Propylene oligomerization

A few other complexes with N-N coordinating atoms have been tested as olefin polymerization catalysts. The aminopyridinato complex 181 is only able to oligomerize propylene and 1-butene (Mn < 3500) with low activity.1222 The /3-diketiminato Zr complex 182 exhibits moderate ethylene polymerization activity ( 50gPE(mmol M)-1 h-1 bar-1), but molecular masses were disappointingly low (Mn up to 30000).1117 Finally, at 100°C, the MAO-activated Ti complex 183, with a tridentate triazacyclononane ligand, yields PE with very high activity (104gPE(mmol M)-1 h-1 bar-1) but rather low molecular masses and broad polydispersity (Mn = 39500 Mw/Mn = 7.0).1223... 

Figure 1. 1H-NMR spectrum of a living oligomeric propylene oxide prepared with TPPAICI. (Reproduced from Ref. 6. Copyright 1981 American Chemical Society.)...

Palladium Catalysts. In general, Pd catalysts have considerably lower activities than Ni catalysts in olefin oligomerization. Propylene is selectively dimerized to up to 95% linear hexenes by the catalyst [Pd(acac)2]/Et2AlCl/PR3 in 1,2-dichloroethane. The heterogeneous Pd(II) catalyst system, prepared by treatment of sepiolite with [Pd( 17 -03115)2], exhibits high activity in the styrene dimerization to give exclusively ( )-... 

ME1 Medved, Z.N. and Starikova, N.A., Enthalpies of mixing of oligomeric propylene oxides and water (Russ.), Zh. Fiz. Khim., 57, 2590, 1983. 

HCo(N2)(PPh3)3 has been used to oligomerize propylene [577]. 2-Methyl-l-pentene is the main product. The addition of 3 moles of tri-n-butyl-phosphine/ mol of cobalt complex considerably reduced the oligomerization rate. A mechanism as shown in the following reactions is proposed (5771 ... 

Generally, nickel complexes do not oligomerize propylene to higher molecular weight olefins. Dimers and trimers are mainly the products of this reaction. The predominant literature propylene dimerization is based on the nature of the activity of complex organometallic catalysts based on nickel compounds and the effects of ligands attached to the nickel on the selectivity of the process [544,580-582]. 

Pillared montmorillonites were used to oligomerize propylene at 30-50 atm [68]. One of the catalysts was pillared with a mixed aluminum-zirconium polymer. The PILCS were much less active than H-zeolite omega or an aluminosilicate catalyst. However, the selectivity for gasoline was greater. The Al-Zr PILC exhibited a high selectivity for aromatics and less coke formation than the Al-PILC. The observed behavior was attributed to the large niimber of Lewis acid sites relative to Br nsted acid sites and to the microporosity of the PILCS. 

In refining, the oligomerization process produces gasoline from C3 fractions containing approximately 75% propylene or fuel-gas containing ethylene and propylene. 

Cryogenic recovery before oligomerization Ethylene Propylene 95% 100%... 

Polymer-type antioxidants have been prepared by Eriedel-Crafts reaction of -cresol andp- and/or y -chloromethylstyrene in the presence of boron trifluoride-etherate (198). The oligomeric product resulting from the alkylation of phenyl-a-naphthylamine using C12—15 propylene oligomer in the presence of AlCl or activated white clays is used as an antioxidant additive for lubricating oils (199). 

Manufacture of Monomers. The monomers of the greatest interest are those produced by oligomerization of ethylene (qv) and propylene (qv). Some olefins are also available as by-products from refining of petroleum products or as the products of hydrocarbon (qv) thermal cracking. 

These products are characterized in terms of moles of substitution (MS) rather than DS. MS is used because the reaction of an ethylene oxide or propylene oxide molecule with ceUulose leads to the formation of a new hydroxyl group with which another alkylene oxide molecule can react to form an oligomeric side chain. Therefore, theoreticaUy, there is no limit to the moles of substituent that can be added to each D-glucopyranosyl unit. MS denotes the average number of moles of alkylene oxide that has reacted per D-glucopyranosyl unit. Because starch is usuaUy derivatized to a considerably lesser degree than is ceUulose, formation of substituent poly(alkylene oxide) chains does not usuaUy occur when starch is hydroxyalkylated and DS = MS. 

Diaminopropane Processes. 1,2-Propylenediamine can be produced by the reductive amination of propylene oxide (142), 1,2-propylene glycol [57-55-6] (143), or monoisopropanolamine [78-96-6] (144). 1,3-Propanediol [504-63-2] can be used to make 1,3-diaminopropane (143). Various propaneamines are produced by reducing the appropriate acrylonitrile—amine adducts (145—147). Polypropaneamines can be obtained by the oligomerization of 1,3-diaminopropane (148,149). 

In addition, Lagowski and Simons showed (80) that the black, nickel-containing substances produced by the cocondensation of nickel atoms and alkynes are active, homogeneous catalysts for the oligomerization of terminal acetylenes under mild conditions. Table XVIII shows the yields of the oligomerization of propylene by these catalysts. 

ZSM-5 Cracking of n-octane Higher activity Higher propylene selectivity Reduced oligomerization [71]... 

A recent example where Co2(CO)8 serves as a precatalyst is in the preparation of linear and branched aldehydes via propylene hydroformylation in supercritical C02 (93-186 bar 66-108 °C). Cyclohexane carbaldehyde is produced from cyclohexene using Co2(CO)8 and an acid RCOOH, or else is successful with another established Co catalyst, Co(OOCR)2, assumed to form in situ in the former case. Oligomerization of aldehydes such as n-butanal is achieved with Co2(CO)6L2 as catalyst (L = CO, PR3).1364... 

The acidic character of 5A zeolite as a function of the calcium content has been explored by different techniques propylene adsorption experiments, ammonia thermodesorption followed by microgravimetry and FTIR spectroscopy. Propylene is chemisorbed and slowly transformed in carbonaceous compounds (coke) which remain trapped inside the zeolite pores. The coke quantities increase with the Ca2+ content. Olefin transformation results from an oligomerization catalytic process involving acidic adsorption sites. Ammonia thermodesorption studies as well as FTIR experiments have revealed the presence of acidic sites able to protonate NH3 molecules. This site number is also correlated to the Ca2+ ion content. As it has been observed for FAU zeolite exchanged with di- or trivalent metal cations, these sites are probably CaOH+ species whose vas(OH) mode have a spectral signature around 3567 cm"1. 

Olefin metathesis technology, in polymer synthesis, 26 944-948 Olefin oligomerization, 16 111 Olefin oxides, alkanolamines from (with ammonia), 2 122-140 Olefin polymerization, organic titanium compounds in, 25 122 Olefin(ic) polymers, 17 699-709 ethylene-propylene elastomers, 17 705-707... 

AE and AP surfactants are synthesised by polymerisation of monomeric or short chain oligomeric glycol moieties. If mixtures of ethylene and propylene glycols, however, were applied for the synthesis, so called EO/PO block polymers in the form of complex mixtures with the general formula R-0-(E0)m-(P0) -H and the structure as shown with their... 

Contents G. Henrici-Olive, S. Olive Oligomerization of Ethylene with Soluble Transition-Metal Catalysts. A. Zambelli, C. Tosi Stereochemistry of Propylene Polymerization. C.-D.S. Lee, W.H. Daly Mercaptan-Containing Polymers. Yu. V. Kissin Structures of CopolymerS of High Olefins. 

Wood wafers were treated with mixtures of propylene oxide and oligomeric isocyanate (Guevera and Moslemi, 1983). The best treatment was found to be a mixture of 9 1 propylene oxide to isocyanate. In another study, Guevera and Moslemi (1984) studied the swelling properties of wood modified with propylene or butylene oxide and compared the data with modifications using a furan resin, or vinylpyrrolidinone. The best results were obtained by the use of alkylene oxides in combination with a cross-linking agent (trimethylol propane trimethacrylate). 

---