Nanostructured Materials with Conducting and Magnetic Properties: Preparation of Magnetite/Conducting Copolymer Hybrid Nanocomposites by Ultrasonic Irradiation

Conducting copolymer poly(aniline-co-p-phenylenediamine) [poly(Ani-co-pPD)] and surface-modified magnetite (Fe₃O₄) composites were synthesized by ultrasonically-assisted chemical oxidative polymerization. Fe₃O₄ nanoparticles were surface-modified with silane coupling agent methacryloxypropyltrimethoxysilane (MPTMS) in order that they would be well dispersed for the reaction process. It was also found that the aggregation of Fe₃O₄ nanoparticles could be reduced under ultrasonic irradiation. TEM analysis confirmed that the resulting poly(Ani-co-pPD)/Fe₃O₄ nanocomposite showed core–shell morphology, in which Fe₃O₄ nanoparticles were well dispersed. The incorporation of Fe₃O₄ in the nanocomposites was endorsed by FT-IR. The nanocomposites were also confirmed by UV-visible, TGA and XRD. Conductivity of the nanocomposites was found to be in the range of 7.02 × 10^?4–6.54 × 10^?6 S/cm. Higher saturated magnetization of 12 emu/g was observed for composite with 20% Fe₃O₄.     

Composites of Reactive Silica Nanoparticles and Poly(glycidyl methacrylate) with Linear and Crosslinked Chains by in situ Bulk Polymerization

Composites of poly(glycidyl methacrylate) (PGMA) and L-lysine-coated silica nanoparticles with varying contents were prepared by in situ bulk polymerization using benzoyl peroxide (BPO) as free radical initiator. Silica nanoparticles covered by L-lysine molecules were synthesized using emulsion method. Dynamic light scattering measurements confirmed that the particles are highly monodisperse with the diameter of 10 nm and free of aggregates in the monomer (glycidyl methacrylate, GMA). Upon polymerization of the homogeneous particle/monomer dispersion, aggregates of individual silica nanoparticles are observed by tapping mode atomic force microscope (AFM). Amine and/or carboxylic acid sites on particle surface covalently react with the oxirane groups of the polymer backbone. The aggregation was substantially suppressed by using a difunctional comonomer divinyl benzene (DVB) in polymerization. A three-dimensional polymer network, P(GMA-DVB), forms throughout the system. This structure leads to significant progress in particle dispersion, therefore in physical properties of the resulting composite. We demonstrated that the composites prepared by crosslinked chains are thermally more stable and mechanically stiffer than those prepared by linear ones.     

Intercalative polymerization of cyclic esters in layered silicates: thermal vs. catalytic activation

Poly(ε-caprolactone) layered silicate nanocomposites were synthesized by in situ intercalative ring-opening polymerization (ROP) of ε-caprolactone. The polymerization was promoted by thermal or catalytic initiation starting from either non-modified natural sodium-montmorillonite (MMT-Na) or montmorillonite modified by different ammonium cations bearing either non-functional alkyl chains or chains terminated by carboxylic acid or hydroxyl functions. The resulting compositions were analyzed by small-angle X-ray diffraction and transmission electron microscopy. The clay dispersion depended on the structure of the alkyl ammonium. Exfoliated nanocomposites were formed when hydroxyl-containing alkyl ammonium was used; otherwise, partially intercalated/partially exfoliated structures were observed. Moreover, owing to the inherent catalytic properties of the montmorillonite surface, it was also possible to prepare intercalated nanocomposites by in situ polymerization of ε-caprolactone in presence of non-modified montmorillonite-Na (MMT-Na) without any added catalyst.     

SO4^2/MxOy型固体超强酸在有机合成中的应用

SO4^2/MxOy（M=Ti，Zr，Fe）是一新型的固体超强酸催化剂。综述了近年来 SO4^2/MxOy型经剂在有机合成中的应用，并对其今后的发展趋势作了预测。     

MESOPOROUS ACID SOLID AS A CARRIER FOR METALLOCENE CATALYST IN ETHYLENE POLYMERIZATION AND A CATALYST IN CATALYTIC DEGRADATION OF POLYETHYLENE

The possibility of mesoporous acid solid as a carder for metallocene catalyst in ethylene polymerization and catalyst for polyethylene （PE） catalytic degradation was investigated. Here, HMCM-41 and AIMCM-41, and mesoporous silicoaluminophosphate molecular sieves （SAPO1 and SAPO2） were synthesized and used as acid solid. Much more gases were produced during catalytic degradation in PE/acid solid mixtures via in situ polymerization than those via physical mixing. The particle size distribution results exhibited that the particle size of SAPO1 in the PE/SAPOI mixture via in situ polymerization was about 1/14 times of that of the original SAPO1 or SAPO1-supported metallocene catalyst. This work shows a novel technology for chemical recycling of polyolefin.     

MORPHOLOGY EVOLUTION OF POLY（St-co-BuA）/SILICA NANOCOMPOSITE PARTICLES SYNTHESIZED BY EMULSION POLYMERIZATION

Poly（St-co-BuA）/silica nanocomposite latexes were synthesized via conventional emulsion polymerization in the presence of 3-（trimethoxysilyl）propyl methacrylate modified colloidal nano-silica. The effects of surface property, particle size and content of colloidal nano-silica as well as the concentrations of monomer and surfactant on the morphology of nanocomposite latex particles were investigated by transmission electron microscope （TEM） and scanning electron microscope （SEM） in detail. Various interesting morphologies such as grape-like, Chinese gooseberry-like, pomegranate-like and normal core-shell structures were observed. Droplet nucleation mechanism competing with micelle nucleation mechanism was proposed to explain the morphological evolution of the nanocomposite particles.     

铁芳烃配合物光引发剂的敏化研究

本文对铁芳烃配合物的敏化光解问题进行了研究,发现敏化剂双二甲基氨基苄叉酮类化合物在敏化过程中不仅存在有电子转移和能量转移过程,而且还可能有分解产物与敏化剂间的成盐反应.另外还发现经电子转移反应的产物中存在着能引烯类单体聚合的活性自由基,可以引发甲基丙烯酸甲酯聚合.本文对可能的光化学反应机制进行了讨论.     

SURFACE MODIFICATION OF MICROPOROUS POLYPROPYLENE MEMBRANES BY GRAFT POLYMERIZATION OF N,N-DIMETHYLAMINOETHYL METHACRYLATE

Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer concentration and pre-adsorbed amount of benzoyl peroxide on grafting degree were studied respectively. It was found that the appropriate graft temperature was 75℃, at which the grafting degree was the highest and the hydrolytic decomposition of DMAEMA the lowest. Scanning electron photomicrography and the average pore diameters of the modified membranes demonstrated that part of the micropores on the membrane surface was plugged by the grafted polyDMAEMA chains, especially at high grafting degree. Contact angle and water swelling experiments showed that a moderate grafting degree could improve the hydrophilicity of the membranes. In the range of I 1.3%o-12.0% grafting degree, the water swelling percentage reached its maximum (51.1%) and the contact angle reached its minimum (74 degrees). The bovine serum albumin (BSA) adsorption experiment indicated that the grafted polyDMAEMA had a dual effect on protein adsorption. At the first stage, the BSA adsorption decreased with increasing of DMAEMA grafting degree. As the interaction between BSA and polyDMAEMA on membrane surface increased, the BSA adsorption increased with increasing of DMAEMA grafting degree.     

水杨亚胺基钯催化聚合丙烯的密度泛函理论研究

Grubbs水杨亚胺基镍/钯催化剂是一类新型含氮、氧配位杂原子的中性单组分 烯烃聚合催化剂。以不带取代基的水杨亚胺钯为模型催化剂，采用密度泛函理论 在B2LYP/LANL2DZ水平上对其催化聚合丙烯的链增长机理进行了研究。与催化剂配 位原子氮的对位进攻相比，丙烯从氧的对位进攻的复合能大、插入能低。当烷基链 在配位原子O的对位时1，2-插入速率低于2，1-插入；当烷基链在配位原子N对位时 ，1，2-插入速率高于2，1-插生产方式。能量量低的插入路径是烷基链在N对位是 的1，2-插入。2，1-插入路径中的γ-氢桥键烷基配合物能异构化得三个β-氢桥键 的烷基配合物，空间位阻最小的最稳定。1，2-插往前只生成一个β-氢桥键烷基配 合物。与氮原子对位的配合物相比，所有在配位原子氧对位的β-氢桥键的烷基配 合物都是更稳定的配合物构型。     

NEW INITIATION SYSTEMS FOR ATOM TRANSFER RADICAL POLYMERIZATION

This review summarizes our achievements in designing new initiation systems for atom transfer radical polymerization (ATRP). First-order kinetics and extension experiments revealed the living nature of these reactions. Tailormade vinyl polymers with functional end groups were characterized by ^1H-NMR and UV-vis spectroscopic analyses. Replacing traditional radical initiators AIBN and BPO, carbon-carbon bond compounds, 1,1,2,2-tetraphenyl-l,2-ethanediol, diethyl 2,3-dicyano-2,3-diphenylsuccinate and diethyl 2,3-dicyano-2,3-di(p-tolyl)succinate, were utilized in reverse ATRP to produce the initiating radical. Sulfur-sulfur bond iniferter, tetraethylthiuram disulfide (TD), in conjunction with CuBr/bpy or NiCI2/PPh3 complex could control the styrene polymerization via redox reaction. Pseudo-halogen transfer reaction was demonstrated to maintain the dormant-active species equilibrium in normal and reverse ATRP with Cu(S2CNEt2), Cu(S2CNEt2)CI and Fe(S2CNEt2)3 as catalysts. The organic halide initiator and reduced transition metal compound that started the living polymerization were produced in situ from the components of TD/FeCI3/PPh3, TD/CuBr2/bpy and Fe(S2CNEt2)3/FeCI3/PPh3 systems. Accurate control of UV irradiation time favored the radical generation process in photo ATRP with the 2,2-dimethoxy-2-phenylacetophenone/Fe(S2CNEt2)3 initiation system.