PREPARATION OF POLY（METHYL METHACRYLATE）/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

An exfoliated layered double hydroxides/poly(methyl methacrylate)(LDHs/PMMA)nanocomposite was prepared by in situ solution polymerization of methyl methacrylate(MMA)in the presence of 4-vinylbenzenesulfonate intercalated LDHs(MgAl-VBS LDHs).MgAl-VBS LDHs was prepared by the ion exchange method,and the structure and composition of the MgA1-VBS LDHs were determined by X-ray diffraction(XRD),infrared spectroscopy and elemental analysis.XRD and transmission electron microscopy(TEM)were employed to examine the structure of LDHs/PMMA nanocomposite.It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix.The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.     

KINETIC ANALYSIS OF CO-CONDENSATION POLYMERIZATION OF AB2 AND AB MONOMERS

This work deals with the kinetics of co-condensation polymerization of AB2 and AB monomers, giving expressions of the two-dimensional molecular weight distribution function and the number/weight average molecular weights of the resulting copolymers. The two-dimensional molecular weight distribution depends on two indices, n and l, which are the respective numbers of AB2 and AB units in a copolymer species. The evolution of the two-dimensional weight and z distributions during the co-condensation polymerization has been evaluated systematically. Finally, the two-dimensional distribution was transformed into a one-dimensional molecular weight distribution with only one variable (the molecular weight of the products instead of the degree of polymerization). The calculated results show that the highly branched copolymer has a very broad molecular weight distribution when the co-condensation polymerization approaches completion.     

STUDY ON 1-HEXENE POLYMERIZATION BASED ON ZIEGLER-NATTA CATALYSTS WITH DOPED SUPPORT

A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst.     

NARROW-DISPERSED CROSSLINKED CORE-SHELL POLYMER MICROSPHERES PREPARED BY SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION＊

Grafting of polystyrene with narrowly dispersed polymer microspheres through surface-initiated atom transfer radical polymerization (ATRP) was investigated. Polydivinylbenzene (PDVB) microspheres were prepared by dispersion polymerization with poly(N-vinyl pyrrolidone) (PVP) as stabilizer. The surfaces of PDVB microspheres were chloromethylated by chloromethyl methyl ether in the presence of zinc chloride as catalyst to form chloromethylbenzene initiating core sites for subsequent ATRP grafting of styrene using CuCl/bpy as catalytic system. Polystyrene was found to be grafted not only from the particle surfaces but also from within a thin shell layer, resulting in the formation of particles size increased from 2.38-2.58μm, which can further grow to 2.93μm during secondary grafting polymerization of styrene. This demonstrates that grafting polymerization proceeds through a typical ATRP procedure with living nature. All of the prepared microspheres have narrow particle size distribution with coefficient of variation around 10%.     

A MORPHOLOGICAL STUDY OF POLY（DIVINYLBENZENE-co-ACRYLIC ACID） IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.     

Preparation of Encapsulated Polymer Adhesion Beads and Adhesion with Porous Fibers

Adhesion beads of 10–130 μm, prepared by suspension polymerization, were encapsulated by melamine–formaldehyde. The capsule-type adhesives prepared consist of core and shell structure where the core region is sticky and viscous and the shell region consists of a hard shell at room temperature. The air permeable pads are made by hot pressing the mixture of capsule-type adhesives and porous materials including charcoal chips and Camellia sinensis fibers, which have a porous structure. The interfacial adhesion between polymer adhesion bead and porous fibers after processing shows a good porous sheet structure, which can penetrate air.     

Preparation of nanocomposite superabsorbents based on hydrotalcite and poly(acrylic-co-acrylamide) by inverse suspension polymerization

Firstly, hydrotalcite (HT) was synthesized by the urea method. Then, sodium methyl allyl sulfonate (SMAS) was used as intercalation agent to prepare intercalated HT (SMAS–HT). Finally, a novel poly(acrylic-co-acrylamide)/HT nanocomposite superabsorbent was prepared by inverse suspension polymerization, using N,N′-methylenebisacrylamide (NMBA) as a cross-linking agent and potassium persulfate (KPS) as an initiator. The morphology of the superabsorbents was characterized by FT-IR, XRD, SEM and TEM. The influences of the amount of SMAS–HT on the water (salt) absorbency were investigated. Results showed that the intercalation was successful and the intercalated SMAS–HT incorporated into the superabsorbent was completely exfoliated. The superabsorbent particles approach a spherical shape and the average size is 200–300 nm. The particle sizes of the superabsorbents decrease with increasing the content of SMAS–HT. In addition, the superabsorbent acquired its highest water (salt) absorbency when the content of SMAS–HT is 3 wt%. The highest absorbencies of the superabsorbent for deionized water and 0.9% NaCl_(aq) were 900 g/g and 140 g/g, respectively.     

Preparation of Al(OH)3/Acrylic Copolymer Latex by Emulsion Polymerization

The Al(OH)₃/acrylic copolymer latexes were synthesized through the emulsion polymerization of acrylic monomers, butyl acrylate and 2-ethylhexyl acrylate in the presence of surface-functionalized Al(OH)₃ filler particles. The polymerization was stabilized by polyoxyethylene (50) nonyl phenyl ether (NP-1050, nonionic surfactant) and ammonium (POE) alkyl aryl ether sulfate (EU-S133D, anionic surfactant) to produce stable composite latexes. The improved compatibility of Al(OH)₃ surface with acrylic monomers was achieved by the modification with 3-(trimethoxysilyl) propyl methacrylate (γ-MPS). Transmission electron microscopy showed that nano-sized Al(OH)₃ particles were slightly agglomerated in the copolymer latex. When pristine Al(OH)₃ was used as a filler or γ-MPS-modified Al(OH)₃ particles were added above 30 wt% with respect to monomers, unstable latexes were obtained, which were partially precipitated out on standing for prolonged time. The flame retardation effect was not apparent with the incorporation of Al(OH)₃ in the latexes by 30 wt% as shown by LOI test.     

预辐射苯乙烯形成过氧化物组分结构及其引发活性研究

本文研究了苯乙烯在空气存在下的γ辐照。用硅胶柱层析分离在辐射总剂量为5×10^4Gy, 辐射剂量率分别为2.9, 0.7, 0.5和0.3Gy/s的条件下形成的过氧化物,发现剂量率在0.5Gy/s以上时产物都可分成三种组分, 而组分布随剂量率不同而异。当剂量率为0.3Gy/s时, 产物只包含单一的, 相当于第二组分的过氧化物。对剂量率为0.7Gy/s时生成的三种过氧化物组分用红外光谱, 核磁共振谱和质谱进行了组分结构测定及其引发活性测定, 发现具有交替结构的第二组分有较强发引发活性, 它在较低温度和较短时间内就能引发苯乙烯聚合, 获得分子量166578的聚合物。它还能引发其它乙烯类单体聚合, 且聚合过程较用BPO引发剂平稳。