STUDY ON THE SYNTHESIS OF COPOLYMER CONTAINING N-SUBSTITUTED ACRYLAMIDE COMPONENT

In this paper the synthesis of linear and crosslinked N-substituted acrylamide copolymer is reported. In order to obtain the terpolymer with appropriate hydrophilicity, the conditions of aminolysis of St-MMA copolymer have been selected.It is shown that the copolymer with predictable hydrophilicity possesses good blood compatibility.     

PLASMA POLYMERIZATION OF HEXAMETHYLCYCLOTRISILOXANE

In a capacitively coupled RF discharge system with external electrodes ,hexamethyicyclotrisiloxane was polymerized, and the effects of discharge power and plasma gas on polymer deposition rate were studied. The polymer structures and properties were studied by IR spectroscopy, XPS measurement, PGC/MS combined technique, TG analysis and contact angle measuring. The results showed that the polymers prepared in H_2 or O_2 have higher C/Si ratio in comparison with those prepared in inert gases. PGC/MS results revealed the existence of many short carbon chains in the polymer structure .TG analysis suggested that the polymers prepared in the inert gas would possess better thermal stabilities.     

SYNTHESIS, CHARACTERIZATION AND RING-OPENING POLYMERIZATION OF CYCLIC (ARYLENE PHOSPHONATE) OLIGOMERS

INTRODUCTIONThe use of cyclic oligomers as macrocyclic precursors for the preparation of high performance polymers byring-opening polymerization (ROP) has sparked much interest in recent years. It could produce a revolutionarychange in the preparation of advanced composite materials, and is of great importance in the polymerizationprocess yielding polymers such as the reinforced reactive injection model (RRIM) and the resin transfer model(RTM) etc. Within the last 10 years, the synthes…     

SYNTHESIS AND CHARACERIZATION OF LADDER-LIKE POLYDECYLSILSESQUIOXANE*

Ladder-like polydecylsilsesquioxane (LPDS) was synthesized by a preamminolysis reaction ofdecyltrichlorosilane with ethylene diamine, followed by hydrolysis and polycondensation reaction. LPDS issoluble in a nonpolar solvent such as heptane and insoluble in a high polar solvent such as methanol. It wascharaterized by IR, ~1H-NMR, ~(29)Si-NMR, GPC and X-ray diffraction.     

SYNTHESIS AND CHARACTERIZATION OF COMB-SHAPED POLYBUTADIENES

Polybutadiene (PB) was chlorinated with t-BuOCl without chain crosslinking and degradation togive chlorinated polybutadiene (Cl--PB) with active allylic chlorine atoms on the backbone. Comb-shaped PB was prepared by coupling of Cl--PB with "living" PB anions in a mixed solvent of cyc-lohexane and tetrahydrofuran. Characterization by GPC and osmometry showed that purifiedproducts were welldefined comb-shaped PB composed of low polydispersity backbone chain andrandomly distributed grafts of uniform length. The averagr number of branches could be variedin a wide range to meet the needs of structure-properties relationship studies.     

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,~(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ~(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.     

SYNTHESIS OF POLYTETRAPHENYLPORPHYRIN AND ITS MANGANESE COMPLEX

A new polymeric tetraphenylporphyrin and its manganese complex were synthesized. Their structures were identified by examining the visible absorption, IR, ~1H-NMR spectra.     

SYNTHESIS AND PROPERTIES OF POLY-1,3,5-TRIAZINES

Two new polytriazines: poly[2-methyl-4, 6-(4,′4″-diphenylene)-1, 3, 5-triazine] (Ⅰ) and poly[2-phenyl-4, 6-(4′, 4″-diphenylene)-1, 3, 5-triazine] (Ⅱ) were synthesized from the solution condensation of biphenyl-4, 4′-diamidine dihydrochloride with acetic anhydride and biphenyl-4, 4′-diamidine with benzaldehyde respectively. These two polymers were characterized by TGA, DTA, elemental analysis and IR spectroscopy. They exhibited good thermal oxidative stability as shown by the fact that the powders of these polymers suffered 5.4%, 2.4% weight loss after isothermal aging in air at 300℃for 200 hours. The decomposition temperature of (Ⅱ) was 583℃in air and 590℃in N_2. These linear poly-1, 3, 5-triazines were soluble in concentrated sulfuric acid, phosphoric acid and trifluoroacetic acid whereas the erosslinked poly-1, 3, 5-triazines reported in the literature were insoluble and infusible.It is interesting that these polymers can form complexes with metal halides as determined by X-ray photoelectron spectroscopy (XPS). The polymer metal complex (Ⅲ). PdCl_2 possesses catalytic activity for hydrogenation.     

SYNTHESIS AND CHARACTERIZATION OF TITANOCENE POLYMER DERIVATIVES

Titanocene polymer derivatives with potential antitumor properties were synthesized by interfacial condensation. The preformed polymers used are PAA (polyacrylic acid), CPSMA (1:1 alternating copolymer of styrene and maleic anhydride) and DVEMA (1:2 copolymer of divinyl ether and maleic anhydride). The ratio of practical and theoretical titanium content is 73.6%, 92.2% and 86.2% for PAA, CPSMA and DVEMA polymer derivatives respectively. The IR spectra of the polymer derivatives possess the characteristic absorptions of titanocene. XPS (X-ray photoelectron spectroscopy) of O_(1s) and Ti_(2p3/2) supports the existence of Ti-O bonding.     

DESIGN AND SYNTHESIS OF NOVEL CHIRAL IONIC LIQUIDS AND THEIR APPLICATION IN FREE RADICAL POLYMERIZATION OF METHYL METHACRYLATE

Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.     

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.     

叔胺中的取代基团对其促进烯类聚合活性的影响

<正> 过硫酸盐和水溶性脂肪胺可以组成引发体系用于烯类聚合反应。脂肪胺的促进聚合活性随其结构不同而异。为了研究清楚脂肪胺促进聚合活性与结构的关系,本文合成了几种甲基取代的脂肪叔胺,分别与过硫酸盐组成引发体系用于烯类聚合反应。研究结果表明,甲基取代基团的效果较好。     

SYNTHESIS AND CHARACTERIZATION OF ORGANOMONTMORILLONITE AND POLYAMIDE 66/MONTMORILLONITE NANOCOMPOSITES

The montmorillonites (MMTs), layered, smectite-type silicates, were premodified by two different methods priorto the polymer melt intercalation. In one case MMTs were modified with cetyltrimethylammonium bromide (CTAB), andtermed as organomontmorillonites (OMMTs); in the other case MMTs were modified by nylon, and the products were calledmodified montmorillonites (MMMTs). The effects of CTAB and nylon on the MMTs were investigated by using TG andWAXD. The results show that interlayer spacings of CTAN and nylon modified MMTs are larger than that of sodium MMTs.Then, polyamide 66 (PA 66)/MMT nanocomposites were obtained through the method of melt intercalation of polymers. Thenanocomposites were characterized by WAXD, TEM and Molau experiments. The results indicate that the MMTs dispersehomogeneously in the PA 66 matrix. The mechanical properties of nanocomposites, such as tensile properties and flexuralproperties, were also measured and show a tendency to increase with increase of MMT content and reach the maximumvalues at 5phr MMT content. The heat distortion temperature (HDT) of the nanocomposites (7 phr) is about 32 K higher thanthat of pure PA 66.     

SYNTHESIS OF CHIRAL BINAPHTHYL CROWN ETHERS AND THEIR USE IN ANIONIC POLYMERIZATION OF METHYL METHACRYLATE AS INITIATOR LIGANDS

INTRODUCTIONAnionic polymerization of MMA could be carried out with alkyllithium or Grignard reagent etc. in a non-polarsolvent. However, this polymerization system often involves multiple active species and side reactions dependingon initiator, countercation, solvent and polymerization temperature etc. Therefore, the molecular weightdistribution and stereomicrostructure of PMMA obtained would be very different[1-4]. These differences wouldbe mainly caused by the nucleophilic attack of…     

SYNTHESIS AND CHARACTERIZATION OF DVE-CO-MA DERIVATIVES OF CIS- PLATINUM COMPLEXES

Copolymer of divinyl ether and maleic anhydride (DVE-co-MA) derivatives of cis-platinum complexes were synthesized and characterized by elementary analysis, IR and XPS ( X-ray photoelectron spectroscopy). The behavior of the products in biological environment was also studied. UV-visible and fluorescence spectra show that these polymer derivatives are able to exchange ligands with selected nucleophilic groups in biological environment.     

KINETICS OF SUSPENDED EMULSION POLYMERIZATION OF METHYL METHACRYLATE*

 The kinetics of suspended emulsion polymerization of methyl methacrylate (MMA), in which water acted as the dispersed phase and the mixture of MMA and cyclohexane as the continuous phase, was investigated. It showed that the initial polymerization rate (R_p0) and steady-state polymerization rate (R_p) were proportional to the mass ratio between water and oil phase, and increased as the polymerization temperature, the potassium persulphate concentration ([I]) and the Tween20 emulsifier concentration ([S]) increased. The relationships between the polymerization rate and [I] and [S] were obtained as follows: R_p0∝[I]^0.71[S]^0.23.The above exponents were close to those obtained from normal MMA emulsion polymerization. It also showed that the average molecular weight of the resulting poly(methylmethacrylate) decreased as the polymerization temperature,[I]and [S] increased. Thus, MMA suspended emulsion polymerization could be considered as a combination of many miniature emulsion polymerizations proceeding in water drops and obeyed the classical kinetics of MMA emulsion polymerization.     

SYNTHESIS OF POLYBUTADIENE MACROINITIATOR AND POLYBUTADIENE/POLYACRYLAMIDE BLOCK COPOLYMERS

An azo-group containing polybutadiene macroinitiator was prepared by Pinner synthesisand characterized by IR, NMR, GPC, viscosity and elemental measurements. Themacroinitiator was further used to polymerize acrylamide (AAm) in benzene to formpolybutadiene/polyacrylamide (PBD/PAAm) block copolymers. High conversion of AAm wasobtained over a wide range of monomer/macroinitiator ratios. The PBD/PAAm blockcopolymers.were found to have excellent solvent resistance.     

SYNTHESIS AND PROPERTIES OF NEW MESOGEN-JACKETED LIQUID CRYSTALLINE POLYMERS*

Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, andmesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of thesepolymers was examined using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Theirliquid crystallinity is influenced by the variation of polymer backbone, spacer, mesogenic unit and its terminal groups. Theresults show that 1) a more flexible polymer main-chain is more favorable to the formation of a liquid crystal phase, while 2)a flexible spacer will decrease the "Jacket Effect" and the liquid crystallinity and 3) a subtle modification of the terminalgroups on the mesogenic unit may also have a significant influence on properties of the polymers.     

POLYMERIZATION OF OCTAMETHYLCYCLOTETRASILOXANE WITH HEXAMETHYLDISILAZYL-LITHIUM AS INITIATOR*

 This work focused on the anionic polymerization of octamethylcyclotetrasiloxane (D₄, D = Me₂SiO_2/2) initiated by a new kind of initiator hexamethyldisilazyl-lithium (MM^NLi). ²⁹Si-NMR spectroscopy and gas chromatography (GC) were used to characterize the polymerization products. The process was accelerated by adding a small amount of high activity monomer D₃ and by raising the polymerization temperature. At the end of polymerization more than 95% of the monomer was converted to polymer and only a very small amount ofD₄ and D₅ remained in the polymers.     

SYNTHESIS OF SILICON MONOMERS AND OLIGOMERS CONTAINING CYCLOHEXYLENE RING

1,3-Bis(trichlorosilyl) cyclohexane was obtained by addition of HSiCl_3, to cyclohexadiene-1,3in the presence of H_2PtCl_6.6H_2O in isopropyl alcohol. The new compound was ethanolysed andmethylated to form di-methyl tetra-ethoxy disilyl, tri-methyl tri-ethoxy disilyl and terta-methyldi-ethoxy disilyl cyclohexanes. These di-to tetra-functional monomers were hydrolyzed by hydrochloric acid in ether. The di-functional monomer yielded cyclic dimer similar to octamethylcyclotetrasiloxane and the tri-functionalmonomer, a cyclic tetramer, while in the case of tetra-functional monomer a cyclic octamer wasobtained. These compounds have not been reported in literature.