VISCOMETRIC STUDY OF POLY(METHYL METHACRYLATE) AND POLYSTYRENE BLENDS IN DIFFERENT SOLVENTS

The intermolecular interaction between poly(methyl methacrylate) (PMMA) and polystyrene (PS) intetrahydrofuran (THF) and N,N'-dimethyl formamide (DMF) solvents was studied at 28℃ using a dilute solution viscometrymethod. Solvent is believed to play a key role in characterizing the viscosity behavior of the polymer solution. The intrinsicviscosity and viscosity interaction parameter were experimentally measured for the binary (solvent/polymer) and for theternary systems in two solvents. The compatibility of the polymer mixture was discussed in terms of the sign of △b_m. Theresults show that the compatibility of PMMA/PS blend in DMF is larger than that in THF.     

SOLVENT QUALITY AND SOLUTION BEHAVIOR OF NYLON 12

The refractive index increment,dynamic and static laser light scattering,intrinsic viscosity[η]and Huggins constant(K_H)of nylon 12 have been measured in m-cresol and sulphuric acid/water system at 10-60℃.The intrinsic viscosity,R_H,R_g,A_2,and(~2)~(1/2)(calculated from viscosity data)and"a"values of nylon 12 are found to be higher in m-cresol than in sulphuric acid.All these parameters decrease with the increase in water contents in sulphuric acid.The refractive index increment,K_H and activation energy show an opposite trend to that of[η].The intrinsic viscosity,R_H,R_g,A_2, and(~2)~(1/2) have maximum values around 30-40℃in sulphuric acid/water system,whereas in m-cresol they fall at about 20℃.It has been concluded that the variation in size,interaction parameter(second virial coefficient),[η]and K_H of the polymer solutions with the alteration in solvent composition and temperature are the out come of change in thermodynamic quality of solvents,selective adsorption,hydrogen bonding and conformational transitions.It has also been concluded that the increase in temperature first enhances the quality of the solvent,encourages hydrogen bonding and specific adsorption, and then deteriorates,bringing conformational transitions in the polymer molecules.However,the addition of water to sulphuric acid continuously deteriorates the solvent quality.This characteristic of the solvent system brings conformational changes in the polymer especially at low temperatures.     

EFFECT OF THE COMPOSITION OF m-CRESOL/H2O SOLVENT ON HYDRODYNAMIC PROPERTIES OF NYLON 6

The intrinsic viscosity [ η], Huggins constant (KH), [ η]0, α3 and flow activation energy values of nylon 6 have been measured in water/m-cresol (0/100-20/80) systems at different temperatures (20-60℃). It has been found that the intrinsic viscosity, [η]0 and α3 increase with the increase in water contents in m-cresol up to 15% and then decrease. They increase with the increase in temperature irrespective of solvent composition. It has been noted that the percent increase of α3 is the highest at 60℃ and the lowest at 20℃ for a particular solvent system. The intrinsic viscosity data obey Arrhenius equation over the considered conditions. The activation energy and the KH values decrease very sharply with the addition of water,giving a minimum value at 15% of water and then increase slowly. The variation of all the parameters has been explained in terms of variation in thermodynamic quality of solvent with the addition of water to m-cresol and change in temperature,resulting in the change of conformational and orientational properties of polymer molecules. This change of solvent quality also results in variation of selective sorption of solvent over the polymer, such as hydrogen bonding, etc.     

Molecular dynamics simulations of the hydration of poly(vinyl methyl ether):Hydrogen bonds and quasi-hydrogen bonds

Atomistic detailed hydration structures of poly(vinyl methyl ether)(PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution functions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain,and there still exists a significant amount(10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentration as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer,which leads to inefficient contacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds,but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry(DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME,which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ～27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ～27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition,at the concentration of 86%,each ether oxygen atom bonded with water is assigned 1.56 water molecules on average,and 'free' water molecules emerge at the concentration of around 54%.     

EFFECTS OF COUPLING AGENTS ON THE RHEOLOGICAL BEHAVIOR OF KAOLIN FILLED POLYAMIDE 6

An experimental study was carried out to investigate the effects of coupling agents on the rheological properties of kaolin filled polyamide 6(PA6). We have investigated the state of dispersion and interfacial interaction of the filled systems, using 'h:anning electron microscopy (SEM) and Molau test, respectively. It is found that the addition of the coupling agents to the PA6/ kaolin (20 wt percent) significantly decreases the melt viscosity and the melt elasticity (first normal stress difference). Moreover, the states of dispersion and the polymer/filler interactions have significant influences on the rheological properties of kaolin/PA6 systems. The rheological behavior of KH550 kaolin /PA6 system is different from that of KH560 kaolin/PA6 system, although chemical reactions have taken place between the surface of KH550 kaolin (or KH560 kaolin) and PA6 matrix during melt processing. This is attributable, in part, to the differences in the state of dispersion of kaolins in PA6 matrix and, to a great extent, to the differences in the extent of chemical reactions that have taken place between the filler and polymer matrix.     

High-efficiency single and tandem fullerene solar cells with asymmetric monofluorinated diketopyrrolopyrrole-based polymer

Design and synthesis of low bandgap(LBG) polymer donors is inevitably challenging and their processability from a non-halogenated solvent system remains a hurdle to overcome in the area of highperformance polymer solar cells(PSCs).Due to a high aggregation tendency of LBG polymers,especially diketopyrrolopyrrole(DPP)-based polymers coupled with bithiophenes in the polymer backbones,their widespread adoption in non-ha logena ted solvent-processed PSCs has been limited.Herein,a novel LBG DPP-based polymer,called PDPP4 T-1 F with asymmetric arrangement of fluorine atom,has been successfully synthesized and showed an outstanding power conversion efficiency(PCE) of 10.10% in a singlejunction fullerene-based PSCs.Furthermore,an impressive PCE of 13.21% has been achieved in a tandem device from a fully non-halogenated solvent system,which integrates a wide bandgap PDTBTBz-2 F polymer in the bottom cell and LBG PDPP4 T-1 F polymer in the top cell.The achieved efficiency is the highest value reported in the literature to date in fullerene-based tandem PSCs.We found that a uniformly distributed interpenetrating fibril network with nano-scale phase separation and anisotropy of the polymer backbone orientation for efficient charge transfer/transport and suppressed charge recombination in PDPP4 T-1 F-based PSCs led to outstanding PCEs in single and tandem-junction PSCs.     

Photoinduced intramolecular electron transfer of fluorescein and violgen, carbazole

A series of polyads consisting of covalently-(CH2)4-linked fluorescein with carbazole and violger.Live been synthesized and characterized The studies of absorption,emission spectra and fluorescence lifetime quenching indicated that the intramolecular fluorescence quenching of fluorescein by violgen is mainly a static process through the formation of non emission complex (fluorescence quenching efficiency φQ=0.97,lifetime quenching efficiency φH 0,quenching efficiency of formation of non-emission complex φC=0.97); while the quenching by carbazole is mainly a dynamic electron transfer process (φQ=0.63,φET=0.63,φC=0).In the violgen-fluorescein-carbazole triads,φQ=0.97,Q ET=0.65,φC=0.32,which suggests that the photoinduced interaction of fluorescein-carbazole pair and that of violgen-fluorescein pair are in a competitive process,the dynamic electron transfer from carbazole to fluorecein is dominant in the process The free energy change of the photoinduced electron transfer and the back reac-tiorns i     

VISCOMETRIC INVESTIGATIONS OF POLYVINYLPYRROLIDONE IN MIXED SOLVENTS AND WITH VARYING TEMPERATURE

The viscosity behavior of polyvinylpyrrolidone (PVP) has been determined at 25℃ in mixed solvents comprising water/dimethylformamide (DMF) and water /methanol (MeOH). Analysis of the data has considered the PVP as being both host and guest polymer in solution. The intrinsic viscosity of PVP in DMF is higher than in water and in MeOH, but also increases in a mixed solvent with high water content because of the effect of polymer-solvent interactions. It was also found that the intrinsic viscosity of PVP at finite concentration, [ηpvp]c decreases with an increase in the concentration of PVP in solution. The viscosity behavior of PVP in a mixed solvent is affected by the concentration-dependent intermolecular excluded volume effect, which can be quantitatively expressed by the parameter, bY, which reflects the shrinkage of PVP chain coils, resulting in a decrease of [ηpvp]c. The effect of temperature on the viscosity behavior of PVP in MeOH shows that the interaction parameter increases up to a maximum value, and then decreases after a certain temperature.     

STUDY ON THE MECHANISM OF NYLON 6, 6 DISSOLVING PROCESS USING CaCl_2/MeOH AS THE SOLVENT

A discussion of the mechanism of nylon 6, 6 dissolving process using CaCl_2/MeOH as the sol-vent is presented. The calcium chloride forms a complex compound with nylon 6, 6 by breakingthe hydrogen bonds. The melting point of the CaCl_2 --nylon 6, 6 complex was found to be reducedby 91K relative to the pure nylon 6, 6 polymer. The role of methanol is somewhat similar to acatalyst. The results demonstrate that the complexation of a Lewis acid (CaCl_2) and a Lewis base(nylon 6, 6) can be used to probe intermolecular interactions such as hydrogen bonding in polymers, to modify the polymer properties and mediate its solubility and processing.     

STUDY OF PHOTOSENSITIZED INITIATION SYSTEMS CONTAINING OXYGEN Ⅴ. THE EFFECT OF MERCAPTAN ADDITIVES

A kinetic study on the photopolymerization of methyl methacrylate (MMA) with benzophenone(BP)/triethylamine (TEA)/mercaptan systems as initiator has been carried out in the presence of oxygen.It was found that both aliphatic and aromatic thiols promote the photooxidation process, leadingto obvious decrease in induction period of photopolymerization. The rate-aereleration of aromaticthiols is more effective than that of aliphatic ones, such as p-toluene thiol used as additive increasesthe relative quantum yield φ_(O2)/φ_(N2) to 1.8.     

A 13C NMR study of the structure of sulfur-stabilized carbanions

The structure of the lithium and potassium salts of φSCH₃,φSOCH₃,φSO₂CH₃,φSO(NCH₃)CH₃ has been studied by ¹³C NMR in different solvents. The results show that the metalated carbon is nearly pyramidal in and nearly planar in φSOCH₂^?M⁺, whatever the solvent are cation are φSO₂CH₂^? φSCH₂^?M⁺ and φSO(NCH₃)CH₂^?M⁺ are in an intermediate hydridization state, cation and solvent dependent. For the sulfoxide, a four-center chelate is proposed, stable to strong solvating agents and only disrupted by cryptands. It is very likely responsible for the planar configuration of the anionic carbon.The low temperature study of φSOCH₂Li shows the existence of aggregates in THF. HMPA or external lithium salts disrupt these associations, giving rise to other species.The ¹³C NMR parameters of the whole series of sulfur-stabilized carbanions are quite consistent with the date reported for phosphorous and arsenic ylids: the

coupling constants appear to be a good probe of the geometry of the anionic carbon, whereas the chemical shifts are rather insensitive to its hybridization state.     

ZnTBPPc光物理化学性质的溶剂化效应

The solvent viscosity dependence of the photophysical and photochemical properties of tetra(tert-butylphenoxy)phthalocyaninato zinc(II) (ZnTBPPc) is presented. The fluorescence quantum yields (ΦF) and Stern-Volmer′s constant (KSV) for ZnTBPPc fluorescence quenching by benzoquinone in all the solutions followed a semi-empirical law that depends only on the solvent viscosity. ΦF values vary between 0.08 in tetrahydrofuran (THF) and 0.14 in dimethylsulphoxide (DMSO). Triplet quantum yields (ΦT) and lifetimes (...     

Concerning the Conformation of Isolated Benzylideneaniline

From PE.-spectroscopical studies the torsional angle φ of the N-phenyl ring in isolated benzylideneaniline 1 has been found to be definitely smaller than φ= 90°. An approximate valueφ= 36°has been estimated which is even smaller than the one observed in the crystal (φ= 55°) and suggested to prevail also in solutions of 1 . A reevaluation of the gas phase optical spectrum of isolated 1 supports a torsional angle similar to that found in the other phases. Calculations of the most stable conformation of 1 as well as of stilbene and azobenzene by the MINDO/3-technique lead to torsional angles φ= 90° for both phenyl rings in all cases. These results are at variance with the experimental results and suggest that MINDO/3-like its less advanced precursor MINDO/2 or like CNDO/2–is unreliable for low energy processes involving rotation of π-systems connected by essential single bonds. It is concluded that the π-energy of benzylideneaniline, like that of stilbene or azobenzene, would favor a planar conformation. The increased torsional angle in 1 as compared to the other two iso-conjugate systems arises from a larger steric interaction between phenyl- and bridgeprotons.     

9,10-二氰基蒽敏化光氧化反应的溶剂效应

本文通过α,β-蒎烯及1,4-二苯基-1,3-丁二烯的9,10-二氰基蒽(DCA)敏化光氧化反应在一系列溶剂中产物生成的相对量子效率及单线态氧(¹O₂)产物的含量,对β-蒎烯在乙腈中的反应动力学分析,讨论了反应的溶剂效应,证明了DCA敏化光氧化反应,包括¹O₂产物都是经由电子转移的反应机理。     

Solvent effect on 1O2 yield and the mechanism of polycyclic hydrocarbon triplet-state quenching by oxygen

The yield of singlet oxygen (φ_1O2) in quenching of the triplets of 1,2,5,6-dibenzanthracene, 1,2-benzanthracene, anthracene, pyranthrene and duroquinone by oxygen has been studied using the laser photolysis technique. It was found that in toluene φ_1O2 = 1.0 ± 0.1 and the quenching occurs via the energy transfer mechanism on account of an exchange interaction in the encounter complex. In benzonitrile the charge transfer contributes to a significant extent, leading to a considerable decrease in φ_1O2.     

Effect of liquid-liquid demixing on the membrane morphology,gas permeation,thermal and mechanical properties of cellulose acetate hollow fibers

The polymer/solvent/nonsolvent systems with different L-L demixing rates were prepared by employing a binary solvent mixture consisting of two solvents - one exhibits an instantaneous liquid-liquid (L-L) demixing process, while the other exhibits a delayed L-L demixing process. It was found that an increase in the delay time of L-L demixing results in a denser membrane structure, an increase in fiber mechanical strength, a delay desorption of moisture in membrane, and a decrease in gas permeance, for a hollow fiber fabrication system consisting of cellulose acetate (CA) (polymer), N-methyl-pyrrolidone (NMP) (solvent having an instantaneous L-L demixing property), tetrahydrofuran (THF) (solvent having a delayed L-L demixing property) and water (nonsolvent). Hollow fibers prepared under an instantaneous L-L demixing process tends to have more mechanically weak points (flaws) than those prepared under a delayed L-L demixing process. Surprisingly, SEM observation suggests that membranes wet-spun from solutions containing both THF and NMP tend to have a rough outer skin morphology. Inconsistent demixing and the collapse of the outer nascent skin may be the main causes. In addition, the effect of bore fluid chemistry on fiber performance is much more pronounced for systems having a delayed L-L demixing mechanism than that having an instantaneous L-L demixing.     

Demixing effects in thin-layer chromatography with NH2-modified silica gel precoated plates

Summary Demixing effects in thin-layer chromatography have been investigated with NH₂-modified silica gel precoated plates and for frequently used hydroorganic binary solvents of various compositions with salt addition.The position of the solvent demixing front depends on: (1) solvent composition, (2) nature of the organic modifier and (3) salt concentration. Whatever the organic modifier, for a given water percentage in the developing solvent, solvent demixing is found to occur at the same concentration of NaCl.     

The Differential Relationships of Thermodynamic Variables for the Equilibrium of Heterogeneous Substances

For the system without adiabatic walls, rigid walls or semi-permeable walls and without chemical reactions or without other restrictions except restrictions of phase equilibrium conditions, if the number of components of the system is k and the number of phases is φ, the degree of freedom of the system at equilibrium is f=k-φ+2. Because the degree of freedom is incapable of being negative, f=k-φ+2≥0, viz.φ≤k+2. For the heterogeneous equilibrium, the number of phases is at least 2, so φ=k+2-f≥2, viz. f≤k. Hence the range of change of φ and f is 2≤φ≤k+2,0≤f≤k, respectitvely. If φ=k+2, there are no independent variables in the system at equilibrium. If φ=k+1, there is one independent variable; if the temperature is selected as the independent variable, the other dependent variables can be expressed as the function of the temperature. If φ=k, there are two independent variables; if the temperature and pressure are selected as the independent variables, the other dependent variables can be expressed as the function of the temperature and pressure. If 2≤φ≤k-1, there are more than two independent variables; if the temperature, pressure and some concentrations are selected as independent variables, the other dependent variables can be expressed as the function of the temperature, pressure and these concentrations. The differential relationships of dependent variables and independent variables are educed out according to the principle of phase equilibriums for 2≤φ≤k-1. In any phase the number of the variables is(k+1), viz. temperature T, pressure p and (k-1) mole fractions x1, x2,…, xk-1. The temperature and pressure are common variables of every phase. The number of independent variables is at best k for the heterogeneous equilibriums of k components. The temperature, pressure and (k-2) concentrations are selected as independent variables. The independent concentration variables are selected entirely from the first phase and the concentration variables of the other phases all act as dependent variables. There is at least one dependent concentration variable in the first phase.     

THE EFFECT OF MEDIUM POLARITY ON THE HEMATOPORPHYRIN-SENSITIZED PHOTOOXIDATION OF l-TRYPTOPHAN

Abstract The 83 μM hematoporphyrin (HP)-sensitized photooxidation of 0.1 mM tryptophan in aqueous solution buffered at pH 7.4 or in binary mixtures of phosphate buffer and organic solvents of higher (formamide) or lower (N,N-dimethylformamide, methanol, ethanol, tetrahydrofuran) polarity proceeds by a pure singlet oxygen (¹O₂) mechanism as suggested by azide quenching experiments, the rate-enhancing action of deuterated solvents, and the lack of any significant reaction between triplet HP and tryptophan. Both the first-order rate constant of the photoprocess and the photooxidation quantum yield (φ= 0.011 in phosphate buffer at pH 7.4) increase when the medium polarity is increased (e.g. φ= 0.024 in 90% formamide); this results mainly from the greater quantum yield of ¹O₂ generation and the longer lifetime of ¹O₂. The intrinsic reactivity of ¹O₂ with tryptophan is independent of formamide concentration. A moderate decrease in the medium polarity (e.g. in the range 0-30% methanol) enhances the efficiency of tryptophan photooxidation (φ= 0.014 in 30% methanol) as a result of the enhanced quantum yields of triplet HP and ¹O₂ formation. In contrast, the overall photooxidation rate is depressed at high concentrations of low-polarity organic solvents (e.g. φ= 0.0039 in 90% methanol) due to a 5.5-fold drop of the rate constant for the ¹O₂-tryptophan reaction which counteracts the enhancement of the lifetime and quantum yield of triplet HP and ¹O₂. The solvent composition also affects the equilibria between monomeric and multimeric forms of HP. However, under our experimental conditions, the aggregation state of HP appears to exert only a minor influence on the efficiency of tryptophan photooxidation.     

含氧光敏引发体系的研究——V.硫醇添加剂的作用

采用二笨甲酮/三乙胺/硫醇体系作为引发剂,在含氧条件下进行了MMA光聚合反应的动力学研究。实验结果指出,芳香族和脂肪族的硫醇都能加速体系中的光氧化反应,使聚合反应诱导期缩短,芳香族硫醇对聚合反应的加速作(?)比脂肪族硫醇有效。例如,对-甲苯硫酚作添加剂时,使相对量子收率φO_2/φN_2增加到1.8。