearly three and two times larger than the strengths of the 2,5 and 2,4 isomers. The 2,4 isomer presents a mechanical α peak the intensity of which is nearly two times that of the other two isomers. Both the mechanical and dielectric relaxation spectra display a subglass process, called γ relaxation, centered in the vicinity of −50 °C at 1 Hz and, in some cases, a subglass β absorption is detected at higher temperature partially masked by the glass–rubber relaxation. The mean‐square dipole moments per repeating unit, 〈μ2〉/x, measured at 25 °C in benzene solutions, are 2.5 D², 1.9 D², and 5.0 D² for poly(2,4‐difluorobenzyl methacrylate), poly(2,5‐difluorobenzyl methacrylate) and poly(2,6‐difluorobenzyl methacrylate), respectively. These results, in conjunction with Onsager type equations, permit to conclude that auto and cross‐correlation contributions to the dipolar correlation coefficient may have the same time‐dependence. On the other hand, dipole intermolecular interactions, rather than differences in the flexibility of the chains, seem to be responsible for the relatively high calorimetric glass‐transition temperature of the 2,6 diphenyl isomer, which is, respectively, nearly 36 °C and 32 °C above the T_g's of the 2,4 and 2,5 isomers. Molecular Mechanics calculations give a good account of the differences observed in the polarity of the polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2179–2188, 2000     

Structure of water incorporated in sulfobetaine polymer films as studied by ATR-FTIR

The structure and hydrogen bonding of water in the vicinity of a thin film of a sulfobetaine copolymer (poly[(N,N-dimethyl-N-(3-sulfopropyl)-3'-methacrylamidopropanaminium inner salt)-ran-(butyl methacrylate)], poly(SPB-r-BMA)), were analyzed with band shapes of O-H stretching of attenuated total reflection infrared (ATR-IR) spectra. The copolymer could be cast as a thin film, of approximate thickness 10 microm, on a ZnSe crystal for the ATR-IR spectroscopy. At an early stage of sorption of water into the polymer film, the O-H stretching band of the IR spectra for the water incorporated in the film was similar to that for free water. This is consistent with the tendency for another zwitterionic polymeric material, poly[(2-methacryloyloxyethylphosphorylcholine)-ran-(butyl methacrylate)] (poly(MPC-r-BMA). It is, however, contradictory to the drastic change in the O-H stretching band for water incorporated into films of polymers such as poly(2-hydroxyethyl methacrylate), poly(methyl methacrylate) and poly(butyl methacrylate). These results suggest that polymers with a zwitterionic structure do not significantly disturb the hydrogen bonding between water molecules incorporated in the thin films. The investigation into the blood-compatibility of both the poly(SPB-r-BMA) and the poly(MPC-r-BMA) films indicate a definite correlation between the blood-compatibility of the polymers and the lack of effect of the polymeric materials on the structure of the incorporated water.     

Linear polymers of allyl acrylate and allyl methacrylate

Allyl acrylate and allyl methacrylate were polymerized by anionic initiators to soluble linear polymers containing allyl groups in the pendant side chains. The pendant unpolymerized allyl groups of the resulting linear poly(allyl acrylates) were shown to be present by: (1) the disappearance of the acrylyl and methacrylyl double bond absorptions in the infrared spectra in the conversions of monomers to polymers; (2) postbromination of the allyl bonds in the linear polymer; (3) the disappearance of the allyl groups absorptions in the infrared spectra of the brominated linear polymers; and (4) the thermal- and radical-initiated crosslinking of the linear polymers through the allyl groups. Allyl acrylate and allyl methacrylate show great reluctance to copolymerize with styrene under anionic initiation, but copolymerize readily with methyl methacrylate and acrylonitrile. Block copolymers were prepared by reacting allyl methacrylate with preformed polystyrene and poly(methyl methacrylate) anions. The linear polymers and copolymers of allyl acrylate may be classified as “self-reactive” polymers which yield thermosetting polymers. Bromination of the linear polymers offers a convenient method of producing self-extinguishing polymers.     

Graft polymers from poly(vinyl chloride) and chlorinated rubber

Graft polymers from poly(vinyl chloride) (PVC) and chlorinated rubber (CIR) with side chains of poly(methyl methacrylate) (PMMA), poly(methyl acrylate) (PMA), or poly(ethyl methacrylate) (PEMA) were synthesized. For this purpose, a vinyl monomer was polymerized in the presence of small quantities of PVC or CIR with benzoyl peroxide as catalyst. The graft polymers were separated from both homopolymers by precipitation with methanol from methyl ethyl ketone solutions of the reaction products and the grafting efficiency was calculated. The graft polymers were characterized by infrared spectra, elemental analysis, NMR, and osmometric or light-scattering determinations. From the results it is concluded that the PVC or CIR molecules contain side chains of PMMA, PMA, or PEMA. The graft polymers showed higher molecular weights, and the values of second virial coefficient for these polymers were much different from those of the starting polymers.     

DSC analysis of compatibility of poly(phenyl methacrylate) and some poly(xylenyl methacrylates)

Glass transition temperatures of blends of (1) poly-(phenyl methacrylate) and poly(2,3-xylenyl methacrylate), (2) poly-(phenyl methacrylate) and poly(2,6-xylenyl methacrylates and (3) poly-(2,3-xylenyl-) and poly(2,6-xylenyl methacrylate) were measured. The data obtained suggest the existance of compatibility for blends of poly(xylenyl methacrylates) mentioned and incompatibility for both poly(phenyl methacrylate)/poly(xylenyl methacrylate) systems.     

Utilizing matrix-assisted laser desorption/ionization-collision induced dissociation for the generation of structural information from poly(alkyl methacrylate)s

Matrix-assisted laser desorption/ionization-collision induced dissociation (MALDI-CID) has been employed for the analysis of poly(alkyl methacrylate)s in a tandem hybrid sector-time of flight instrument. Spectra are shown for adducts of poly(ethyl methacrylate) and poly(butyl methacrylate) with sodium ions. It is proposed that the masses of the end groups may be inferred from the data for the polymers. Mechanisms are proposed for the formation of some of the series of ion peaks that are observed in the MALDI-CID spectra.     

A Facile Photo-cross-linking Method for Polymer Gate Dielectrics and Their Applications in Fully Solution Processed Low Voltage Organic Field-effect Transistors on Plastic Substrate

A simple and effective photochemical method was developed for cross-linking of polymer gate dielectrics.Laborious synthetic processes for functionalizing polymer dielectrics with photo-cross-linkable groups were avoided.The photo-cross-linker,BBP-4,was added into host polymers by simple solution blending process,which was capable of abstracting hydrogen atoms from polymers containing active C―H groups upon exposure to ultraviolet(UV) radiation.The cross-linking can be completed with a relatively long wavelength UV light(365 nm).The approach has been applied to methacrylate and styrenic polymers such as commercial poly(methylmethacrylate)(PMMA),poly(iso-butylmethacrylate)(Pi BMA) and poly(4-methylstyrene)(PMS).The cross-linked networks enhanced dielectric properties and solvent resistance of the thin films.The bottom-gate organic field-effect transistors(OFETs) through all solution processes on plastic substrate were fabricated.The OFET devices showed low voltage operation and steep subthreshold swing at relatively small gate dielectric capacitance.     

Desorption electrospray ionisation mass spectrometry and tandem mass spectrometry of low molecular weight synthetic polymers

A range of low molecular weight synthetic polymers has been characterised by means of desorption electrospray ionisation (DESI) combined with both mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Accurate mass experiments were used to aid the structural determination of some of the oligomeric materials. The polymers analysed were poly(ethylene glycol) (PEG), polypropylene glycol (PPG), poly(methyl methacrylate) (PMMA) and poly(alpha-methyl styrene). An application of the technique for characterisation of a polymer used as part of an active ingredient in a pharmaceutical tablet is described. The mass spectra and tandem mass spectra of all of the polymers were obtained in seconds, indicating the sensitivity of the technique.     

Deconvolution of the relaxations associated with local and segmental motions in poly(methacrylate)s containing dichlorinated benzyl moieties in the ester residue

The relaxation behavior of poly(2,3-dichlorobenzyl methacrylate) is studied by broadband dielectric spectroscopy in the frequency range of 10(-1)-10(9) Hz and temperature interval of 303-423 K. The isotherms representing the dielectric loss of the glassy polymer in the frequency domain present a single absorption, called beta process. At temperatures close to Tg, the dynamical alpha relaxation already overlaps with the beta process, the degree of overlapping increasing with temperature. The deconvolution of the alpha and beta relaxations is facilitated using the retardation spectra calculated from the isotherms utilizing linear programming regularization parameter techniques. The temperature dependence of the beta relaxation presents a crossover associated with a change in activation energy of the local processes. The distance between the alpha and beta peaks, expressed as log(fmax;beta/fmax;alpha) where fmax is the frequency at the peak maximum, follows Arrhenius behavior in the temperature range of 310-384 K. Above 384 K, the distance between the peaks remains nearly constant and, as a result, the a onset temperature exhibited for many polymers is not reached in this system. The fraction of relaxation carried out through the alpha process, without beta assistance, is larger than 60% in the temperature range of 310-384 K where the so-called Williams ansatz holds.     

New Electrochemically Active Highly Sulfurized Polyconjugated Polymers

The electrochemical activity of new highly sulfurized polyconjugated polymers is studied. The polymers, polythienothiophene, poly(4,5,6,7-tetrathieno-4,5,6,7-tetrahydro-2,3-dehydrobenzothiophene), poly(6-methylthieno[2,3-b]pyridine-4-thione-5-thiol), and poly(6H-thieno[2,3-b]-azepine-6,7(8H)-dithione) are obtained in a deep sulfurization of polyethylene, polystyrene, and poly(5-vinyl-2-methylpyridine) by elemental sulfur. Employed as active cathodic material in lithium batteries, these polymers ensure their prolonged cycling with specific discharge capacity of up to 339 mA h/g. The effect of the conducting additive and electrolyte on the energy capacity and cycling of polymer cathodes in lithium batteries is discussed.     

Noncontact dielectric friction

Dielectric fluctuations are shown to be the dominant source of noncontact friction in high-sensitivity scanning probe microscopy of dielectric materials. Recent measurements have directly determined the friction acting on custom-fabricated single-crystal silicon cantilevers whose capacitively charged tips are located 3-200 nm above thin films of poly(methyl methacrylate), poly(vinyl acetate), and polystyrene. Differences in measured friction among these polymers are explained here by relating electric field fluctuations at the cantilever tip to dielectric relaxation of the polymer.     

Surface Functionalization at Atmospheric Pressure by DBD-Based Pulsed Plasma Polymerization

Dielectric barrier discharge (DBD)-based plasma deposition at atmospheric pressure, using glycidyl methacrylate (GMA, methacrylic acid-[2,3-epoxy-propyl ester]) as a prototype precursor was investigated in order to evaluate the applicability of dielectric barrier discharges to obtain plasma polymers with a high degree of structural retention of the starting precursor. Using pulsed excitation of the discharge, up to about 90% of the epoxy groups of GMA can be retained in plasma polymers obtainableat deposition rates in the order of 3–5nm/s. Preliminary investigations of the mechanism of film formation under pulsed plasma conditions indicate that the reaction of intact monomer molecules withsurface radicals generated during the pulses play a prominent role.     

聚甲基丙烯酸锡酯的NMR研究——Ⅰ.高分辨~(13)C-NMR谱归属和聚合物立构规整度

本文研究的样品是由自由基溶液聚合而成的聚甲基丙烯酸锡酯系列,对其~(13)C-NMR谱进行了详细的归属,并且定量研究了样品在CDCl_3溶液中的空间构型。结果表明,样品的空间立构以间规立构为主,随着取代基极性的减弱和体积的增大,间规立构的含量相应减少。