Comparison of RSM and ANN for the investigation of linear alkylbenzene synthesis over H14[NaP5W30O110]/SiO2 catalyst

Design of experiments (DOE) and artificial neural networks (ANNs) were successfully applied for studying the operating parameters of benzene alkylation with 1-decene over H₁₄[NaP₅W₃₀O₁₁₀]/SiO₂ catalyst. In this reaction catalyst loading, catalyst weight percent and benzene to 1-decene molar ratio (Bz/C₁₀) were chosen as independent variables in experimental design. Prediction of 1-decene conversion and 2-phenyldecane selectivity was performed applying response surface method (RSM) and ANN models. Final selected multi-layer (3-6-2-2) ANN model resulted a coefficient of determination (R²) of 0.95 for 1-decene conversion and 0.99 for 2-phenyldecane selectivity, while the R² of RSM was 0.93 and 0.92 for these two parameters.     

Copolymerization of styrene by diphenylzinc-additive systems. Part II: Copolymerization of styrene/1-alkene by Ph2Zn-metallocene-MAO systems

Summary The copolymerization of styrene with 1-alkene (1-hexene, 1-decene and 1-hexadecene) has been tested using combined diphenylzinc-additive initiator systems, including diphenylzinc (Ph₂Zn), a metallocene and methylaluminoxane (MAO). The metallocene were biscyclopentadienyltitanium dichloride, bis(n-butylcyclopentadienyl)titanium dichloride, cyclopentadienyltitanium trichloride and bisindenylzirconium dichloride. For Ph₂Zn-metallocene-MAO systems, titanocenes gave mainly syndiotactic homo polystyrene irrespective of the styrene/1-alkene proportion in the initial feed. Systems including Ind₂ZrCl₂ were able to copolymerize styrene 1-alkene with the copolymers incorporating alkene in a lower proportion than the present in the initial feed. Keywords: Styrene copolymerization; diphenylzinc; metallocene catalysts; tacticity. Received: 17 November 2000/Revised version: 9 May 2001/Accepted: 10 May 2001     

Oligomerization of 1-decene with Ziegler-Natta catalysts

The catalytic oligomerization of 1-decene has been carried out employing several transition metal complexes of Co(II), Co(III), Zr(IV), Ti(IV), Cr(III), V(V) in combination with alkyl aluminum halides as cocatalysts. The chromium(III)-Et₃Al₂Cl₃ system exhibits good oligomerizing activity yielding dimers (C₂₀), trimers (C₃₀) and tetramers (C₄₀) of 1-decene. The kinematic viscosities and pour points of hydrogenated oligomers have been determined and compared with those of commercial samples. The probable mechanism of oligomerization of 1-decene on this catalyst is described.     

Microwave Discharge of O2 and CO2 as a Synthetic Tool for Oxidations of Unsaturated Compounds Adsorbed on Solid Supports

Cis and trans stilbene, styrene, 1-decene and 6-dodecene adsorbed on silica gel were reacted with oxygen atoms produced by microwave discharge of O₂ and CO₂. At 0°C these compounds gave mainly epoxides and carbonyl compounds as in neat liquid reactions. Below — 60°C ozonolysis products were formed; cis and trans stilbene and styrene gave benzaldehyde while 1-decene and 6-dodecene resulted mainly in ozonides.     

Co-metathesis reaction of crude palm oil and ethene

The co-metathesis reaction of crude palm oil with ethene in the presence of WCL₆/Me₄Sn, followed by termination of this reaction with methanol, gives terminal alkenes. The major metathesis products are 1-decene and methyl 9-decenoate.     

Kinetics of hydroformylation of 1-decene using homogeneous HRh(CO)(PPh3)3 catalyst: a molecular level approach

The kinetics of hydroformylation of 1-decene using homogenous HRh(CO)(PPh₃)₃ catalyst has been reported in the temperature range of 50–70 °C. The effect of catalyst,P _{H 2},P _CO, and 1-decene concentration on the rate of hydroformylation has been studied. Based on the analysis of initial rate data, a rate equation has been proposed and kinetic parameters evaluated. The activation energy was found to be 11.76 kcal/mol. A molecular level approach to kinetic modelling has also been illustrated. The rate equation derived assuming oxidative addition of H₂ as a rate determining step, has been found to represent the data satisfactorily. The rate parameters for the mechanistic model have been evaluated for the data at 60 °C.NCL Communication No. 5735.     

Hydroformylation of Alkenes with Rhodium Catalyst in Supercritical Carbon Dioxide

1-Octene, 1-decene and styrene have been hydroformylated using a CO₂-philic fluorous ligand associated with a rhodium catalyst. The effect of P/Rh molar ratio, partial pressure of CO/H₂ and total pressure of carbon dioxide were studied. When 1-octene was used as the substrate, high conversion and selectivity in aldehydes were observed using low rhodium concentration and low P/Rh ratios.     

Metathese ungesättigter Fettsäureester – ein einfacher Zugang zu langkettigen Dicarbonsäuren

Metathesis of Unsaturated Fatty Acid Esters – a Simple Approach to Long-Chained Dicarboxylic Acids Long-chained, symmetric unsaturated C₁₈-, C₂₀- und C₂₆-dicarboxylic acid esters are easily accessible from natural fatty acid esters by metathesis in a two-step procedure. In the first step unsaturated fatty acid esters are cleaved by metathesis with ethylene. Pure oleic acid ester or fatty acid methylesters, produced from high-oleic sunflower oil or from rapeseed oil by transesterification with methanol, are converted to 1-decene and 9-decenoic acid methylester. From erucic acid methylester 1-decene and 13-tetradecenoic acid methylester are achieved. Using our newly developed high efficient catalytic system B₂O₃-Re₂O₇/Al₂O₃-SiO₂ + SnBu₄ conversion rates of 86 – 96% are obtained and the terminally unsaturated fatty acid esters are isolated in yields of 61 – 83%. In the second step 9-decenoic and 13-tetradecenoic acid methylester as well as 10-undecenoic methylester, which is commercially obtained by pyrolysis of ricinoleic acid ester, are converted to 9-octadecenedioic-, 13-hexacosenedioic- and 10-eicosenedioic acid dimethylester, by which process ethylene is eliminated. The conversion rates are 89 – 99% and the dicarboxylic acid dimethylesters are isolated in yields of 77 – 84%.     

活性炭负载磷钨酸催化1-癸烯齐聚反应的研究

使用活性炭负载磷钨酸催化剂,对1-癸烯齐聚反应进行研究,考察磷钨酸负载量、催化剂活化温度、活化时间、反应温度、反应压力和反应时间对1-癸烯转化率的影响。确定最佳的工艺条件为:磷钨酸负载质量分数37%,催化剂活化温度200℃,活化时间3 h,反应温度180℃,反应压力0.5 MPa,反应时间4 h。在此条件下,对聚烯烃合成油的物化性能进行研究,结果表明,采用活性炭负载磷钨酸催化剂催化1-癸烯齐聚合成油100℃黏度为4.60 mm2·s-1,黏度指数为126,凝点为-58℃,1-癸烯转化率为83.5%。     

离子液体催化1-癸烯齐聚反应

分别以氯化1-甲基-3-丁基咪唑([Bmim]Cl)、溴化1-甲基-3-乙基咪唑([Emim]Br)和盐酸三乙胺为阳离子,氯化铝、氯化铁和氯化锌为阴离子合成酸性液体催化剂,用于1-癸烯齐聚反应研究。结果表明,以[Emim]Br-AlCl_3制备的催化剂活性和选择性较好。较佳工艺条件:催化剂用量为1-癸烯质量的7%,n(AlCl_3)∶n([Emim]Br)=3∶1,反应时间5 h,反应温度160℃,搅拌速率240 r·min~(-1)。气相色谱分析可知,1-癸烯转化率达70%以上,产物主要是二聚物、三聚物、四聚物和较少的五聚物,无裂解产物。     

Catalysts Based on Molybdenum Carbide Modified with Nickel and Alumina in Hydrogenation of Hydrocarbons and Hydrodesulfurization

The Ni–Mo₂C/С and Mo₂C/Al₂O₃ catalysts produced by microwave synthesis are highly active in hydrogenation of alkenes (cyclohexene, 1-decene) and naphthalene and in hydrodesulfurization of a mixture modeling the diesel fraction. The obtained results were compared with the activity of stoichiometric Mo₂C and a study was made of the effect of temperature (250–400°C), hydrogen pressure (10–40 atm), and the amount of the catalyst on the conversion of the substrates.

     

Isomerizations accompanying friedel-crafts alkylations of benzene by detergent range alkylating agents

The Friedel-Crafts alkylation of benzene with linear detergent range olefins and chloroparaffins in the presence of AlCl₃ and HF catalysts was investigated. Evidence is presented to support the argument that isomerization occurs both in the alkylating agent prior to alkylation and in the product arenes following alkylation. Data on product phenylalkane isomer distributions is presented. The alkylation of benzene with 2-hexyl-1-decene in the presence of AlCl₃ was shown to initially yield only one phenylhexadecane isomer, probably 7-methyl-7-phenylpentadecane, with subsequent product isomerization to other isomeric hydrocarbons.     

1-癸烯齐聚物的催化合成与反应动力学行为研究

以1-癸烯为原料,分别采用AlCl3/TiCl4和氯化铝催化体系进行了合成1-癸烯齐聚化合物的研究。研究结果表明两催化剂均可实现1-癸烯齐聚化合物的合成,但两者聚合度有差异,考虑后续处理和环境污染问题,宜采用AlCl3/TiCl4催化体系,并初步确定该反应体系最佳反应温度为40℃、反应时间为4h;齐聚反应动力学过程测试表明,随着齐聚反应的进行,CH2双键逐步减少同时伴随CH不断的生成和消耗,均呈现出同步下降趋势,表明齐聚反应过程中存在着α-烯烃的歧化反应,且歧化产物参与了齐聚反应;连续在线各官能团红外谱图分析反映出的可能反应过程与以最终反应产物的信息来推断反应过程研究文献报道基本吻合。     

N-phenylaminomethylation: A one-step route to N-substituted anilines from unsaturated fatty derivatives and olefins

Unsaturated fatty materials, such as ethyl oleate and oleonitrile, are found to react with carbon monoxide, hydrogen and aniline at 150 C to give N-monoalkylanilines. The alkyl group is derived from the unsaturated fatty material plus the group H-CH₂ added across the double bond. Similarly 1-decene, in a rapid reaction, gives N,N-di-n-undecylaniline and N-undecylaniline as major and minor products respectively. 1,2,3-Tris-(triphenylphosphine)trichlorohodium is an excellent catalyst for this reaction. Presented at the AOCS Meeting, San Francisco, April 1969.     

马来酸酐/1-十烯共聚物在聚丙烯木塑复合材料中的应用

采用红外光谱、核磁共振氢谱和凝胶渗透色谱表征了自行合成的马来酸酐(MAH)/1-十烯共聚物,探讨了该共聚物作为相容剂在聚丙烯(PP)基木塑复合材料中的应用。结果表明:MAH/1-十烯共聚物可改善木粉在PP中的分散性和相容性,提高PP与木粉间的界面黏合力,进而改善复合材料的力学性能;当相容剂用量为5份时,复合材料的拉伸强度提高了59.3%,弯曲强度提高了44.6%,冲击强度提高了82.6%。     

新型离子液体催化1-癸烯齐聚反应研究

选择盐酸-三氯化铝1-乙基-3-甲基咪唑溴盐([Emim]Br-A1Cl3-HCl)为离子液体催化剂,用于催化1-癸烯齐聚。研究了阴阳离子物质的量比和共催化剂用量以及聚合反应条件,如反应温度、催化剂用量、反应时间等对反应结果的影响,实验结果表明较佳的工艺条件为:阴阳离子物质的量比为3∶1,共催化剂用量0.09 mL,反应温度为120℃、m(催化剂)∶m(1-癸烯)=5∶100、反应时间3 h。在常压下,1-癸烯齐聚产物的转化率达到80%以上,并且符合聚α-烯烃(PAO)性能要求。     

Carbon nuclear magnetic resonance characterization of ethylene-propylene-1-octadecene terpolymers and comparison with ethylene-propylene-1-hexene and 1-decene terpolymers

In this paper, we report the complete ¹³C NMR characterization of a set of ethylene-propylene-1-octadecene terpolymers obtained with the metallocenic system rac-ethylene bis-indenyl zirconium dichloride, using different comonomer ratios. A detailed study of ¹³C NMR chemical shifts, triad sequence distributions, monomer average sequence lengths and reactivity ratios for these terpolymers is presented. The incorporations of 1-octadecene were superior of those obtained using 1-hexene and 1-decene in the same conditions. Catalytic activities of terpolymers of ethylene-propylene and α-olefins (α-olefins:1-hexene, 1-decene and 1-octadecene) were compared showing that they increase with the amount of propylene in the feed.     

Non-volatilea-branched chain fatty acid derivatives: IV. Addition of aryl esters to long chain olefins

The di-tertiary butyl peroxide initiated free radical addition of methyl phenylacetate, methylp-tolylacetate and methylp-methoxyphenylacetate to 1-decene gives two types of products. In addition to the expecteda-branched esters, dehydrodimer (bothmeso anddl) esters were also obtained. The highest yield ofa-branched ester was obtained from methyl phenylacetate. Higher yields of the dehydrodimer esters were obtained from the substituted phenyl esters. Attempts to add methylp-nitrophenylacetate to 1-decene were not successful and no evidence for the formation of a dehydrodimer product was observed.     

Polymerization and characterization of ethylene/propylene and ethylene/1-octene copolymers produced with bridged Zr- and Hf-based metallocenes

Ethylene/propylene (E/P) and ethylene/1-octene (E/O) copolymers were polymerized with two bridged metallocene catalyst systems, Et(Ind)₂ZrCl₂/MAO and Et(Ind)₂HfCl₂/MAO, respectively. The copolymers produced and some commercial reference copolymers were characterized by DSC, SEC, DMA and ¹³C NMR. The Hf-catalysed E/P polymerizations showed much lower activities than the corresponding Zr-catalysed polymerizations but gave polymers with high molar mass. The Hf-based copolymers also showed two melting peaks which may be indicative of several active sites of the catalyst. A comparison of E/P copolymers, containing about 20 mol-% propylene and produced with Zr, Hf and homogeneous V-catalysts, respectively, indicated that the Hf and V-catalysts gave material more similar to each other. The E/O copolymers produced with Zr-catalysts gave very low molar masses and the reactivity ratios, calculated from the NMR data, indicated that the Hf-catalyst has a slightly higher reactivity for 1-octene and the Zr-catalyst some better reactivity for ethylene. Segregation fractionation studies by DSC indicated that a lower 1-octene feed gives more heterogeneous copolymers and the DMA measurements reveal the existence of a linear correlation between the 1-octene content and the intensity of the tan δ_max peak.     

Behavior of poly(ethylene‐co‐olefin) polymers as elastomeric materials

The properties of two new ethylene‐α‐olefin copolymers, namely, ethylene–1‐hexene copolymer (EHC) and ethylene–1‐octadecene copolymers (EOC), synthesized via metallocene catalysts were evaluated. The copolymerization was carried out in an autoclave reactor with Et(Indenyl)₂ZrCl₂/methylaluminoxane as a catalyst system. These single‐site catalysts (metallocene type) allow one to obtain very homogeneous copolymers with excellent control of the molecular weight distribution and proportion of comonomer incorporation. So, copolymers with 18 mol % comonomer in the case of EHC and 12 mol % for EOC were shaped, and activities around 100,000 kg of polymer mol^?1 of Zr bar^?1 h^?1 were reached. The properties of these copolymers were compared with other commercial elastomers, such as ethylene–propylene copolymers synthesized by Ziegler–Natta catalysts and an ethylene–octene copolymer obtained via metallocene catalysts. The results show that these new copolymers, in particular, EOC, had excellent elastomeric properties. Furthermore, they had a relatively low viscosity, which implied a good response during processing. Moreover, the effectiveness of these copolymers as impact modifiers for polyolefins was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3008–3015, 2004