THE MOLECULAR WEIGHT AND ITS DISTRIBUTION OF 1, 2-POLYBUTADIENES PREPARED WITH MOLYBDENUM CATALYST SYSTEMS

The study on the molecular weight and its distribution of 1, 2-polybutadienes prepared with MoCl_4OR-i-Bu_2AlOR' catalyst systems has been carded out by viscosity and GPC methods. 1, 2-Polybutadienes with (?)=1.2-2.0can be obtained with these catalyst systems at 30—70℃. There is a linear relation between the (?) and the polymerization temperature. It was found by extrapolation that these catalyst systems may possibly initiate a living polymerization at the temperature near 18℃. The molecular weight of the polymers can be regulated either by polymerization temperature or by adding polar compounds such as allyl halides.     

A STUDY OF LOW-TEMPERATURE CRYSTALLIZATION BEHAVIOR THE cis-1,4 POLYBUTADIENE PREPARED WITH RARE-EARTH CATALYST SYSTEM

The effects of molecular weight and temperature on crystallization processes at low tempera-ture for cis-1,4 polybutadiene prepared with rare-earth catalyst (Ln-PB) have been studied by WAXDmethod. In the range of molecular weight from     

STUDIES ON RADICAL POLYMERIZATION OF METHYL METHACRYLATE INITIATED WITH ORGANIC PEROXIDE-AMINE SYSTEMS

Radical polymerization of methyl mcthacrylate (MMA) initiated with various diacyl peroxideamine systems was studied. Benzoyl peroxide (BPO) and lauroyl peroxide (LPO) were used as diacyl peroxide component, N,N-dimethyl aniline (DMA) and its para substituted derivatives, i.e., N,N-dimethyl-p-toluidine (DMT), p-hydroxymethyl-N,N-dimethyl aniline (HDMA), p-nitro-N,N-dimethyl aniline (NDMA) and p-dimethylamino benzaldehyde (DMAB) were used as amine components. It was found that the peroxide-DMT systems give higher rates of bulk polymerization R_p of MMA than the organic hydroperoxide-DMT systems with the following descending order BPO-DMT>LPO-DMT>CHP (cumene hydroperoxide)-DMT>TBH (tert-butyl hydroperoxide)-DMT. The aromatic tertiary amines possess obvious structural effect on the R_p values in the diacyl peroxideamine system. The overall activation energy of MMA polymerization was determined and thekinetics of polymerization of MMA initiated with BPO-DMT system was investigated.     

STUDIES ON THE ORGANIC PEROXIDE-DITERTIARY AMINE INITIATION SYSTEMS

Radical polperization of methyl methacrylate (MMA) initiated with organic peroxide-ditertiaryamine binary systems was studied. Benzoyl peroxide (BPO), lauroyl peroxide (LPO), t-butyl hydro-peroxide (TBH), and t-butyl peroxybenzoate (TBPB) were used as organic peroxide components,aromatic ditertiay amine 4, 4′-tetramethyldiaminodiphenylmethane (TMDAPM) an d aliphatic di-tertiary amine tetramethylethylenediamine (TMEDA) were used as amine components. The polymeri-zation rate R_P, the overall activation energy of polymerization E_a, the rate equation of MMA poly-merization, and the end group of polymer formed were determined.     

RHEOLOGICAL MODIFICATION OF EPOXY RESINS WITH NANO SILICA PREPARED BY THE SOL-GEL PROCESS*

Nano silica-modified epoxy resins were synthesized by the sol-gel process. The materials have themorphological structure of nano particales dispersed in the epoxy matrix. The dispersed phase formed aphysical network in the resin and thus influenced the rheological behavior greatly. However, the nano silicadid not show a significant influence on the mechanical properties of the cured resins.     

DYE-SENSITIZED PHOTOLYSIS OF o-Cl-HEXAARYLBIIMIDAZOLE AND PHOTOPOLYMERIZATION KINETICS STUDY OF THE LONG WAVE-LENGTH DYE/HEXAARYLBIIMIDAZOLE SYSTEMS*

o-Chloro-hexaarylbiimidazole (o-Cl-HABI) can be sensitized efficiently by the dyes 1-ethyl-3'-methyl thiacyaninebromide (C 1), 3,3'-diethyl thiacarbocyanine iodide (C 2), and cyclopentanone 2,5-bis[2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylidene] (C 3) through electron transfer proceses. When exposed to a xenon lamp (filtered by Pyrex glass),the photosensitive systems composed of o-Cl-HABI and the above dyes can produce free radicals which initiate thepolymerization of MMA. The photopolymerization kinetics equation was obtained for the o-Cl-HABI/C2 system, R_p=K [C2]~(0.75)[o-Cl-HABI]~(0.44)[MTA]~(0.12)[MMA]~(10). A comparison of the influence of different dyes on the conversion of MMA photopolymerization was conducted.     

STUDIES ON THE MECHANISM OF VINYL PHOTOPOLYMERIZATION INITIATED BY CONDENSED AROMATIC HYDROCARBON-ANILINE SYSTEMS

Initiation mechanism of the photopolymerization of acrylonitrile and methyl methacrylate, usingbinary condensed aromatic hydrocarbon (CAH)-aniline systems as initiator, was studied. The strongerthe electron-donating ability of the aniline derivatives, the faster the the of photopolymerizationwill be. The radical intermediates produced by photoreaction between anthracene and anilinewere detected with ESR spectra. The initiation scheme involves the formation of exciplex betweenthe excited singlet state of CAH and the ground state of aniline as the first step, and then followedby proton transfer, leading to the generation of two kinds of radicals. From the end-group analysisof the polymers obtained, it is suggested that both kinds of radicals are involved in the initiation.     

STUDIES ON THE KINETICS OF VINYL PHOTOPOLYMERIZATION INITIATED BY CONDENSED AROMATIC HYDROCARBON-ANILINE SYSTEMS

The photopolymerization of acrylonitrile and methyl methacrylate initiated by condensed aro-matic hydrocarbon-aniline systenis was studied at 25℃under irradiation of 365 nm wavelengthlight. From kinetic data the monomer exponent has been measured to be 1.1. Within the concen-tration of 10~(-4)--10~(-3)M, the aromatic hydrocarbon exponents changrd from 0.30 to 0.40, depedingon the values of molar extinction coefficient of the hydrocarbons at 365 nm (ε_(365)). The greater theε_(365), the Iower the exponents. The aniline exponents were measured to be in the range of 0.30--0.45. The aromatic hydrocarbon-aniline systems with the lower aniline exponent showed a lower ratioof the fiuorescence quenching of the hydrocarbon by aniline and by the monomer.     

PHOTOPOLYMERIZATION IN THE MICELLAR SYSTEMS Ⅳ THE PHOTOSENSITIZATION EFFECTS OF THE BENZOPHENONES WITH DIFFERENT CHARGE IN IONIC MICELLAR SYSTEMS*

The photosensitization effects of the benzophenone derivatives having different charges, such as cationic BP(BP—CH_2—N~+ (C_2H_5)_3Br~-) (PKT-1), anionic BP(BP—COONa) and the neutral BP in the various ionic micellar systems were studied. From the photopolymerization of MMA initiated by the various BP/TEA in different micellar systems, the results obtained show that the polymerization rate is in the order of PKT-1>BP>BP—COONa in the SDS anionic micelle. On the contrary, the order changes to BP—COONa>BP>PKT-1 in the CTAB cationic mieelle, and to BP—COONa≈PKT-1>BP in the PKT-3 functional micelle. It is noteworthy that the PKT-1/SDS system is more efficient with its quantum yield more than 50 times compared with that of simple BP/H_2O system.     

THE ELECTROCHEMICAL PREPARATION OF POLYPHENOL WITH CONDUCTIBILITY

Polyphenol film deposited on platinum foil can continuously grow with time during the electrolysis of a phenolsolution consisting of 0. 1 mol L~(-1) phenol, 3 mol L~(-1) NaOH and 0.5 mol L~(-1) Na_2SO_4, as has been proved by the methods ofsweep potential, constant potential and constant current, and visible spectra during the electrolysis of phenol. A polyphenolfilm with thickness of 0.11 mm was obtained by the electrolysis of phenol at a constant potential of 0.70 V (versus Ag/AClwith saturated KCl solution). Polyphenol film is inactive and stable in 2 mol L~(-1) H_2SO_4 solution, neutral solution and3 mol L~(-1) NaOH solution and in the potential range between -0.95 and 1.35 V. The usable potential range is dependent onthe pH value. Polyphenol has an ESR signal with a g factor of 2.0049. The conductivity of polyphenol is 1.2×10~(-4) S cm~(-1). Inthe solution of polyphenol dissolved in DMSO, the mobility of polyphenol anions is 8×10~(-9) m~2 s~(-1) V~(-1) at 20℃.     

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.     

CURE OF A MICROGEL-EPOXY RESIN TWO-PHASE POLYMER WITH ETHYLENE DIAMINE

The curing of a microgel-epoxy resin two phase polymer prepared by in situ copolymerization of unsaturated polyester with acrylic monomer was studied. The unsaturated unit reacted with N—H during the cure of the resin with ethylene diamine. The Michael type reaction was ten times more rapid than the addition of N—H to epoxide.This was accounted for the lower apparent activation energy of the curing of the two phase resin.     

REINFORCEMENT OF CALCIUM PHOSPHATE CEMENTS WITH PHOSPHORYLATED CHITIN

Phosphorylated chitins (P-chitins) as the additives of calcium phosphate cements (CPCs) were prepared by thephosphorylation of chitin with phosphorus pentoxide in methanesulfonic acid. Their physical properties and effects on CPCsfrom monocalcium phosphate monohydrate (MCPM) and calcium oxide (CaO) or dicalcium phosphate dihydrate (DCPD)and calcium hydroxide [Ca(OH)_2] were investigated. Addition of P-chitin (M_w = 2.60×10~4; degree of substitution, DS =0.68) to the liquid phase in amounts up to 3 wt% for MCPM and CaO cements or 1.5 wt% for DCPD and Ca(OH)_2 cementscould enhance the mechanical strength considerably while little influence on the setting time was observed. However, furtheraddition of P-chitin will cause no setting.     

SYNTHESIS OF MESOGENIC POLYESTERS WITH 2-DICHLOROMETHYLHYDROQUINONE MOIETIES

A series of novel mesogenic polyesters with 2-dich1oromethylhydroquinone moieties weresynthesized by polycondensation of the novel diacyl chloride monomer 2-dichloromethyl-1, 4-bis (4'-chloroformylbenzoyl) oxybenzene-(I) with α,ω-polymethylenediols including ethyleneglycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 10-decanediol. The diacyl chloride monomerwas synthesized by simultaneous transformations of both the carboxy and formaldehydegroups of 2-formyl-1, 4-bis (4'-carboxybenzoyl) oxybenzene into acyl chloride anddichloromethyl groups respectively. The syntheses of the monomer (I) and the polymers werereported.     

HETEROJUNCTION DIODES OF POROUS SILICON WITH SOLUBLE POLYANILINE*

Two kinds of heterojunction diodes of porous silicon (PS) with soluble polyaniline (PANI) werefabricated. One is a heterojunction diode of PS with water-soluble copolymer of polyaniline (PAOABSA),Al/PS-PAOABSA/Au cell as rectifying diode. Another is a heterojunction diode of PS with solublepolyaniline doped with DBSA, Al/PS-PANI (DBSA)/Au cell as light emitting diode (LED). The rectifyingcharacteristics of the rectifying diodes were measured as a function of the degree of sulfonation and thicknessof the copolymers, as well as oxidation of PS. The rectifying ratio of the heterojunction can reach 5.0×10~4 at±3 V bias. For the LED, the photoluminescence (PL) and electroluminescence (EL) spectra were measuredand discussed.     

INTERACTION OF POLYVINYLPYRROLIDONE WITH METAL CHLORIDE AQUEOUS SOLUTIONS

Interactions of polyvinylpyrrolidone (PVP) with metal chlorides (MgCl2, CaCl2, KC1 and BaC12) have been investigated by viscometric and spectrophotometric techniques in aqueous solutions. Intrinsic viscosity [η] of (PVP) has shown a discontinuity with varying concentration of metal chlorides. The decreasing order of effectiveness of cation is K1 ＞Ca2 ＞ Mg2 ＞ Ba2 for poly(vinylpyrrolidone) solution. Changes in the absorption spectra of the cosolutes were observed in the presence of PVP in the lower limit of the UV-visible region i.e. 200-210 nm. These changes were attributed to interaction of PVP molecules with the cosolute molecules. As the concentration of the cosolute increased, a red shift in the peaks was observed, indicating an increase in interaction between PVP and cosolutes.     

GRAFT COPOLYMERIZATION OF DENTAL COLLAGEN WITH METHYL METHACRYLATE

The graft copolymerization of MMA onto human dentin was studied with the redox system usingK_2S_2O_8+NaHSO_3 as initiator. The IR spectrum of the copolymer showed the presence of C=Oband at 1720 cm~(-1),C--O at 1260~(-1), CH_3, at 2850 cm~(-1). indicating the presence of polymerized me-thacrylate on the detin. The ppt. of the acid hydrolysis of the graft copolymer showed an -NH_3~+band of amino acid at 3200 cm~(-1). Most marked percent decreases in contents of amino acids inthe acid hydrolysate were observed in serine, tyrosine and methionine. The absolute amounts ofglycine, alanine and proline have also decreased markedly. This suggests that it was most proba-ble that the graft copolymerization occurred at these residues. The tubular stripes and cross sectioncavities of dentin tublets were covered with a high polymer graft which could be seen from the SEMpictures. The mol. wt. of this grafted high polymer, as determined by GPC, was higher than thatof the homopolymer and the former had a broader mol. wt. distribution. All these facts suggest-ed that a genuine graft copolymerization of MMA onto human dentin occurred.     

不同催化体系聚乙炔的热裂解反应

<正> 自从白川英树等合成聚乙炔(PA)膜,并用电子受体或给体掺杂使其变为P型或n型半导体之后,近年来对PA的合成、结构及性能进行了大量研究,但采用PGC法对PA热裂解反应的研究,只有为数不多的报道。本文介绍了热异构化前后的稀土(Ln)和钛(Ti)两体系合成的PA的热裂解反应,提出一个适于比较两体系PA的参数,并观察了     

CONTROLLED RELEASE FROM PDMAEMA GELS PREPARED BY GAMMA RADIATION

Poly(N, N-dimethylaminoethyl methacrylate) (polyDMAEMA) hydrogels prepared by γ-irradiation showed obvioustemperature-sensitivity in a temperature range of 38-40℃ and pH-sensitivity at pH = 2.5. They also showed clectric responsebehavior although it was not typical. The hydrogels were used in controlled release at different pH, temperature, and electricvoltage. The release rates of methylene blue (MB) from the gels at 52℃ and pH = 1.24 were fatter than those at 20℃ and pH= 10.56, respectively. In addition, the release rate at a field voltage of 5.0 was also faster than that without electric field.     

SURFACE MODIFICATION OF CaCO_3 WITH DENDRITIC CARBOXYLIC ACIDS

Nanometer calcium carbonate was modified with Frechet type polyether dendrons bearing a COOH group at thefocal point by a wet-coating technique in dichloromethane at room temperature. The interaction between CaCO_3 and thedendritic modifier was proven by IR and mass spectroscopy of the modified CaCO_3 after thorough extraction withdichloromethane. The amount of tightly bonded organic modifier was estimated by TGA. It was shown that the amount ofbonded molecules decreased with increasing generation number due to the larger number of branches. Compared tounmodified CaCO_3, the modified CaCO_3 possess different dispersibility in water and in organic solvents.