PREPARATION OF POLYMER MICROSPHERES WITH PYRIDYL GROUP AND THEIR STABILIZED GOLD METALLIC COLLOIDS

Narrow disperse poly(ethyleneglycol dimethacrylate-co-4-vinylpyridine)(poly(EGDMA-co-4-VPy))microspheres were prepared by distillation-precipitation copolymerization of ethyleneglycol dimethacrylate(EGDMA)and 4-vinylpyridine (4-VPy)with 2,2'-azobisisobutyronitrile(AIBN)as initiator in neat acetonitrile.The polymer microspheres containing pyridyl group were then utilized as stabilizer for gold metallic colloids with the diameter around 7 nm,which were prepared by the in situ reduction of gold chloride trihydrate with sodium borohydride through the coordination of the pyridyl group on the gel layer and surface of the microsphere with the gold metallic nano-particles.The catalytic properties of the pyridyl- functionalized microsphere-stabilized gold metallic colloids and the behavior of the stabilized-catalyst for the recycling were investigated with reduction of 4-nitrophenol to 4-aminophenol as a model reaction.     

POLYMERIZATION MECHANISM OF N-VINYLCARBAZOLE WITH CHIRALLY ORGANIC SALT AS CATALYST

The polymerization mechanism is described by the conductance changewith the time during the polymerization. The mechanism can be explained by the equi-librium feature (i.e. main ion-pairs) between the free ions and the ion-pairs dissociated bythe organic salt (-) Sp~/(*~+) (+) CSA~(*~-) (An asterisk represents the chirality) and the schemeof the polymerization process is described mainly by the charge transfer complexes havingchiral induction power.     

ENDOR AND ESR STUDIES OF RADICALS FORMED IN FRIEDEL-CRAFTS REACTIONS

The present study deals with the study of some Friedel-Crafts alkylating system and the accurate measurement of hyperfine coupling constants by ESR and ENDOR techniques. The results indicate that the observed ESR spectra are due to polycyclic aromatic radical cations formed from their parent hydrocarbons.It is suggested that benzyl halides produced in the Friedel-Crafts alkylating reaction undergo Scholl condensation reaction to give polycyclic aromatic hydrocarbons, which were converted into the corresponding polycyclic aromatic radical cations in the presence of aluminum chloride.     

MOLECULAR VOLUMES OF SALTS. WITH TRIANGULAR RADICALS

The present paper discusses some characteristics of the molecular volumes of carbonates, nitrates and borates. It confirms that the molecular volume of H_2O in the hydrates of this kind of salts approximates to a constant. When the coordination numbers of cations in mixed salts are identical with those in the single salts, the additivity of the molecular volume is quite accurate. Over 100 sets of data demonstrate that a general additivity is true, the average relative error being ±2.31%. The concept of the topological molecular volume is proposed based, on the additivity. For salts with the same radical and equally charged cations, the molecular volume varies linearly with the cation radius. The volume effects of CO_3~(2-) NO_3~- and BO_3~(3-) in packing can be obtained by extrapolation. They are equal to a large sphere whose volume is the sum of those of three O~(2-). This paper also discusses the possibility of compiling a table of ionic volumes.     

REACTIONS OF ORGANODILITHIUM COMPOUND WITH ALKYL HALIDES

The mechanism of the electron transfer reaction of 1,4-dilithio-tetraphenyl-1,3-butadiene with methyl iodide was studied.     

THEORETICAL STUDY OF POLYMERIZATION WITH POSITIONAL ISOMERISM

The polymerization with positional isomerism has been theoretically studied by means ofthe nonsteady-state kinetic method. The distribution function of head-to-tail sequence, theexpressions of the concentrations of head-to-head and tail-to- tail enchainments, and variousdyad and triad fractions have been rigorously derived on the basis of the reaction scheme.Finally, the relationships between the microstructural parameters of the resultant polymerand the polymerization conditions have been established, so that the microstructure of thepolymer with positional isomerism can be predicted from the polymerization conditions. In thecase of the reaction time being long enough, the expressions of dyad and triad fractionsgiven in this paper are simplified into those derived from the probability method.     

POLYMER—SUPPORTED SINGLE AND MIXED AMMONIUM AND PHOSPHONIUM SALTS AS CATALYSTS FOR PHASE—TRANSFER REACTIONS

In this study was to investigate,by phase-transfer catalysis,the activity of single and mixed ammonium and phosphonium salts grafted on a “gel-type“ stryene-7% divinylbenzene copolymer in the oxidation of benzyl alcohol with hydrogen peroxide.A wide variety of catalysts with different quaternary groups and different quaternary chain length substitutents were examined.The activity of single“onium“salts increases as a consequence of the association of ammonium and phosphonium salts grafted onn the same polymeric support.The activity of polymer-supported ammonium and phosphonium salts increases with the number of carbon atoms contained in the alkyl radicals of the -onium and of the functionalization degree with phosphonium groups.     

A STUDY OF THE REACTIONS OF BENZYL ETHERS WITH DIBROMOCARBENE

Using potassium carbonate as base and a polyethylene glycol with an average molecular weight of 600 (PGE600) as phase transfer catalyst, reaction of benzyl ethers with dibromocarbene leads to benzylic C—H bond insertion products, aromatic aldehydes are also formed as one of the products.     

STUDIES ON CHARGE TRANSFER POLYMERIZATION——POLYMERIZATION OF ACRYLONITRILE INITIATED WITH PHENYL HYDRAZINE AND ITS DERIVATIVES

The photopolymerization of acrylonitrile (AN) initiated with phenyl hydrazine (PHZ) and its derivatives has been studied. The initiator exponent and monomer exponent were determined from the kinetic investigation to be 0.66th and 2.1th respectively and the overall activation energy was 33.4KJ/mol for the PHZ-AN system. Spectral analysis and other data indicate that a charge transfer complex between PHZ as a donor and AN as an aceeptor is formed. The initiation mechanism was proposed.     

PHOTOINDUCED ADDITION REACTIONS OF CHLORANIL WITH FURAN DERIVATIVES

Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential electron and proton transfer from la or 1b to ~3TCBQ followed by coupling of the furfuryl and semiquinone radical pairs was proposed and is evidenced by the photo-CIDNP studies of the TCBQ-1a and TCBQ-1b systems.     

RUPTURING OF POLYMER FILMS WITH RUBBING-INDUCED SURFACE DEFECTS

It has been a long-standing question whether dewetting of polymer film from non-wettable substrate surfaceswherein the bicontinuous morphology never forms in the dewetting film is due to spinodal instability or heterogeneousnucleation. In this experiment, we use a simple method to make the distinction through introduction of topographical defectsof the films by rubbing the sample surface with a rayon cloth. Spinodal dewetting is identified for those films that dewet by acharateristic wavevector, q, independent of the density of rubbing-induced defects. Heterogeneous nucleation, on the otherhand, is identified for those with q increasing with increasing density of defects. Our result shows that PS films on oxidecoated silicon with thickness less than ≈ 13 nm are dominated by spinodal dewetting, but the thicker films are dominated bynucleation dewetting. We also confirm that spinodal dewetting does not necessarily lead to a bicontinuous morphology in thedewetting film, contrary to the classic theory of Cahn.     

PREPARATION OF POLY（ETHYLENEGLYCOL-co-ACRYLIC ACID） MICROSPHERES WITH DIVINYLBENZNE AS CROSSLINKER BY DISTILLATION-PRECIPITATION POLYMERIZATION

Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.     

KINETIC STUDY OF THE REACTIONS OF TRIARYLPHOSPHINES WITH α-HALO SULFONES

Abstract

Reaction of a series of triarylphosphines with α-halo-m-cyanobenzyl phenyl sulfones gives the following Hammett ρ values: (CI) ρ = ?1.84; (Br) ρ = ?3.03; (I) ρ = ?3.36.     

POLYMERIZATION MECHANISM OF DIENES WITH HOMOGENEOUS RARE EARTH CATALYSTS

The reaction mechanisms of diene polymerization with homogeneous rare earth catalyst are studied by means of the spectra of ~1H-NMR, one-and two-dimensions ~(13)C-NMR. Based on the data of above NMR spectra, it is proposed that the polymerization reaction proceeds according to the following mechanism: η~4-diene (cis-(?)trans-)and η~3-allyl (syn-(?)anti-).     

STUDY ON POLYMERIZATION OF OILLESS ALKYD RESIN WITH PHENYLTRIETHOXYSILANE

Oilless alkyd resin modified with the silicoorganic compounds has been obtainedsuccessfully by polymerization.At appropriate proportion of silicoorganic compounds,thepolymerized product has higher hardness and lustre than that of oilless alkyd resin.     

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.     

PREPARATION OF MONODISPERSE CROSSLINKED POLYMER MICROSPHERES HAVING CHLOROMETHYL GROUP BY DISTILLATION-PRECIPITATION POLYMERIZATION

Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene) (poly(CMSt-co-DVB)) microspheres were prepared by distillation-precipitation copolymerization of chloromethylstyrene (CMSt) and divinylbenzene (DVB) in neat acetonitrile. The polymer particles had clean surfaces due to the absence of any added stabilizer. The size of the particles ranges from 2.59 μm to 3.19 μm and with mono-dispersity around 1.002-1.014. The effects of monomer feed in copolymerization on the microsphere formation were described. The polymer microspheres were characterized by SEM and chlorinity elemental analysis.     

CHEMISTRY OF DENUDATINE I. THE REACTIONS OF DENUDATINE AND DIACETYLDENUDATINE WITH NBS-HOAc

The reactions of denudatine 1 and diacetyldenudatine 2 with NBS-50% HOAc soln. afforded 4 and 6, respectively, in high yields.Treatment of 6 with (Ac)_2CO-Pyr. gives 7. The structures of 3,6 and 7 were deduced on the basis of spectral and chemical methods.     

SYNTHESIS OF N,N''''-DISUBSTITUTED MONOTHIOXAMIDE AND STUDY OF THEIR REACTIONS WITH DIAMINES

In this paper, six N,N'-disubstituted aonothioxamides were synthesized and the reactions between these monothioxamines and diamines (1,2-diamino ethane and 1,3-diamino propane) were studied. Some new compounds were synthesized by using these reactions.     

GROUP TRANSFER POLYMERIZATION OF ETHYL ACRYLATE WITH LEWIS ACID CATALYST

This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃and above 0℃. The amount of catalyst used was studied. When zinc iodide catalyst used is more than 10mol% relative to monomer, the rate of polymerization is proportional to the concentration of monomer, whereas zinc iodide catalyst used is less than 10 mol% of the monomer, the rate of polymerization is independent of the monomer concentration.In the GTP of EA an induction period was observed when the zinc iodide contents are less than l0mol%. If the reaction temperature is over 0℃, living species become unstable and diminish, leading to incomplete monomer conversion. The reaction curves equations are obtained. The polymers have narrow molecular weight distributions which are not changed as decreasing zinc iodide contents. The polydispersity is about 1.2.