苯二胺对聚苯胺电化学合成及其降解的影响

运用循环伏安法和紫外 可见吸收光谱分别研究了邻、间、对 3种苯二胺单体对苯胺聚合及其生成膜降解过程的影响 .结果表明 ,对苯二胺在催化苯胺聚合的同时加速了膜的降解 ,而邻、间苯二胺对聚合与膜的降解均起抑制作用 .这可能是由于 3种苯二胺结构的不同影响了聚合机理 ,并在一定程度上改变了膜的化学物理性质所致 .扫描电镜显示 ,苯二胺的加入对聚合膜的形态结构也有明显影响 ,与纯聚苯胺膜相比 ,共聚膜变得更加致密、光滑 .     

EFFECT OF ADSORPTION ON THE VISCOSITY OF DILUTE POLYMER SOLUTION*

Careful measurements of the dilute solution viscosities of polyethylene glycol and polyvinylalcohol in water were carried out. The reduced viscosities of both polymer solutions plot upward curves atextremely dilute concentration levels similar to the phenomena observed for many polymer solutions in theearly 1950's. Upon observation of the changes of the flow times of pure water in and the wall surfacewettability of the viscometer after measuring solution viscosity, a view was formed that the observed viscosityabnormality at extremely dilute concentration regions is solely due to the effect of adsorption of polymerchains onto the wall surface of viscometer. A theory of adsorption effect based on the Langmuir isothermswas proposed and a mathematical analysis for data treatment was performed. The theory could adequatelydescribe the existing viscosity data. It seems necessary to correct the viscosity result of dilute polymersolutions measured by glass capillary viscometer by taking into account the effect of adsorption in all cases.     

EFFECT OF POLYMERIZATION CONDITIONS ON THE MOLECULAR WEIGHT OF POLYPHENYLSILSISQUIOXANE

Samples of polyphenylsilsisquioxane (PPSQ)using CaF_2 or MgF_2 as the main catalysts hadbeen prepared under different polymerization conditions. The results were treated on anorthogonal design L_9 (3~4). All weight-average molecular weights (M_W ) of PPSQ had beenmeasured by gel permeation chromatography (GPC). Effects of polymerization conditionsincluding reaction temperature, composition of the dual catalysts (CaF_2 or MgF_2 and DCC),mixture of solvents and reaction time on M_W of PPSQ have been discussed. The quantity of thecatalysts is the most important factor that affects M_W of PPSQ. Reaction temperature is thesecond important factor. Appropriate polymerization condition has been established to get PPSQwith high M_W.     

THE EFFECT OF HOT DRAWN ON THE PHYSICAL AGING OF ATACTIC POLYSTYRENE

The physical aging behavior of atactic polystyrene (aPS) films achievedunder different drawing conditions has been studied by optical birefringence and modulatedifferential scanning calorimeter (m.d.s.c.). The results show that on annealing at specifictemperature below glass transition temperatue (T_g), the enthalpy relaxation (△H) and T_gdecrease with increasing of birefringence (△n). On the other hand, the effect of moleculardraw ratio (MDR) is confusing: △H and T_g decrease with increasing of MDR in the earlystage of aging, but the MDR's effect become unobvious with the development of aging.It may be concluded that the ordered domain generated by the drawing below or aboveglass transition temperature will affect the development of physical aging behavior. Theviewpoint of cohesional entanglement is used to account for the above observations.     

STUDY ON THE EFFECT OF POLYSTYRENE SULFONIC ACID MACROMOLECULES ON THE POLYMERIZATION OF ACRYLAMIDE

The effect of polystyrene sulfonic acid (PSSA) macromolecules on the polymerization of acrylamide (AM) has been studied. It was found that the rates of polymerization of AM were greatly increased in the presence of PSSA in the polymerization system.The maximum value of the rate of polymerization of AM was obtained when the ratio of [—SO_3H]: [AM] reached 3:1. When the insoluble crosslinked PSSA was used instead of the soluble one, this effect decreased considerably. The interaction between molecules of PSSA and AM was determined by infrared spectroscopy, elementary analysis and X-ray photoelectron spectroscopy. The combination form, —SO_3-NH_3~ CO—, formed between sulfonic group and amide group was found to be existed since the infrared absorption band of —NH_2 shifted from 3400cm~(-1) to 3150 cm~(-1), the binding energy of electron N_(18) changed from 399.7 eV to 401.3 eV, and the atomic ratio of N to S of the products was similar to the ratio of reagents. Based on these experimental results, the mechanism of AM polymerization in the presence of PSSA is proposed. The initial step is the combination of AM with sulfonic group to form —CONH_3~ , then followed by polymerization on the PSSA macromolecule. The role of PSSA on the polymerization of AM is discussed.     

电聚合苯胺过程的在线紫外-可见光谱

用在线紫外-可见光谱电化学的方法对0.5mol/L硫酸水溶液中苯胺在ITO导电玻璃电极上的电化学聚的过程进行了研究.结果表明在循环伏安条件下苯胺发生了电聚合,聚合速率与苯胺浓度成正关系;而且在线紫外-可见电化学光谱表明,在0.01mol/L苯胺溶液的电聚合过程的诱导期较长.恒电位条件下的在线紫外-可见电化学光谱显示苯胺浓度为0.05mol/L,电位为0.8V时,在ITO电极上苯胺低聚合物中间体可能产生于聚苯胺形成之前;而0.01mol/L苯胺在0.8V电位下不发生聚合,但在线紫外-可见光谱又显示此时在电极上可能存在小的苯胺低聚物的中间体;在线紫外-可见光谱表明这种中间体是可能产生并存在电极表面上的.     

THE EFFECT OF POLAR ADDITIVES ON THE γ RADIATION INDUCED POLYMERIZATION OF STYRENE*

The γ induced polymerization of styrene in the presence of polar additives such as tributylphosphate, triethyl amine and ethanol was studied at dose rate of 5.0×10~(17) eV/ml. min. The re-sult shows that radiation induced polymerization of styrene was sensitized by the three kinds ofadditives at the approximate same rate and the experimental results were in agreement with thetheoretical calculation of WAS equation. The cause of sensitization is due to the proton transfer.     

THE EFFECT OF MATRIX TOUGHNESS ON THE BRITTLE-DUCTILE TRANSITION OF HDPE/CaCO_3 BLENDS

The effects of HDPE matrix toughness on the brittle-ductile transition of HDPE/CaCO_3blends are investigated. Not all HDPE can be toughened by CaCO_3 particles. The ability of thematrix to yield plays a fundamental role in determing whether HDPE can be toughened or not.There exists a critical matrix toughness (I_(sc)≈45J/m) below which HDPE can not be toughenedobservably by CaCO_3 particle at given average size, and above which the critical matrix ligamentthickness (τ_?) is proportional to matrix impact strength.     

THE EFFECT OF CLAY DISPERSION ON THE CRYSTALLIZATION AND MORPHOLOGY OF POLYPROPYLENE／CLAY COMPOSITES

PP/clay composites with different dispersions, namely, exfoliated dispersion, intercalated dispersion and agglomerates and particle-like dispersion, were prepared by direct melt intercalation or compounding. The effect of clay dispersion on the crystallization and morphology of PP was investigated via PLM, SAXS and DSC. Experimental results show that exfoliated clay layers are much more efficient than intercalated clay and agglomerates of clay in serving as nucleation agent due to the nano-scale dispersion of clay, resulting in a dramatic decrease in crystal size (lamellar thickness and spherulites) and an increase of crystallization temperature and crystallization rate. On the other hand, a decrease of melting temperature and crystallinity was also observed in PP/clay composites with exfoliated dispersion, due to the strong interaction between PP and clay. Compared with exfoliated clay layers, the intercalated clay layers have a less important effect on the crystallization and crystal morphology. No effect is seen for samples with agglomerates and particle-like dispersion, in regard to melting temperature, crystallization temperature, crystal thickness and crystallinity.     

EFFECT OF ACIDITY ON ACID-SENSITIVE UV CURING SYSTEM*

By using diphenyliodonium salts with different counterions as photo acid generators (PAGs), theeffect of acidity on ring-opening polymerization of epoxy monomers and polycondensation of polyol withhexamethoxymethyl melamine (HMMM) was studied. The result shows that the rate of ring-openingpolymerization is evidently dependent on the acidity of the acid and strong photo-generated acid is required.However, there is a leveling effect in the polycondensation system; if the photo-generated acid is strongerthan protonated HMMM, the acidity does not obviously affect the polycondensation rate.     

NOVEL POLYPYRROLE MICROSTRUCTURES GENERATED BY DIRECT ELECTROCHEMICAL OXIDATION OF PYRROLE ON p-TYPE SILICON SUBSTRATE

Polypyrrole microstructrues with morphology like bowls, cups, goblets and bottles have been electrochemicallygenerated by direct oxidation of pyrrole on p-silicon substrate in the aqueous solution of camphorsulfonic acid. The well-ordered microstructures can stand upright on the working electrode surface and their morphological features can be easilycontrolled by changing the electrochemical polymerization conditions. The growing process of microstructures was studiedby scanning electron microscopy. The microstryctures made of polypyrrole films in doped state were charaterized by Raman and Infrared spectra.     

EFFECT OF PAN-MILLING ON RHEOLOGICAL PROPERTIES OF HIGH DENSITY POLYETHYLENE*

The effect of pan-milling on the rheological properties of high density polyethylene (HDPE) was studied. Aninnovative milling apparatus, viz. an inlaid pan-mill, was used. Melt indexer, capillary rheometer, Haake Rheocord 90 single-screw extruder and Brabender rheometer were used to evaluate the rheologieal properties of HDPE. HDPE with higher initialmolecular weight and larger particle size was easier to degrade under pan-milling stress, as indicated by the melt index.Pressure oscillation in capillary flow occurred at significantly higher shear stress and shear rate for milled HDPE than forunmilled HDPE. The apparent shear viscosity of HDPE decreased with increasing times of milling. After milling, the flowactivation energy decreased and thus the sensitivity of viscosity to temperature was reduced. Die pressure and torque duringsingle screw extrusion were reduced significantly after milling. Plasticizing time as measured in a Brabander mixer decreasedmarkedly with increasing milling times.     

SYNTHESIS OF MBS RESIN BASED ON MOLECULE DESIGN

The relationships between the properties of PVC-MBS polyblend and of the MBS multiphase structure and between the MBS structure and polymerization parameters are studied theoretically and experimentally. MBS resin synthesized from the molecule design principle is suitable to prepare PVC-MBS polyblend with good transparency and high impact strength.     

SPECIAL EFFECT OF ULTRA-FINE RUBBER PARTICLES ON PLASTIC TOUGHENING

According to the present theories of plastic toughening, it is impossible to enhance the toughness, stiffness and/orheat resistance of plastics simultaneously by using rubber. A series of novel nano-rubber particles (UFPR) were introduced,which were prepared through irradiating common rubber lattices and spray drying them. Epoxies toughened with UFPRshowed a much better toughening effect than those with CTBN, and the heat resistance of epoxy was unexpectedly elevated.For polypropylene toughening, UFPR can improve the toughness, stiffness and heat resistance of PP simultaneously. Thesespecial toughening effects overcome the deficiencies in rubber toughening technology and are worth further investigating.     

THE EFFECT OF MONOMERS FEEDING METHODS ON EMULSION COPOLYMERIZATION OF VINYLIDENE CHLORIDE AND ACRYLATES

The emulsion copolymerization of vinylidene chloride (VDC) with methyl-methacrylate(MMA) and acrylonitrile (AN) was carried out by batch, seeded batch and semicontinuous pro-cesses,respectively. Significant differences were found in the physical and mechanical propertiesof the latexes and films, depending on the methods of monomer feeding. The results both intheory and experiments demonstrated that the copolymer composition and the length of the VDC sequences in the copolymer could be controlled by the modes of monomer feeding process.     

EFFECT OF PAN-MILLING STRESS ON CRYSTAL STRUCTURES OF HIGH DENSITY POLYETHYLENE

A detailed study was performed on the crystal structures of pan-milled high-density polyethylene (HDPE) usingdifferential scanning calorimetry (DSC) and X-ray diffraction. The crystallinity of HDPE first decreased slightly, followed bya gradual increase with increasing milling times. Monoclinic crystals appeared after 4 cycles of milling. With increasingtimes of milling, the proportion of monoclinic crystals increased significantly while the proportion of orthorhombic crystalsdecreased gradually. With increasing times of milling, the crystallite size of orthorhombic form decreased greatly, while thesize of monoclinic crystallites kept almost constant during milling.     

THE EFFECT OF ETHERS ON ALTERNATING COPOLYMERIZATION OF BUTADIENE AND PROPYLENE CATALYZED BY VANADIUM-ALUMINUM SYSTEM

The effect of five ethers on alternating copolymerization of br(?)adiene and propylene were investigated. It was found that under appropriate conditions, by adding ether into reaction system, the conversion could be increased by 10-20% and the catalytic efficiency doubled at -45℃. The interaction between ether and active center was also studied.     

SHAPE MEMORY EFFECT OF SLIGHTLY-CROSSLINKED POLYETHYLENE

A series of slightly crosslinked polyethylenes (SXLPE) was prepared by aone-step method using dicumyl peroxide as crosslinking agent in a Haake Mixer. The gelcontents G (Soxhlet extracted) of the samples are in the range from 5% to 20% by weight.Their shear viscosity, crystallization and melting behavior, dynamic mechanical propertiesand shape recovery effect were systematically investigated in terms of the content of thecrosslinking agent. It shows that under certain experimental conditions the SXLPE's mayexhibit good shape fixation ability and shape memory properties, which are similar to thoseof the commercially available shape memory polyethylenes prepared by gamma-irradiationtechnique. However the shape memory behavior of these samples is not very stable due totheir low crosslinking degree, or gel content. Thus their application is limited in specialcases with fast strain fixing procedures.     

STUDIES ON THE KINETICS OF PROPYLENE POLYMERIZATION WITH THE COMPLEXTYPE TiCl_3 CATALYST

The active center concentration C_p, the rate constant k_p, and the activation energy of chain propagation E_p in the polymerization of propylene with complex-type TiCl_3-(C_2H_5)_2AlCl catalyst system were studied. The Mn was corrected by (?) value determined by GPC. The values thus obtained for C_p, k_p, and E_p at 50℃were 3.01 mol/mol Ti, 6.27 1/mol·sec, and 5.10 Kcal/mol respectively.The kinetic parameters were compared with those obtained from conventional TiCl_3·AlCl_2 catalyst, showing that the higher activity of the complex-type catalyst over the conventional catalyst is not only due to the higher C_p of the former, but to a greater extent due to the increase of the k_p value.     

EFFECT OF TACTICITY OF PMMA ON CRYSTALLINE STRUCTURE OF POLY VINYLIDENE FLUORIDE

Fourier transform infrared spectroscopy (FTIR) has been used to study the effect of tacticityof PMMA on β phase formation of poly vinylidene fluoride (PVF_2) during quenching process.For pure PVF_2, quenching at lower temperature results in the formation of β phase crystallites.The critical quenching temperature for β phase formation is about 30℃. Adding a given amountof PMMA (30%) results in the increase of the critical quenching temperature. For the blends ofPVF_2 with atactic PMMA (a-PMMA), the critical quenching temperature is about 45℃, whilefor the blends with syndiotactic PMMA (s-PMMA), attains to about 70℃.