Neodymium oxide-assisted melt free-radical grafting of maleic anhydride on isotactic-polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd2O3), -assisted melt free-radical grafting of maleic anhydride (MAH) on isotactic-polypropylene (i-PP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd2O3 into reactive system leads to an enhancement of the grafting degree of MAH, along with an elevated degradation of i-PP matrix. When Nd2O3 content is 4.5 mmol %, the increment of the grafting degree of MAH (maximally) is up to about 30% compared with that of the related system without adding Nd2O3, while the severest degradation of i-PP matrix simultaneously occurs. On the basis of the reaction mechanism of PP-g-MAH proposed before, the sequence of beta-scission and grafting reaction is discussed in detail. It is found that, for the reactive system studied, most tertiary macroradicals first undergo beta-scission, and then, grafting reaction with MAH takes place at the new radical chain ends. The imported Nd2O3 has no effect on the aforementioned reaction mechanism, whereas it enhances the initiating efficiency of the initiator, dicumyl peroxide (DCP).

Synthesis and free-radical ring opening polymerization of macrocyclic aryl thioether ether ketone (sulfone) oligomers

Two kinds of novel macrocyclic aryl thioether ether oligomers were synthesized by nucleophilic condensation reaction in high yields under pseudo-high-dilution condition. A combination of H-1 NMR, GPC and MALDI-TOF MS analyses unambiguously confirmed the cyclic nature and their distributions, Macrocyclic thioether ether ketone oligomers can undergo facile melt ring opening polymerization(ROP) initiated by thiyl radical to give a high molecular weight polymer.

Novel macrocyclic aryl thioether ester oligomers: structure characterization and free-radical ring opening polymerization

Novel macrocyclic aryl thioether ester oligomers have been synthesized in high yield from phthaloyl dichloride and 4,4'-thiodiphenol under pseudo high dilution conditions. The cyclic nature was unambiguously confirmed by a combination of MALDI-TOF MS, gel permeation chromatography and NMR analyses. Single-crystal X-ray diffraction of cyclic ester dimer reveals no severe strain on the cyclic structure. The free-radical ring opening polymerization (ROP) of the macrocyclic oligomers was achieved to give high molecular weight polymers via a transthioetherification reaction. The molecular weight of the polymer resulting from ROP decreases as the conversion of cyclic oligomers increases after a polymerization period of 30 min.

Iron(II)-8-quinolinol/MCM-41-catalyzed phenol hydroxylation and reaction mechanism

Iron(II)-8-quinolino/MCM-41 is prepared. Its catalysis is studied in phenol hydroxylation using H2O2 (30%) as oxidant. The experiment shows that Iron(II)-8-quinolinol/MCM-41 has good catalytic activity and desired stability. Based on cyclic voltammetry, ESR, and UV-visible spectra studies of iron(II)-8-quinolinol complex in liquid phase, a radical substitution mechanism is proposed and used to demonstrate the experimental facts clearly. (C) 1997 Academic Press.

Phenol hydroxylation by iron(II) phenanthroline: The reaction mechanism

Phenol hydroxylation catalyzed by iron(II)-1,10-phenanthroline is investigated through kinetics, ESR, W-Vis as well as cyclic voltammogram studies. The optimum reaction conditions are obtained for diphenols production. Radical substitution mechanism is first proposed to explain the effects of pH, reaction medium and other factors on the phenol hydroxylation with H2O2 as oxidant, and found that the coexisting of iron(II)-1,10-phenanthroline and iron(III)-1,10-phenanthroline is the key for phenol hydroxylation to occur with H2O2 as oxygen donor.

Reactions of C-60 with R(3)SnH: A new synthetic route to C-60(RH)(n) and the property of C-60 to catalyze radical reactions

A new method for the preparation of polyalkyl and polyarenefullerene derivatives C-60(RH)(n)(R=Bu,n=1-3; R=Ph,n=1-10) by the reaction of C-60 with organotin hydride in toluene is described. Another series of products of stannanes R(a)Sn(b)H(c) (R=Bu, a=3-8, b=1-4, c=0-3 R=Ph, a=3-11, b=1-5, c=0-4) were also obtained, which shows that C-60 can catalyze polymerization of organic-tin. These products were determined by mass and infrared spectrometry. And the possible reaction mechanisms are discussed.

THEORETICAL-STUDIES ON THE CYCLIZATION PROCESS OF A NEW ORGANOSULFUR REACTION

The cyclization process of a new organosulfur reaction was studied by the MNDO (UHF) method. The first reaction path was assumed to be via the organosulfur radical intermediate, the second via the ionic (cationic and anionic) intermediates. The dehydroxylation process was assumed to occur with the synergistic cyclization. The results obtained indicate that the potential energy barrier of the first reaction path was about 102 kcal mol(-1), and although the formation of the ionic intermediate is comparatively difficult, the potential energy barrier of the second path is comparable to the first. The sequential reaction path via the radical intermediate, i.e. first cyclization, then dehydroxylation, was investigated for comparison. The cyclization reaction was found to be the thermodynamically favored process, while the ensuing dehydroxylation process was found to have a potential energy barrier of about 62 kcal mol(-1).

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF BENZOYL PEROXIDE - A RADICAL AROMATIC-SUBSTITUTION RESULTING IN BIPHENYLCARBOXYLIC ACID IN THE GAS-PHASE

A radical aromatic substitution resulting in biphenylcarboxylic acid is inferred for the decomposition of benzoyl peroxide from the chemical ionization and collision-induced dissociation mass spectra. The thermolysis of benzoyl peroxide gives rise to a benzoyloxy radical, which undergoes rapid decarboxylation and hydrogen abstraction leading to phenyl radical and benzoic acid, respectively. Attack of the resulting phenyl radical on the benzoic acid results in bipbenylcarboxylic acid. On the other hand, the phenyl radical abstracts a hydrogen atom to yield benzene, which is then subjected to the attack of a benzoyloxy radical, affording phenyl benzoate. This substitution reaction rather than the recombination of benzoyloxy and phenyl radicals is found to be responsible for the formation of phenyl benzoate under the present conditions.

Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid

To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.

Numerical Simulation of Gaseous Detonation of H_2-O_2 Mixture with Detailed Chemical Reaction Model

采用高精度的ENO格式和基于基元化学反应的真实化学反应模型求解氢氧混合气体一维爆轰波的精细结构。采用直接起爆方法得到稳定传播的爆轰波,计算的爆轰波阵面参数和实验相当符合。对爆轰波反应区化学反应的研究表明,参与反应的不同组分具有不同类型的变化特征。网格尺寸影响的研究表明,计算结果的精度随着网格尺寸的增加而增加,并能保持较好的收敛性。移动网格研究结果表明,网格运动速度和爆轰速度接近时,两者的相互作用对计算结果产生一定影响。

Microscopic theory of chemical-reaction rate

In this paper we deduce the formulae for rate-constant of microreaction with high resolving power of energy from the time-dependent Schrdinger equation for the general case when there is a depression on the reaetional potential surface (when the depression is zero in depth, the case is reduced to that of Eyring). Based on the assumption that Bolzmann distribution is appropriate to the description of reactants, the formula for the constant of macrorate in a form similar to Eyring's is deduced and the expression for the coefficient of transmission is given. When there is no depression on the reactional potential surface and the coefficient of transmission does not seriously depend upon temperature, it is reduced to Eyring's. Thus Eyring's is a special case of the present work.