Photochromic organic-inorganic polymer hybrids from spiropyran-modified poly(N,N-dimethylacrylamide)

Summary Photochromic organic-inorganic polymer hybrids were prepared by the sol-gel reaction of tetramethoxysilane (TMOS) in the presence of spiropyran-modified poly(N,N-dimethylacrylamide) 3. The obtained polymer hybrids were characterized by thermogravimetric analysis (TGA) and FT-IR, and photochromic behavior was followed by electronic absorption spectroscopy. Upon an irradiation of ultraviolet light, an absorption around 557 nm appeared in the visible region and the color of the hybrid turned to be violet. The effect of silica gel on the isomerization behavior seemed to be relatively small. Received: 8 November 1999/Revised version: 13 December 1999/Accepted: 15 December 1999     

Structural and magnetic characterization of norbornene-deuterated norbornene dicarboxylic acid diblock copolymers doped with iron oxide nanoparticles

A series of iron oxide doped norbornene (NOR)/deuterated norbornene dicarboxylic acid (NORCOOH) diblock copolymers were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), small angle neutron scattering (SANS) and superconducting quantum interference device (SQUID) experiments. γ-Fe₂O₃ nanoparticles were synthesized within the microdomains of diblock copolymers with volume fractions of NOR/NORCOOH 0.64/0.36, 0.50/0.50 and 0.40/0.60. A spherical nanoparticle morphology was displayed in the polymer with 0.64/0.36 volume fraction. Polymers with 0.50/0.50 and 0.40/0.60 volume fractions exhibited interconnected metal oxide nanostructures. The observed changes in the shape and peak positions of the small-angle neutron scattering profiles of polymers after metal doping were related to the scattering from the metal oxide particles and to the possible deformed morphologies due to the strong interparticle interactions between metal particles, which may influence the polymer microphase separation. The combined scattering from both polymer domains and magnetic particles was depicted in SANS profiles of metal oxide doped polymers. γ-Fe₂O₃ containing block copolymers were superparamagnetic at room temperature. An increase in the blocking temperature (T_b) of interconnected nanoparticles was observed and was related to the interparticle interactions, which depends on the average distance (d) between particles and individual particle diameter (2R). The sample with volume fraction of 0.4/0.6 have the lowest d/(2R) ratio and exhibit the highest T_b at 115 K.     

Determination of the conformation of polymers in the amorphous solid state and in concentrated solution by neutron diffraction

From the coherent neutron scattering on dilute solid solutions of the ordinary polymer within the deuterated polymer, conformation parameters of polymer chains in amorphous solid states can be determined. In this way vitreous poly(methyl methacrylate) (PMMA) has been investigated. The chains form unperturbed coils and the radius of gyration is very near to the corresponding value in dilute solutions of the same polymer in the low molecular θ-solvent butyl chloride. The same principle of measurement has been applied to concentrated solutions of PMMA in D-acetone. The solutions contained 50% polymer, the main part of which (98% and more) was deuterated so that the system was optically dilute for neutron scattering on H-PMMA. A monotonic dependence of the radius of gyration and of thermodynamic parameters on the concentration has been found. A first result is presented for a mixture of two polymers. A dilute solid dispersion of poly(α-methylstyrene) (PMS) within D-PMMA has been investigated at M_w = 250 000. The samples are limpid. The PMS forms micelles of 16 molecules (weight average). The radius of gyration of the micelles, r_z is 170 Å.     

Synthesis of polyurethanes containing dioxynitrostilbene as a NLO-chromophore and their properties

Summary 3,4-Di-(2'-hydroxyethoxy)-4'-nitrostilbene (2) were prepared by the reaction of 2-iodoethanol with 3,4-dihydroxy-4'-nitrostilbene (1). Diol 2 was condensed with 2,4-toluenediisocyanate and 3,3'-dimethoxy-4,4'-biphenylenediisocynate to yield polyurethanes 3 and 4 containing the NLO-chromophore 3,4-dioxy-4'-nitrostilbene. Polymers 3 and 4 were soluble in common organic solvents such as acetone and DMSO. T _g value of the resulting polymers was in the range of 109–114°C. Electrooptic coefficient (r₃₃) of the poled polymer films were in the range of 20–25 pm/V at 633 nm. Polymers 3 and 4 showed a thermal stability up to 300°C in TGA thermograms, which is acceptable for NLO device applications. Received: 29 September 1999/Revised version: 19 November 1999/Accepted: 25 November 1999     

The effect of composition and the introduction of positive charge group (?N(CH3)2) on the multiphase morphology of polyurethane/polyacrylates interpenetrating polymer networks

A series of interpenetrating polymer networks (IPNs) of polyurethane/polyacrylates were synthesized. Their morphology was investigated by means of small‐angle X‐ray scattering (SAXS) and transmission electron microscope (TEM). The influence of an active positive charge group ( N(CH₃)₂) on the phase structure of the aforementioned IPNs was studied. The results show not only that the size of phase segregation zones varies with composition but also that the specific interfacial surface areas have a maximum when the weight ratio of polyurethane and polyacrylates is 1 : 2. Moreover, the introduction of an active positive charge group ( N(CH₃)₂) is an important way of increasing the miscibility between two component polymers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1898–1904, 1999     

Monte Carlo Design and Experiments on the Neutron Shielding Performances of B<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> Glass System

Neutron shielding properties of (90 – x)B₂O₃–10ZnO–xBi₂O₃ glass systems (where x = 15, 20, 25 and 30 mol %) were investigated by Monte Carlo simulations (FLUKA and GEANT4) and experiments. Neutron mass removal cross sections, number of inelastic scattering, elastic scattering, and capture interactions were estimated by simulations. ²⁴¹Am/Be neutron source was used for the neutron equivalent dose rate measurements. As a result, produced glass samples have fine neutron shielding capacity.     

The determination of the thermodynamic interaction parameter χ in polymer blends

The miscibility of polymer blends is related to the polymer-polymer interaction parameter χ₂₃, Several methods can be used to evaluate this parameter and five of the most important ones are reviewed: two equilibrium methods (melting-point depression and vapor sorption), a transport method (inverse-phase gas chromatography) and two scattering methods (neutron scattering and small-angle x-ray scattering). Examples are cited where χ₂₃ values for a given blend were determined by several of these methods. This comparison leads to the conclusion that a reasonable agreement is often reached despite conceptual differences between the methods involved.     

Small angle neutron scattering study of deuterated sodium dodecylsulfate micellization in dilute poly((2-dimethylamino)ethyl methacrylate) solutions

Poly((2-dimethylamino)ethyl methacrylate) with 60,000 g/mol and a narrow polydispersity (1.12) was synthesized using group transfer polymerization in order to investigate the structure of poly((2-dimethylamino)ethyl methacrylate)/sodium dodecylsufate complexes in water. The synthesized polymer chain conformation in water was studied as a function of deuterated sodium dodecylsulfate concentration using small angle neutron scattering. We found three transitions of the poly((2-dimethylamino)ethyl methacrylate) chain conformation induced by the added deuterated sodium dodecylsulfate. The transitions resulted from interactions between the polymer and the surfactant, so that micelles are formed along the polymer backbone above the critical aggregation concentration. The structure of micelles in a poly((2-dimethylamino)ethyl methacrylate)/deuterated sodium dodecylsulfate solution was analyzed through model fitting of the small angle neutron scattering data measured at the condition where the poly((2-dimethylamino)ethyl methacrylate) was contrast-matched with a mixture of 80% H₂O and 20% D₂O.     

Concentration effects of methylalumoxane, palladium and nickel pre-catalyst and monomer in the vinyl polymerization of norbornene

Summary The vinyl polymerization of norbornene with di-μ-chloro-bis-(6-methoxybicyclo-[2.2.1]hept-2-ene-5σ,2π)-palladium(II), Ni(acetylacetonate)₂ and Ni(2-ethylhexanoate)₂ in combination with methylalumoxane (MAO) was investigated by varying the molar MAO:metal-complex ratio, the norbornene:metal ratio and the metal concentration. The effects on the catalyst activity could be explained with a complexation equilibrium for the active homogeneous complex. Activity data in combination with polymer analyses suggest that at low, yet economical Al(MAO):metal ratios of 100 the fraction of active metal centers is less than 15%. The turnover frequency for the monomer insertion was found to reach 50 s⁻¹. Polydispersities around M_w/M_n= 2 indicate a coordination polymerization with chain transfer and a single-site character of the active centers. Received:27 February 2001/Revised version:11 November 2001/ Accepted: 20 November 2001     

Structure investigation of poly((2-dimethylamino)ethyl methacrylate)/sodium dodecylsulfate complexes in concentrated poly((2-dimethylamino)ethyl methacrylate) solutions using small angle neutron scattering

The structure of poly((2-dimethylamino)ethyl methacrylate)/sodium dodecylsulfate complexes in water was investigated as a function of poly((2-dimethylamino)ethyl methacrylate) concentration at a fixed sodium dodecylsulfate concentration using small angle neutron scattering. When either hydrogenated or deuterated sodium dodecylsulfate was added to poly((2-dimethylamino)ethyl methacrylate) solutions in D₂O, a peak was observed in the small angle neutron scattering which was characteristic of charged micelles. This peak shifted to higher q in both cases as poly((2-dimethylamino)ethyl methacrylate) concentration increased, indicating that the size and shape of micelles changed due to favorable interactions between poly((2-dimethylamino)ethyl methacrylate) and sodium dodecylsulfate. The small angle neutron scattering intensity of the micelles in the polymer/surfactant solutions was measured at the condition where poly((2-dimethylamino)ethyl methacrylate) was contrast-matched. It was possible to obtain information about the structure of the micelles using the Hayter–Penfold model. Based on the results from the fit of the SANS data, it was found that partial shielding provided by poly((2-dimethylamino)ethyl methacrylate) monomers being incorporated into the micelle shell significantly influenced both the form factor and the structure factor of micelles in the polymer/surfactant solutions. This led to a decrease in the micelle size and an increase in the number of micelles. It was found that any increased repulsive potential resulting from a smaller distance between the charged micelles was relieved by a decrease in the surface charge.     

Synthesis and optical properties of the [2.2]paracyclophane-containing π-conjugated polymer with a diacetylene unit

Summary Novel through-spaceπ-conjugated polymer based on poly(p-henyleneethynylene)/poly(p-phenylenebutadiynylene) hybrids containing a [2.2]paracyclophane unit in the main chain was synthesized by copper-catalyzed alkyne coupling reaction. The structure of the polymer was supported by ¹H NMR and IR spectra. The obtained polymer was soluble in common organic solvents such as THF, CH₂C1₂, CHC1₃ and toluene. The number-average of molecular weight of the polymer was estimated to be 63000 by GPC. The polymer emitted a bluish green light in solution and in the solid state. Received:24 September 2002/Revised version: 19 November 2002/Accepted: 19 November 2002 Correspondence to Yoshiki Chujo     

Conformation of oligo(ethylene glycol) grafted polystyrene in dilute aqueous solutions

Temperature induced conformational changes of poly(p-oligo(ethylene glycol) styrene) (POEGS) in aqueous solutions were investigated by small angle neutron scattering (SANS), neutron transmission and dynamic light scattering (DLS). The molecular weight of the polymer studied was 9400 g/mol with a polydispersity index of 1.18 and each repeat unit of the polymer had four ethylene glycol monomer segments. The polymer was water soluble due to the hydrophilicity of the OEG side chains and these solutions showed lower critical solution temperature (LCST) depending on the concentration of the polymer. Measurements of solution behavior were made as a function of temperature in the range of 25-55 °C for three polymer concentrations (0.1 wt%, 0.3 wt%, and 1.8 wt%). Neutron transmission measurements were used to monitor the amount of polymer which precipitated or remained in solution above the cloud point temperature (T_CP). DLS revealed the presence of large clusters in all solutions both below and above T_CP while SANS provided information on the structure and interactions between individual chains. It was found that in the homogeneous region below T_CP the shape of individual polymers in solution was close to ellipsoidal with the dimensions R_a = 37 Å and R_b = 14 Å and was virtually independent of temperature. The SANS data taken for the most concentrated solution studied (1.8 wt%) were fit to the ellipsoidal model with attractive interactions which were approximated by the Ornstein-Zernike function with a temperature-dependent correlation length in the range of 24-49 Å. The collapse of individual polymers to spherical globules with the radius of 15 Å above T_CP was observed.     

Irradiation effects on electrical properties of cellulose nitrate

Cellulose nitrate (CA-80-15) films were exposed to UV and neutron irradiations. An increase of the electrical conductivity was observed. The values of the activation energy diminish with irradiation from 0.42 to 0.15 eV for UV and to 0.31 eV for neutron irradiation. A sharp increase in the current was observed after exposing CA-80-15 samples to fission neutron fluences of 1*10⁷ n/cm². The electrical conduction in cellulose nitrate is governed by the Shottky mechanism. The value of the electron affinity of the polymer used is 4.46 eV. This value is increased after both types of irradiation. The dielectric permittivity (ε′) of the above samples together with the dielectric loss factor (ε″) were measured over a range of temperatures (293–403 K) at fixed frequencies (1*10³, 1*10⁴, and 1*10⁵Hz). Three neutron exposures (? = 1*10⁵, 1*10⁶, and 1*10⁷ n/cm²) were used. The obtained results made it possible to determine a complete set of conduction parameters including dielectric susceptibility χ, ac conductivity α_ac, and temperature coefficient of permittivity TC. © 1995 John Wiley & Sons, Inc.     

Neutron scattering of hydrophobically modified poly(ethylene oxide) in aqueous solutions in the presence of latex particles

The structure of aqueous solutions of hydrophobically end-capped poly(ethylene oxide), PEOM, in the presence of solid particles (latex) was investigated by small angle neutron scattering. Mono- and di-functionalised PEOMs with the same ratio of hydrophilic to aliphatic (C₁₆H₃₃) hydrophobic groups of molecular weights 16?000 and 32?000 g mol⁻¹, respectively, were compared. We used solvent conditions in which either PEOM or latex were matched by varying the ratio of water to heavy water. Initially, a decrease in the scattering intensity at small angles was observed when PEOM was added to a suspension of latex at constant concentration. A peak was observed in the structure factor which indicated repulsion between particles. The position of the peak lied at a lower q value for mono-functionalised PEO than for di-functionalised PEO. This observation may be explained by the formation of bridges between aggregates by the di-functionalised PEOM. On varying the solvent, the characteristic peak of PEOM alone disappears at low polymer concentrations due to PEOM adsorption onto the latex particles but reappears at higher polymer concentrations.     

(CH3)3SiBr/AlCl3 induced cationic polymerization of 1,3-pentadiene

Cationic polymerizations of 1,3-pentadiene (PD) with AlCl₃ in n-hexane were carried out in the absence and presence of trimethylsilyl bromide (Me₃SiBr or TMSBr). Structural evidence and proton trap experiment demonstrate that in the TMSBr/AlCl₃ induced polymerization the real initiating system is the combination of AlCl₃ with HBr resulting from hydrolysis of TMSBr by adventitious water existing in the system. The conversion of the polymerization is greatly increased by adding TMSBr, but the introduction of TMSBr does not exert an effect on the formation of gel (crosslinked product). The molecular weight of the polymer prepared by TMSBr/AlCl₃ system shows a maximum in the range of [TMSBr]/[AlCl₃] = 1, and excessive TMSBr gives rise to a drop of the polymer molecular weight. Kinetic data show that AlCl₃ and TMSBr/AlCl₃ induced polymerizations have the comparable polymerization rates. Received: 12 September 1997/Revised version: 4 November 1997/Accepted: 14 November 1997     

Investigation of the electrothermo-optical effect of a smectic LCP–nematic LC–chiral dopant ternary composite system based on SA ↔ N* phase transition

A sharp change in transmittance from a transparent state to a light scattering one within a tiny temperature range is induced accompanied with the heat-induced phase transition from a smectic-A (S_A) phase to a chiral nematic (N*) one in a side-chain smectic-A liquid crystalline polymer (S_ALCP)–low-molecular-weight nematic liquid crystal (NLC)–chiral dopant ternary composite system with a homeotropic boundary condition. By adjusting the polymer ratio, an induced N* phase exhibiting strong light scattering over a wide temperature region has been obtained. The resulting scattering texture retained in the S_A phase due to fast cooling from the N* phase can be rather stable and can be easily erased by cooling slowly from the N* phase to the S_A phase after the scattering texture being heated into the N* phase again or by application of an alternating current electric field on the scattering texture directly. Based on these characteristics, it is very possible that this composite system will be used as a novel thermal addressed liquid crystal display material with respect to a fast response, a high contrast, and a durable memory effect. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 623–631, 1999     

Heterogeneous cationic polymerization of 1,3-dioxolane and 1,3-dioxepane using grafted BF3 on silica

Summary A BF₃ complex has been grafted onto silica and used as initiator to polymerize 1,3-dioxolane and 1,3-dioxepane. Grafting the active centers leads to a decrease of the reaction rate. The molecular weight increases steadily, parallel to the monomer conversion and the polydispersity is rapidly stabilized at a low value. MALDI-TOF mass spectrometry analysis shows that most of the polymer chains are initiated by a proton and lost a CH₂O unit. An exchange process between polymer chains bound to the silica and those remaining in the reactional medium was proposed. Finally, a semi-continuous process was investigated by adding continuously dioxolane during a 100 hours period. Received: 21 February 2001/ Revised version: 2 November 2001/ Accepted: 6 November 2001     

Living polymerization of hexaethylcyclotrisiloxane

Summary Living polymerization of hexaethylcyclotrisiloxane was achieved with nBuLi-(nBuO)₃PO at room temperature to produce living poly(diethylsiloxane). The molecular weight of the polymer increased in direct proportion to monomer conversion and to the reciprocal to the initial nBuLi concentration. Molecular weight distribution remained 1.1–1.2 during the polymerization. The polymerization was completed only after 1 day despite no solvent was used. When a compound containing SiOH groups was added to the polymerization system, the number of polymer chain agreed with a sum of nBuLi and SiOH groups. Received: 29 June 1999/Revised version: 23 August 1999/Accepted: 25 August 1999     

Dilute-solution structure of charged arborescent graft polymer

The solutions of charged G1 arborescent polystyrene-graft-poly(2-vinylpyridine) copolymers in methanol-d4 and D₂O were investigated over a dilute concentration range ?=0.005-0.05 (?: mass fraction) using small-angle neutron scattering (SANS). Upon addition of acid (HCl) arborescent graft polymers became charged and a peak appeared in SANS data. The interparticle distance (d_exp) calculated from a peak position corresponded to the expected value (d_uni) for a uniform particle distribution. This indicates the formation of liquid-like ordering due to long-range Coulombic repulsions. The smaller dielectric constant of methanol-d4 resulted in long-range electrostatic repulsions persisting to lower polymer concentration than in D₂O. The slow mode scattering was observed by dynamic light scattering measurements for the same polymer solutions, indicating the presence of structural inhomogeneity in the solutions. Both the peak and slow mode disappeared by addition of NaCl or excess HCl into the solutions due to the screening of electrostatic interactions. The G1 polymer grafted with longer P2VP chains (M_w∼30,000 versus 5000 g mol) formed a gel on addition of HCl. This result reveals that molecular expansion is more significant for arborescent polymers with longer (M_w∼30,000) linear polyelectrolyte branches, resulting in gelation for ?>0.01. Upon addition of NaCl or excess HCl a gel transformed back to a liquid resulted from the screening of electrostatic interactions.     

Molecular structure of CaO–FeOx–SiO2 glassy slags and resultant inorganic polymer binders

The molecular structures of CaO–FeO_x–SiO₂ slags and their inorganic polymer counterparts were determined using neutron and X‐ray scattering with subsequent pair distribution function (PDF) analysis. The slags were synthesized with approximate molar compositions: 0.17CaO–0.83FeO–SiO₂ and 0.33CaO–0.67FeO–SiO₂ (referred to as low‐Ca and high‐Ca, respectively)_. The PDF data on the slags reasserted the predominantly glassy nature of this iron‐rich industrial byproduct. The dominant metal‐metal correlation was Fe–Si (3.20‐3.25 Å), with smaller contributions from Fe–Ca (3.45‐3.50 Å) and Fe–Fe (2.95‐3.00 Å). After inorganic polymer synthesis, a rise in the amount of Fe³⁺ was observed via the shift of the Fe–O bond length to shorter distances. This shortening of the Fe–O distance in the binder is also evidenced by the apparent rise of the Fe–Fe correlation at 2.95‐3.00 Å, although this feature may also suggest a potential aggregation of FeO_x clusters. In general, the atomic arrangements of the reaction product was shown to be very similar to the precursor structure and the dominance of the Fe–Si correlation suggests the participation of Fe in the silicate network. The binder was shown to be glassy, as no distinct atom‐atom correlations were observed beyond 8 Å.