Oxidation of n-Butanol and 2-Pentanol with Molecular Oxygen in Supercritical CO2

Oxidation of n-butanol and 2-pentanol using molecular oxygen in supercritical (SC) CO2 with and without co-solvent is investigated. The results showed that the reaction selectivity is high when the reaction is carried out in SC CO2. It has been observed that co-solvent affects conversion and selectivity of the reaction considerably.     

POLYMERIC NANOPARTICLES FROM SUPERCRITICAL CO2 MICROEMULSION POLYMERIZATION

Herein, we reported the microemulsion polymerization in supercritical carbon dioxide. With the aid of an anionic phosphate fluorosurfactant （bis-[2-（F-hexyl）ethyl]phosphate sodium）, water-soluble/CO2-insoluble acryloxyethyltrimethyl ammonium chloride monomer and N,N＇-methylene-bisacrylamide cross-linker were solubilized into CO2 continuous phase via the formation of water-in-CO2 （w/c） microemulsion water pools. Initiated by a CO2-soluble initiator, 2,2＇-azo-bisisobutyronitrile （AIBN）, cross-linked poly（acryloxyethyltrimethyl ammonium chloride） particles were produced and stabilized in these w/c internal water pools. Nano-sized particles with sizes less than 20 nm in diameter and narrow particle size distributions were obtained.     

–ONNO–四齿配体负载铜(Ⅱ)配合物的合成与结构研究:环二酯开环聚合的高效催化剂(英文)

The –ONNO– tetradentate Schiff base ligand N,N'-bis(2-hydroxy-3- methoxybenzaldehyde) benzene-1,2-diamine(HMBBD) has been synthesized. The ligand was attached to copper(Cu-HMBBD) in methanol under N_2 atmosphere to give a mononuclear complex. The reactivity of this complex in the ring-opening polymerization(ROP) of lactide has been studied. The complex has a square planner geometry, as determined by X-ray diffraction studies. The copper complex is highly active towards the ring-opening polymerization of lactide, and the rate of polymerization is heavily dependent on the initiator used. The copper complex allows controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number average molecular weight. Based on the literature, a mechanism for the ROP of lactide has been proposed.     

Study on the Phase Behavior of Supercritical CO2／Dynol—604／Water System and Solubilization of Methyl Orange in the Microemulsions

It was found that Dynol-604, a non-fluorous and no silicon-containing nonionic surfactant,was soluble in supercritical (SC) CO2. The phase behavior of SC CO2/Dynol-604/water system was studies. The results showed that one-phase water-in-CO2 microemulsions could be fromed. The solubilization of methyl orange in the microemulsions proved further the existence of water domain in the microemulsions.     

Fischer-Tropsch Reaction Kinetics of Cobalt Catalyst in Supercritical Phase

Fischer-Tropsch synthesis under supercritical phase condition was examined in a continuous and a high-pressure fixed bed reactor by employing a cobalt catalyst (Co-R.Ru/γ-Al2O3). An integral reactor model involving Fischer-Tropsch reaction kinetics in the supercritical fluid n-hexane was used to describe the overall performance. On the basis of Langmuir-Hinshelwood-Hougen-Watson (LHHW) model, the reaction rate constants were obtained for the rate equations of CO conversion to CH4 formation under supercritical conditions.     

The Magnetic Field Effect on the Polymerization of Styrene in Supercritical Carbon Dioxide

Over the past decade there has been a growing interest in using supercritical fluids (SCFs) to promote reactions and to replace hazardous solvents with environmentally benign solvents, such as supercritical CO2 and H2O. Many reactions in SCFs have been studied1, including polymerization in scCO22. It is known that a small change in the pressure near critical point of a fluid causes a significant change in density-dependent properties such as the solubility parameter, viscosity, and dielect…     

The reversible addition-fragmentation chain transfer （RAFT） miniemulsion polymerization of vinyl acetate mediated by xanthate

The reversible addition-fragmentation chain transfer(RAFT) miniemulsion polymerization of vinyl acetate(VAc) mediated by methyl(methoxycarbonothioyl) sulfanyl acetate(MMSA) was carried out.The results showed that polymerizations initiated by AIBN and KPS proceeded in a controlled way.The RAFT miniemulsion polymerization of VAc initiated by KPS showed the shorter inhibition period,higher propagation rate coefficient and final conversion than those in experiment initiated by AIBN.When the monomer conversio...     

Preparation of Polystryenylphosphonous Acid of Low Polymerization Degree and Influence of Initiators upon the Free Radical Reaction Mechanism

The polystyrenylphosphonous acid (PSPA) of low polymerization degress was prepared with one step reaction. The reaction mechanism was changed with different initiators. For the reaction with AIBN or BPO as the initiator, therer are 2 or 3 serives of radical reaction chains and 5 or 9 series of polystyrenyl products. The main products are PSPA without or with the fragment of the initiator H[CH(C6H5)-CH2]n-PO2H2 and C6H5CO2-[CH2CH(C6H5)]n-PO2H2 respectively.     

THE PROCESS OF THE EMULSIFIER-FREE POLYMERIZATION IN THE PRESENCE OF BARIUM SULFATE POWDER

The process of emulsifier-free copolymerization of the Styrene-Butyl Acrylate-K_sS_sO_s-water in thepresence of Barium Sulfate(BS)powder was investigated under varied conditions within the range of BSpowder quantity,initiator concentration and reaction temperature.Experimental results showed thatthe rate of polymerization is proportional to 0.3-power of the BS quantity and 1.3-power of theinitiator concentration.There is a linear relationship of 2/3-power for the conversion and time.Aprocess for the polymerization is propose to explain the experimental results.     

Controlled Radical Polymerization of Styrene Mediated by Xanthene-9-thione and Its Derivatives

In our present work, a novel controlled radical polymerization system is developed based on xanthene-9-thione(XT). It was found that the radical polymerization of styrene(St) became controlled in the presence of a small amount of XT. At the early stage of the polymerization, the polymerization rate was relatively low and the as-formed polystyrene(PS) had low number-average molecular weight(Mn) and narrow polydispersity(D). After XT was consumed, the polymerization rate increased dramatically and the Mn of PS increased gradually with polymerization proceeding. When the polymerization of St was carried out with a proper molar ratio of initiator to XT and at an appropriate temperature, shortened slow polymerization stage and good control over Mn could be achieved. To further improve the regulating ability of XT, a series of substituent groups(―CF_3, ―CH(CH_3)_2, ―N(CH_3)_2) were introduced onto the xanthene ring of XT,and the effects of these derivatives on the polymerization of St were investigated in detail. UV-Vis spectroscopy was carried out to monitor the concentration of XT during the polymerization and the chemical structure of the as-formed PS was fully characterized by 1 HNMR and ESI-MS analysis. A possible mechanism involving the formation and evolution of the cross-termination products was proposed to interpret the observed polymerization behavior.     

INVESTIGATION OF THE ATRP OF n-BUTYL METHACRYLATE USING THE Cu(I)/N,N,N′,N″,N″-PENTAMETHYLDIETHYLENETRIAMINE CATALYST SYSTEM

The polymerization of n-butyl methacrylate was investigated using the Atom Transfer Radical Polymerization technique with CuBr and CuCl/N,N,N′,N″,N″-pentamethyldiethylenetriamine catalytic systems. Various combinations of catalyst systems and initiators were utilized in order to optimize the polymerization conditions and to obtain well-defined polymers (i.e. controlled molecular weights and low polydispersities). It has been found that the optimal initiator for this system is a chlorine-based initiator, when the catalyst used is a Cu(I) salt in conjunction with the N,N,N′,N″,N″-pentamethyldiethylenetriamine ligand. Bromine-based initiators tend to result in large amounts of initial termination, leading to polymers with less than ideal chain end functionality, even if CuCl is used as the Cu(I) species to invoke the halogen exchange. Additionally, the effects of the polymerization temperature, copper(1) species and the initiator structure were determined.     

Kinetics of ring-opening polymerization of octamethylcyclotetrasiloxane in microemulsion

Polysiloxane latexes were prepared by microemulsion polymerization of octamethylcyclotetrasiloxane(D4) in the absence of co-emulsifier with octadecyl trimethyl ammonium chloride as a cationic emulsiner and potassium hydrate as an initiator.The particle size was determined by the dynamic light scattering(DLS) technique and the reaction rates of the polymerization were discussed.Furthermore,the kinetics was studied by an initial-rate method,and the effects of the monomer,emulsiner and initiator concentrations and the temperature on polymerization conversions were investigated.From the kinetic results,the rate of polymerization,R_p at 80 ℃ can be expressed as R_p = k[D4]~(0.79)[OTAC]~(0.64)[KOH]~(0.38) and the apparent activation energy(E_a),which was determined by half-period method,is 95.32 kJ mol~(-1).     

INVESTIGATION OF THE ATRP OF n-BUTYL METHACRYLATE USING THE Cu（I）／N,N,N＇ N＂ N＂-PENTAMETHYLDIETHYLENETRIAMINE CATALYST SYSTEM

The polymerization of n-butyl methacrylate was investigated using the Atom Transfer Radical Polymerization technique with CuBr and CuCl/N,N,N‘,N“,N“-pentamethyldiethylenetriamine catalytic systems. Various combinations of catalyst systems and initiators were utilized in order to optimize the polymerization conditions and to obtain well-defined polymers (i.e. controlled molecular weights and low polydispersities). It has been found that the optimal initiator for this system is a chlorine-based initiator, when the catalyst used is a Cu(I) salt in conjunction with the N,N,N‘,N“,N“-pentamethyldiethylenetriamine ligand. Bromine-based initiators tend to result in large amounts of initial termination, leading to polymers with less than ideal chain end functionality, even if CuCI is used as the Cu(I) species to invoke the halogen exchange. Additionally, the effects of the polymerization temperature, copper(I) species and the initiator structure were determined.     

IN SITU INTERFEROMETRIC STUDY ON THE GELATION PROCESS OF POLYACRYLIC ACID GELS*

In situ interferometry was used to investigate the gelation process of polyacrylic acid (PAA) gels. The basicprinciple of the in situ interferometry technique is illustrated. It can give sufficient information for non-destructive andsuccessful investigation of the whole gelation process. The effect of initiator concentration on the gelation process wasstudied. The polymerization rate of AA increases with increasing initiator concentration. The error arising from the thermaleffect in the gelation process can be neglected.     

Kinetics and mechanism studies on scandium calix[6]arene complex initiating ring-opening polymerization of 2,2-dimethyltrimethylene carbonate

Scandium p-tert-butylcalix[6]arene complex has been synthesized from scandium isopropoxide and p-tert-butylcalix[6]arene and used as a single component initiator for the first time. The polymerization of 2,2-dimethyltrimethylene carbonate (DTC) using this complex can proceed under mild conditions. Poly (2,2-dimethyltrimethylene carbonate) (PolyDTC) with weight-average molecular weight of 33700 and molecular weight distribution of 1.21 can be prepared. Kinetics study indicates that the polymeri- zation rate is first order with respect to both monomer and initiator concentrations, and the apparent activation energy of the polymerization is 22.7 kJ/mol. 1H NMR spectrum of the polymer reveals that the monomer ring opens via acyl-oxygen bond cleavage leading to an active center of Sc-O.     

The Absorbance Effect in photopolymerization——O-Acyl - α -Oximinoketone Initiator System

The photopolymerization of acrylonitrile and methyl methacrylate initiated by O-acyl-α-oximinoketone was studied under irradiation at 365nm and 313nm. The kinetic behavior was quite different in high absorbance and in low absorbance systems. In low absorbance, the initiator exponent measured was 0.5, while in high absorbance, the rate of polymerization and molecular weights of the polymers were all independent of the initiator concentrations. The greater the extinction coefficient of the initiator, the lower the concentration at which initiator exponent is zero power.     

VINYL RADICAL POLYMERIZATION INITIATED WITH CERIC ION AND ETHYL N, N-DIETHYLDITHIOCARBAMYL ACETATE SYSTEM

Acrylamide polymerization initiated with a redox initiation system consisting of cericion and ethyl N, N-diethyldithiocarbamyl acetate (EDCA) has been studied. It was foundthat the polymerization rate equation is in good agrement with that of a redox initiatedpolymerization, and the overall activation energy of the polymerization was determinedto be 25.2kJ·mol~(-1). Accordingly, the system belongs to a redox initiator. The initiationmechanism was proposed based on the end group analysis using FT-IR, UV spectroscopies.Analysis results revealed that the N, N-diethyldithiocarbamyl radical produced from theredox reaction of EDCA with ceric ion can initiate acrylonitrile (AN) polymerization andform the end group on PAN. The resulting PAN was photopolymerized with butyl acrylate(BA) to form PAN-b-PBA block copolymer.     

STUDIES ON THE KINETICS OF PHOTOPOLYMERIZATION OF ACRYLONITRILE INITIATED BY ANILINE

The dependence of the rate of polymerization on the aniline concentration in the photopolymerization of acrylonitrile initiated by aniline was studied.The rate of polymerization of acrylonitrile increased with increasing of the aniline concentration and showed a maximum at first, then showed another increase after a minimum.This phenomenon was explained with the extinction coefficient of aniline at 313 nm,334 nm and 365 nm wavelengths.Similar results were obtained for the aniline derivatives.Therefore, the initiator exponents in the photopolymerization varies with the different concentrations of initiator and the square-root dependence can be obtained only at certain low concentrations, i.e. with low absorbance.     

“LIVING”/CONTROLLED RADICAL POLYMERIZATION OF ETHYL METHYLACRYLATE WITH 2,2’-AZOBISISOBUTYRONITRILE/FERRIC CHLORIDE/TRIPHENYLPHOSPHINE INITIATION SYSTEM

"Living"/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85℃. Thc numberaverage molecular weight (M_n) increases linearly with monomer conversion and the rate of polymerization is first order withrespect to monomer concentration. The M_w of PEMA ranges from 3900 to 17600 and the polydispersity indices are quitenarrow (1.09～1.22). The conversion can reach up to～100% and M_w of the polymers obtained is close to that designed. Thepolymerization mechanism belongs to the reverse atom transfer radical polymerization (ATRP). The polymer was end-functionalized by chlorine atom, which acts as a macroinitiator to proceed extension polymerization in the presence ofCuBr/bipy catalyst system via an ATRP process. The presence of ω-chlorine in the PEMA obtained was identified by ~1H-NMR spectrum.     

PHOTOINITIATED INVERSE EMULSION POLYMERIZATION OF SODIUM ACRYLATE

Photoinitiated inverse emulsion polymerization of sodium acrylate (AANa) in kerosene was carded out at room or lower temperature, using 2,2-dimethoxy-2-phenylacetophenone (DMPA) as the initiator. Kinetic investigations indicated that the polymerization could be completed in about 30 min and produce polymer with high molecular weight (10^6-10^7). It was found that monomer droplets are the main sites for the polymerization (nucleation). With the increase of DMPA concentration, polymerization rate (Rp) reaches a maximum value while molecular weight of the produced polymer has an adverse result, but the dependence of Rp on incident light intensity is similar. Influences of other parameters such as monomer concentration, emulsifier content and reaction temperature, etc. were also studied. At lower pH values of water phase, Rp depends strongly on the pH due to the electrostatic interaction between the ionized radicals and the monomer. At higher pH, Rp shows a slight dependence on pH.