Size-controlled preparation of hollow silica spheres and glyphosate release

Different-sized hollow SiO2 spheres of 249–1348 nm in diameter were successfully prepared by using Na2SiO3 as the precursor and using polystyrene and polystyrene-methyl acrylic acid latexes as the templates. The diameter and shell thickness of the hollow SiO2 spheres increase with increasing the latex template diameter at a given mass ratio of SiO2 to latex template. The diameter and shell thickness of the hollow SiO2 spheres also increase with increasing the mass ratios of SiO2 to latex template. The presence of carboxylic acid groups on the surfaces of polystyrene-methyl acrylic acid latex templates favors the formation of dense and uniform SiO2 shells. The hollow SiO2 sphere is constructed by mesoporous shell with large specific surface area. When glyphosate is used as a release model chemical, glyphosate release rate is tuned by varying the shell thickness.

Study and Pilot Scale Development of Catalyst for Ethylebenzene Synthesis THrough Transalkylation of Benzene and Polyethylbenzene

This paper refers to the results of study and development of benzene and polyethylbenzene transalkylation catalyst (type AEB-1) for synthesis of ethylbenzene. The effect of reaction conditions on the reaction performance of the catalyst was investigated in the pressurized microreactor CDS-900. A transalkylation catalyst with high activity, good selectivity and stability was developed following a 2000-hour test on the activity and stability of the catalyst. The preparation of this catalyst was implemented in pilot scale and this catalyst was tested for activity and stability in a 150 t/a pilot unit for production of ethylbenzene. The test results have shown that this transalkylation catalyst has excellent activity, selectivity and stability. The operation of pilot test unit ran smoothly and the process scheme is viable.

Synthesis and Characterization of Poly(St-co-BA) Latex with an Organic-Inorganic Hybrid Compound as Emulsifier

A poly (St-co-BA) latex was successfully synthesized by using an organic-inorganic hybrid compound (OIHC), an aliphatic carboxylate sodium/nano-silica composite, as the emulsifier, and investigated by particle size analyzer, transmission electron microscope (TEM), optical contact angle measurement (OCA) and dynamic mechanical analyzer (DMA). It was found that the protective agent, sodium polyacrylate (PA),could obviously improve the polymerization stability and the functional monomer, glycidyl methacrylate (GMA), could enhance the store stability of the latex. The particle size of poly(St-co-BA) latex decreased and then leveled off as OIHC content increased. TEM shows that the prepared polymers were actually organic-inorganic nanocomposites, and these films have better waterproof property than those prepared by traditional poly(St-co-BA) latex or organic silicone modified poly(St-co-BA) latex. The nanocomposite polymer has much higher glass transition temperature than organic silicone modified poly(St-co-BA) polymer containing the same organic silicone content.

Bulk Polymerization of Styrene Using Benzyl Dithiobenzoate as a Chain Transfer

Bulk polymerization of styrene was carried out in the presence of a reversible addition fragmentation chain transfer (RAFT) of benzyl dithiobenzoate (BDB). The comparison between reaction systems with and without BDB indicates that there is significant retardation in the reaction rate when BDB is used. The molecular weight of styrene polymer prepared with BDB shows linear relationship with the conversion of monomer, polydispersity is as narrow as 1.2, and no gel effects are observed during the polymerization with BDB, which are characteristics of a living radical polymerization. It has been found that the concentrations of BDB and azobis (isobutyronitrile) (AIBN) have opposite effects on the polymerization kinetics, and the AIBN dominates.

Study on the behaviors of poly（p-phenylene benzobisoxazole） in coagulation

Poly（p-phenylene benzobisoxazole）（PBO） is a candidate of high performance materials for many applications. PBO materials＇ properties are considered to be closely related to their fabrication process, especially coagulation. In this paper, the coagulation effect on the chemical and microstructure of PBO was investigated with the help of a PBO model compound, 2, 2＇-（ 1,4-phenylene） bis （5-amino-6-benzoxazolole）. During coagulation, the hetero-cyclic ring of the PBO structure was experienced cleavage and even being broken down completely under some extreme conditions. Wide-angle X-ray diffraction （WAXD） analysis showed that different coagulants could cause the microstructure difference in PBO materials. In a slow coagulation process, PBO molecular chains aligned more orderly in the side-by-side direction （200）.

Photocatalytic hydrogen-evolution dimerization of styrenes to synthesize 1,2-dihydro-1-arylnaphthalene derivatives using Acr^+-Mes and cobaloxime catalysts

We report a hydrogen-evolution dimerization of styrenes via the synergistic merger of Acr＋-Mes photocatalyst and cobaloxime proton reduction catalysts. By utilizing this dual catalyst system, 1,2-dihydro-1-arylnaphthalene derivatives can be directly constructed from commercially available styrenes. Our reaction proceeds smoothly under mild conditions without the need for oxidants or hydrogen atom transfer reagents, and the sole byproduct is hydrogen gas. Mechanistic investigation suggests that the reaction is initiated by photoinduced electron transfer under visible-light irradiation.

Synthesis and characterization of copolymers of poly(m-xylylene adipamide) and poly(ethylene terephthalate) oligomers by melt copolycondensation

Poly（m-xylylene adipamide）/poly（ethylene terephthalate）（MXD6/PET） copolymers are synthesized by melt copolycondensation with 1–5 wt% low molecular weight PET oligomers into the MXD6 oligomers at 260 ℃.FR-IR and1 H NMR analysis results indicate that the interchange reaction has occurred between MXD6 oligomers and PET oligomers. The thermal behavior of copolymers shows that the melting temperature of MXD6/PET copolymers decreases with the increasing of amount of PET oligomers, while the crystallization temperature accordingly increases. And the equilibrium temperature Tm0 is evaluated to be 251.8 ℃ for the copolymers with5 wt% PET oligomer adding, which is very close to that of neat MXD6. The tensile and impact strength of MXD6/PET copolymers are significantly improved than that of pure MXD6 by mechanical properties test, and the microfibril structure in the impact fracture sample＇s surface reveals the feature of ductile fracture.

Charicteristic of a novel optoelectronic polymer and related device fabrication

In this paper a preliminary investigation of a novel optoelectronic polymer, poly (p-phenylene N-4-n-butylphenyl-N,N-bis- 4-vinylenephenylamine) (PNB), is reported. A single layer structure of ITO/PNB/Al was prepared via spin-coating of PNB solution as a thin film on the top of an ITO substrate, while aluminum top electrode was vacuum evaporated. Dark current- voltage characteristics of this device showed a typical rectifying behaviour. Photovoltaic response under a monochromatic illumination at 420 nm was observed, with an open circuit voltage of 0.3 V and fill factor of 0.21. Spectral response and optical absorption were found to be matched well. It was also discovered that the device showed a green electroluminescent emission at a forward bias. Turn-on voltage of the device was about 6 V and light output about 22.6 nW at a forward bias of 10 V. The work demonstrated that the PNB material might possess dual exciton sites resulting in a competition for excitons to be either separated or recombined. Both effects were associated with each other, which limited the photovoltaic or electroluminescence to some degrees.

Kinetic Treatment for Copolymerization of Styrene or Methyl Methacrylate with N-phenylmaleimide

Shirota's kinetic model and our kinetic model were used to treat the kinetic data of styrene (St) and N-phenylmaleimide (PMI) copolymerization in which charge-transfer complex (CTC) was formed. The results obtained by Shirota's kinetic model were disagreed with the experiments and the experimental phenomena could not be explained. The kinetic data of all feed fractions can be treated with our kinetic model, and the experimental phenomena can be explained from the propagation constants and reactivity ratios. Our kinetic model is also suitable for the kinetic data of methyl methacrylate (MMA) and PMI copolymerization in which CTC can not be formed.

CHARACTERIZATION OF NOVEL POLYMERIC INTERMEDIATE POLY(p-BROMOACETYL STYRENE) CROSSLINKED BY DIVINYLBEZENE QU Rongjun

Acetyl crosslinked polystyrene (EPS) and crosslinked bromoacetyl polystyrene (BEPS)beads were synthesized by Fridel-Crafts acetylation of polystyrene (PS) and bromination of EPS respectively. FTIR, XPS, and TG-TDG were employed to characterize their structures. The results revealed there are two types of bromine in the BEPS molecule. One is in the main chain of polystyrene and the other is in the acetyl. The results of TG-DTG showed that the rates of loss weight of PS, EPS, and BEPS were 92.7%, 92.2%, and 81.3% among the 300 ℃～500 ℃; 7.3%, 7.8%, and 18. 7% in 594 ℃, 660 ℃, and 584.8 ℃, respectively.

SYNTHESIS OF MACROPOROUS COPOLYMER OF VCA AND DVB

The reactiving ratios of vinyl acetate (VAc) and divinyl benzene (DVB) werecalculated from the Q and e values. The possibility of the copolymerization of thesetwo monomers was predicted and the copolymerization was carried out by-sin pensionpolymerization technique in the presence of pore producing agent (toluene andgasoline). The relative ratio of acetoxy group and benzene ring in the copolymer weremonitored by IR measurement during the polymerization. The variation of poreproperties, such as specific surface area, porosity and average pore diameter withpolymerization time were determined The copolymers at various polymerization timewere alcoholyzed and thus the variation of the hydroxyl group content withpolymerization time was studied.

SYNTHESIS AND FLUORESCENCE STUDY OF St／DVB COPOLYMERS LABELLED WITH PYRENE GROUPS

Two kinds of St/DVB copolymer beeds containing (1 - pyrenyl) formyl and(1 -pyrenyl) methyl groups respectively have been synthesized by both functionalization and copolymerization. The fluorescence spectra of the swollen polymers synthesized are similar in shape to those of the corresponding model compounds, whilethe intensity ratio of excimer to monomer shows clear dependence on the contents ofthe pyrene groups.

Interface and Surface Properties of Nano-hydroxyapatite /Poly (1,4-PhenyleneSulfide)-Poly(2,4-Phenylene Sulfide Acid) Copolymer Composite

The interface and surface properties of nano-hydroxyapatite(n-HA) and poly( 1, 4-phenylene sulfide)-poly (2,4-phenylene sulfide acid)(PPS-PPSA) copolymer composite were investigated. The results show that there are some strong interface combinations of calcium ion (Ca2+ ), car-boxyl (-COO- ) and phosphate radicle ion (PO_4~3- ) between copolymer and n-HA in the composite. The presence of the 2,4-phenylene sulfide acid in copolymer can increase the affinity to n-HA, which causes the formation of chemical bindings between the PPS-PPSA copolymer and n-HA. XRD analysis and IR surface analysis indicate that n-HA is not encapsulated by copolymer but exposed on the surface of the composite, and has same structure and properties with the origi-nal n-HA. The presence of the interface chemical bindings between the PPS-PPSA copolymer and n-HA can increase the content of n-HA in composite but does not cause the decrease of the composite mechanical strength.

CATALYSIS OF POLYSTYRENE N-HYDROXYL SULFONAMIDE FOR ESTERIFICATION OF BUTANOL WITH ACETIC ANHYDRIDE

Polystyrene N-hydroxyl sulfonamide resin 1 was prepared and used to catalyze the esterification of n-butanol and acetic anhydride. The mechanism of catalytic esterification proved by IR spectra of the resins was found that O-H and N-H of the N-hydroxyl sulfonamide resin reacted with the acetic anhydride respectively to form the active intermediate polystyrene N,O-diacetyl sulfonamate which was cleaved by n-butanol to produce butyl acetate. The catalytic esterification by resin 1 was in good agreement with the kinetic model of 揵i-bi-ping-pong?mechanism.

SOLID PHASE SYNTHESIS OF ISOXAZOLINES

The solid-phase synthesis of isoxazolines on 2-polystyrylsulfonamidoethanol resin is reported. 2-Polystyrylsulfonamidoethanol resin 1 was reacted with acryloyl chloride to afford 2-polystyrylsulfonylamidoethyl acrylate resin 2, which was further reacted with brominated aldoximes by [3+2] cycloaddition to give isoxazoline resin 4. Resin 4 was treated with aqueous 6 mol/L HCl solution to obtain isoxazolines in good yield and purity.

COMPATIBILITY OF POLY (STYRENE-B-2-VINYL PYRIDINE)/IONOMER BLENDS BASED ON ION-LIGAND INTERACTION

In this work, DSC and SEM studies indicate that ion-ligand interaction can be utilized to enhance the interaction of poly (styrene-block-2-vinyl pyridine)[P (S-b-2VP)] and polyethylene based ionomer (Surlyn). The compatibility for this blending system can be improved by this special interaction and 20/80 wt is the optimum blending composition with good compatibility. FTIR results further certify that strong interactions exist in the blending system.

Synthesis of biaryls using palladium nanoparticles immobilized on peptide nanofibers as catalyst and hydroxybenzotriazole as novel phenylating reagent

Peptide nanofibers decorated with palladium nanoparticles catalyzed direct coupling of aryl halides with hydroxybenzotriazole to afford the corresponding biaryls in good to excellent yields.The coupling reactions proceeded under simple,green,and mild conditions.The peptide nanofibers were used as recyclable supports in the coupling reactions.This approach is the first to use hydroxybenzotriazole as a phenylating agent.

Molecular Weight Distribution of Polystyrene Produced in a Starved Feed Reactor

A starved feed reactor (SFR) is a semi-batch polymerization reactor where initiator and monomer are fed slowly into a fixed amount of solvent. The polymerization is carried out isothermally at elevated temperatures. The added initiator decomposes instantaneously and the added monomer polymerizes immediately. The molecular weight (MW) and molecular weight distribution (MWD) of the product polymer can be effectively controlled by the feed ratio of monomer to initiator. This paper presents a study on the MWD of styrene polymerization in a SFR. The MWD model parameters are regressed with experimental data. Although the solids fraction in the SFR is high (higher than 50%), viscosity is not too high and the 'gel effect' is weak due to the low molecular weight of the products. It is found that the termination rate constant is a power function of molecular weight, radicals terminate via 100% combination, the thermal initiation can be neglected even at high reaction temperature studied. And calculated results indicate that in the SFR, the validity of the long chain assumption becomes doubted. It appears that other alterative assumption should be found for an improved model.

SYNTHESIS OF A NOVEL CHELATING RESIN WITH HETEROCYCLIC RING OF S AND N

By the reaction of poly(bromoacetyl styrene) (EBPS) with thiaurea (TU), a kind of novel chelating resin with heterocyaclic ring of sulfur and nitrogen, poly[4-(2-amino)thiazoleyl-4- vinylbenzene], was synthesized. Its structure was characterized by FTIR and elemental analysis. The factors which have influence on the reaction such as reaction time, solvents, and molar ratio of reactants were investigated.

FLUORESCENCE STUDIES ON MORPHOLOGICAL CHANGE OF ST/DVB CROSSLINKED GELS DURING CHLOROMETHYLATION

The morphological change of St/DVB crosslinked gels during chloromethylation wasstudied by fluorescence spectroscopy using St/DVB crosslinked and hypercrosslinked gels as controlsamples. It has been found that with increase of chlorine content, the excimer emission band (~325nm)approaches to vanish, while the intensity of multi-ring aggregate emission band (~420nm) quicklyreaches a maximum, and then decreases sharply accompanied by appearance ofa new broad bandcentred at ca 488nm which roughly coincides with the typical emission band of hypercrossllinkedSt/DVB gels. Mearwhile, the result of IR measurement suggests that methylene bridge between phenylrings forms and increases with chloromethylation process. These results are explained in terms ofaside reaction of post-crosslinking, which densifies the loosely crosslinked networks and undoes thedensely entangled microgel nuclei. As a result, the morphology of the crosslinked gels becom es morehomogeneous with chloromethylation.