Kinetics and mechanism of cationic oligomerization of styrene using poly(styrenesulphonic acid) resin as catalyst

The cationic oligomerization of styrene in benzene using poly(styrenesulphonic acid) resin as catalyst, was carried out under nitrogen. A kinetic model involving initiation, propagation, chain transfer to monomer and spontaneous termination steps, is proposed to fit the experimental kinetic data. It is found that (1) the propagation constant decreases with increasing chain length and remains constant as $\text{n ≧ 5}$; (2) the constant for chain transfer to monomer is also chain length dependent and reaches a maximum at n = 4.     

丁烯齐聚酸性催化剂的研究进展

介绍了丁烯在酸性催化剂上齐聚的反应机理,并以固体磷酸催化剂、分子筛催化剂、负载型催化剂和酸性树脂催化剂为线索,评述了国内、外用于丁烯齐聚反应的酸性催化剂的研究进展。     

超支化大分子桥联水杨醛亚胺钴催化剂催化乙烯低聚

以1.0代（1.0G）超支化大分子、水杨醛和CoCl₂·6H₂O为原料,依次经过希夫碱反应和络合反应合成了3种具有不同烷基链长度的新型超支化大分子桥联水杨醛亚胺钴催化剂。对目标产物的结构进行FT-IR、UV、MS及TG表征,考察了溶剂种类、助催化剂种类、反应温度、反应压力、Al/Co摩尔比等条件对超支化大分子桥联水杨醛亚胺钴催化剂催化乙烯低聚性能的影响。结果表明,超支化大分子桥联水杨醛亚胺钴催化剂催化乙烯低聚表现出良好的催化活性和高碳烯烃（C₁₀₊）的选择性。催化活性随反应温度和Al/Co摩尔比增加先增加后下降,随反应压力增加而增加。以甲苯为溶剂,在一氯二乙基铝（DEAC）活化下,当反应温度为25℃、反应压力为0.5 MPa、Al/Co摩尔比为500时,催化活性可达1.87×10⁵ g·（mol Co）^-1·h^-1,聚合产物中高碳烯烃的含量高达42.90%。     

聚四氟乙烯修饰的固体酸催化剂上异丁烯迭代反应性能

研究了硅胶负载的硅钨酸(H_4SiW_(12)O_(40),缩写HSiW)、Amberlyst-15和Amberlyst-35固体酸催化剂表面被聚四氟乙烯乳液修饰前后对异丁烯迭代反应性能的影响。结果表明,聚四氟乙烯涂敷在催化剂HSiW/SiO_2上,不仅对C_8~=选择性的提高效果较好,在酸性树脂上也同样有效,C_8~=选择性提高约10%。     

Copolymerization and oligomerization by transition metal catalysts

Alternating copolymerization of diolefins and olefins is possible by controlling the coordination site and the coordination ability with alkylvanadium halide as catalyst prepared at extremely low temperature. Alternating structure of the isoprene-propylene copolymer is established by nuclear magnetic resonance spectroscopy and ozonolysis analysis and the alternating addition of isoprene at the 4,1-position and of propylene at the α,β-position is proposed. The model reaction indicates that the π-allylvanadium bond prefers propylene, whereas the ethylvanadium bond prefers butadiene. However, the selectivity is lowered with bulky α-olefins. Acetylene is also copolymerized with nickel catalyst to give random copolymers possessing active methylene groups available for drying oil. Controlling the amount and acidity of the protic component added to Ni⁰, cyclo-, or linear oligomers of butadiene and the 1,3-1,2 adduct of butadiene are prepared selectively. Also, the addition of amine or alcohol to butadiene is successful. The reaction occurs through a π-allyl nickel intermediate and the reaction is extended to π-allyl exchange reactions.     

Kinetics of acetic acid esterification over ion exchange catalysts

Computer simulation showed that catalytic distillation is an attractive process for the removal of dilute acetic acid from wastewater. Selection of catalysts and kinetic data have been obtained for the design of the catalytic distillation column. Kinetic measurements were conducted in a batch reactor. Methanol was added to the dilute acetic acid solutions and reacted with the acid in water to form methyl acetate and water. The reaction can be catalyzed by solid acid catalysts. It was found that Amberlyst 15 was an effective catalyst for this reaction. The effects of stirrer speed, reaction temperature, reactant concentration and catalyst loading on reaction rate were investigated. A complete kinetic equation for describing the reaction catalyzed by Amberlyst 15 was developed. This equation can be used in the simulation and design of the catalytic distillation column for removing acetic acid from wastewater.     

不同类型催化剂对异丁烯齐聚反应过程的影响

采用固定床反应器分别探究了三类催化剂（固体磷酸催化剂、酸性阳离子交换树脂催化剂以及分子筛催化剂）对异丁烯齐聚过程的影响。实验结果表明：固体磷酸催化剂适用于C₈烯烃的生产,酸性阳离子树脂催化剂及改性的分子筛催化剂（Hβ）适合生产C₁₂烯烃。异丁烯齐聚产物C₈～C₁₆（清洁燃料油）因无芳烃、无硫,在石化工业中具有非常广泛的应用潜力;由三种类催化剂的评价结果来看,C₈～C₁₆的选择性最高时均能接近100%,但是固体磷酸催化剂和酸性阳离子树脂催化剂的异丁烯原料转化率比Hβ分子筛催化剂低,Hβ催化作用下异丁烯转化率可以达到88%。     

Syndiospecific oligomerization and polymerization of norbornene with titanium catalysts

Norbornene (NB) has been polymerized with TiCl₄-AlR₂Cl (R = Et, Me, iBu) at various NB/TiCl₄ molar ratio. The products obtained at low ratio (from ca. 5 to 12, depending on the mode of catalyst preparation) are a mixture of oligomers, from which it has been possible to isolate a crystalline heptamer having a 2,3-exo-disyndiotactic structure by single crystal X-ray analysis. The products obtained at higher NB/TiCl₄ ratio have a higher molecular weight (up to ca. 5000 for the soluble products) and consist of amorphous and crystalline polymers. The crystalline polymers, characterized by X-ray and ¹³C NMR, are a new type of stereoregular polynorbornene (PNB), having a 2,3-exo-disyndiotactic structure. Mechanistic aspects are examined and a precise assignment of some resonances in the ¹³C NMR spectrum of vinyl-type PNBs is reported.     

Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2 catalysts

The hydrogenation/hydrodeoxygenation of furfural was studied on a Cu/SiO₂ catalyst at 230–290 °C. Detailed kinetics, density function (DFT) calculations, and spectroscopic studies were combined to investigate this reaction. A Langmuir–Hinshelwood model was found to fit the kinetic data well and provided the parameters of physical significance. The heat of adsorption (ΔH_ads) of furfural, derived from the fitting, was found to be significantly higher than those of furfuryl alcohol and 2-methyl furan. Activation energies for the conversion of furfural and furfuryl alcohol were both about 12 kcal/mol. DFT calculations and DRIFTS provided guidance about the nature of the surface species. Accordingly, the most likely species adsorbed on the Cu surface is suggested to be a top η¹(O)-aldehyde. DFT calculations of the reaction path show that the predicted energy barriers are of the same order as the experimental values and suggest that the hydrogenation of furfural can occur via either an alkoxide or ahydroxyalkyl intermediate.     

丁烯齐聚催化剂研究进展

烯烃催化齐聚是C_４烯烃综合利用的一个重要途径。本文论述了近年来低碳烯烃,特别是C_４烯烃齐聚催化剂的研究进展,介绍了不同催化剂体系的反应特点及工艺状况。     

Kinetics of esterification of palmitic acid with isopropanol using p‐toluene sulfonic acid and zinc ethanoate supported over silica gel as catalysts

Kinetic data on the esterification of palmitic acid with isopropanol were obtained using homogeneous (para‐toluene sulfonic acid, p‐TSA) and heterogeneous (zinc ethanoate coated on silica gel, ZnA/SG) catalysts in a batch reactor. The ZnA/SG catalyst was prepared using a sol–gel technique. The esterification reaction was studied at different reaction temperatures (373–443 K), initial reactants molar ratio (1–5), catalyst loading (1–5 gcat dm^?3) and water concentration in feed (0–15 vol%). A power law rate equation was used for homogeneous kinetics analysis. The Langmuir Hinshelwood Hougen Watson (LHHW) model was used for heterogeneous kinetics. The kinetic parameters of both models were obtained using Polymath software. The reaction parameters were used to obtain simulated values of conversion for both catalytic systems. The simulated values were compared with the experimental values and were in good agreement. Copyright © 2004 Society of Chemical Industry     

Selective hydrogenation with copper catalysts: V. Kinetics and mechanism at high pressure

The mechanism of hydrogenation at 900~950 psi with copper-chromite catalyst was investigated with pure methyl esters as well as their mixtures. A comparison of double bond distribution intrans-monoenes formed during hydrogenation of linoleate and alkali-conjugated linoleate revealed that 85~95% of the double bonds in linoleate conjugated prior to hydrogenation. The mode of hydrogen addition to conjugated triene and diene at high pressure is similar to that at low pressure but positional and geometric isomerizations of unreduced conjugated esters were less at high pressure. Geometric isomerization of methyl linoleate and linolenate was considerable at high pressure whereas it was negligible at low pressure. The absence of conjugated products during hydrogenation of polyunsaturated fatty acid esters resulted from their high reactivity. Conjugated dienes are 12 times more reactive than the triene, methyl linolenate, and 31 times more reactive than the diene, methyl linoleate. The products of methyl linolenate hydrogenation were the same as those predicted by the conjugation mechanism. Presented at the 70th Annual Meeting of the American Oil Chemists' Society, San Francisco, April 29~May 3, 1979.     

Improved synthesis of isostearic acid using zeolite catalysts

“Isostearic acids” (IA) are branched‐chain fatty acids that are nontoxic and biodegradable in nature. They are predominantly used in cosmetics because of their superior moisturizing properties as they are odorless, provide smooth spreading and a non‐tacky feeling when applied onto skin. They can also be used in applications which require excellent thermo‐stability and low flow temperature properties. The existing older technology produces IA at low yields, which limits their commercial adoption; thus, new technologies for preparing IA are needed.     

Toughening of epoxy novolac resin using cardanol based flexibilizers

In this work, two different cardanol based epoxies (Cardolite NC‐514 and Cardanol NC‐547) were employed as flexibilizers to toughen an epoxy novolac resin namely, poly[(phenylglycidyl ether)‐co‐formaldehyde] (PPGEF). 4,4′‐Diamino‐3,3′‐dimethyl dicyclohexyl methane (BMCHA) was used as a curing agent. Differential scanning calorimetry and dynamic mechanical thermal analysis of the composites showed a gradual decrease in glass transition temperatures (T_g) with increase in cardolite content confirming the incorporation of flexible moieties into the brittle resin matrix. Improvement in toughening of PPGEF/Cardolite composites was manifested by increase in the izod impact strength of both the composites. The tensile strength increased marginally for composites with increasing amount of Cardolite NC‐514 but decreased for the composites containing Cardolite NC‐547. This was attributed to the lack of rotational motion in the chain due to close proximity of rigid phenyl rings in NC‐547. SEM of the cryo‐fractured surfaces of composites showed good compatibility between PPGEF and cardanol based flexibilizers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43318.     

Degradation of solvolysis lignin using Lewis acid catalysts

Alcell‐derived lignin was depolymerized in a batch reactor using the Lewis acid catalysts NiCl₂ and FeCl₃. The objective was to investigate the use of Lewis acids in the production of useful liquid products directly from solvolysis lignin. The effects of reaction temperature, time and catalyst were studied on the conversion of this lignin to gas, solid and liquid products. Also, selected monomeric compounds in the ether solubles were monitored in terms of the variation in their yields with different reaction conditions. The highest conversions, 30% and 26% from Ni and Fe, respectively, were both attained at the reaction conditions of 305°C and 1 h reaction time. The Ni produced a somewhat higher yield of ether solubles, reflecting its slightly higher performance. Under the reaction conditions studied, both catalysts apparently favour condensation reactions leading to the formation of insoluble reactor residue from solvolysis lignin. Low quantities of monomeric compounds were produced, with phenols dominating over ketones and aldehydes for both catalysts.     

Kinetics assisted design of catalysts

Whether thermokinetic data obtained on model large single crystals at low surface coverage can be used successfully to calculate yields on real catalysts at high surface coverage is a question that is considered in the conjecture presented in this note.     

乙烯齐聚合锆系催化剂研究进展

综述了锆系催化体系的特点和研究进展,并对各种配体对催化活性和选择性的影响进行了分析比较。在乙烯齐聚合的催化体系中,不同有机铝对催化乙烯齐聚合的活性和选择性有较大的影响。在锆系催化剂中加入第三组分对乙烯齐聚物的相对分子质量分布有明显的调变作用。     

Ethylene oligomerization on phosphoric acid

Conversion of ethylene over phosphoric acid (P₂O₅ content 64–85%) at temperatures 170–250 C was studied. It was shown that the conversion of C₂H₄ proceeds with the participation of polyphosphoric acids, which are the sites of the oligomerization of ethylene, the reaction of hydrogen redistribution and the formation of branched alkanes.