Propylene trimer and tetramer

Other olefins applied in the hydroformylation process with subsequent hydrogenation are propylene trimer and tetramer for the production of decyl and tridecyl alcohols, respectively, and C7 olefins (from copolymers of C3 and C4 olefins) for isodecyl alcohol production. 

This has been found to be a general reaction for many types of olefins. It has also been applied to highly branched structures, such as 2,4,4-trimethyl-2-pen-tane and propylene trimers and tetramers [177], to unbranched olefins with internal double bonds, such as methyl oleate [178] and tricosane, and to a-ole-fins [179], In all cases the data indicate that the reaction occurs at the double... 

The products, which were obtained as viscous, pale amber oils, were purified by vacuum distillation or molecular distillation, whichever was best suited to the particular product. The yield of dialkylated p-cresol was 85-95%. Freedom from appreciable amounts of monoalkylated product was established by vapor phase chromatography (VPC), thin-layer chromatography (TLC), and molecular weight determination. The products obtained from propylene trimer and tetramer had no appreciable antioxidant activity) and will not be considered further here. 

Commercial olefins that are essentially mixtures of aliphatic mono-olefms and that fall within the range of 95 to 165 bromine number (see Note 1). This test method has been found suitable for such materials as commercial propylene trimer and tetramer, butene dimer, and mixed nonenes, octenes, and heptenes. This test method is not satisfactory for normal alpha-olefins. 

Interestingly, if benzene is left out similar conditions are used to manufacture the trimer and tetramer of propylene. The cumene is separated by distillation, bp 153°C. 

CrCUCpylj, CrCl3(4-Etpy)3, and [CrClsCPBus) ] complexes have been used as catalysts for dimerization of propylene [567,568], In addition to dimers, trimers and tetramers are formed. The Cg fraction is composed mainly of 2-methylpentene (69%) and n-hexane (31%). EtAlCh is used as the cocatalyst in these systems. 

Formation of linear trimers and tetramers starting from an a-olefin (Table V) is difficult to vizualize and suggests an intramolecular rearrangement which may be ascribed to a most favored primary carbon— metal bond (or to its higher reactivity), e.g. in the case of propylene ... 

The feedstock, usuaHy consisting of propylene and butylenes (various isomers of C Hg) from cracking processes, may even consist of selective olefins for dimer, trimer, or tetramer production ... 

Specific Optical Rotation (rs > of the Propylene Trimers, Tetramers, and Mixed Oligomers at Various Wave lengths (X) and Various Reaction Temperatures 1... 

In the presence of acid catalysts (for example, phosphoric acid on support), propylene yields a mixture of the trimer and the tetramer. The UOP process is conducted in a... 

A structure of C34F23 (C14F 22)11 C14H23 is proposed, where n = 0, 1, or 2 for the dimer, trimer, or tetramer, respectively. Ethylene-propylene copolymers can contain up to four types of sequence distribution of monomeric units. These are propylene to propylene (head-to-tail and head-to-head), ethylene to propylene, and ethylene to ethylene. These four types of sequence and the average sequence lengths of both monomer units, i.e., the value of w in the structures opposite, can be measured by the Tanaka and Hatada [48] method. 

APE use is limited to commercial and industrial applications which are not considered likely to make a large contribution to municipal sewage treatment plants, such as in textile chemicals. The alkyl chain is usually (diisobutylene), C9 (propylene trimer), or C12 (propylene tetramer). The nonylphenol ethoxylates (NPE) are used in much greater volume than the others, perhaps 80% of the market. Octylphenol ethoxylates (OPE) have about 15% of the market and dinonylphenol- and dodecylphenolethoxylates are at about 1% each. All are excellent for the removal of oily soils and can be produced at lower cost than the more abundant alcohol ethoxylates. 

Further protonation of the trimer produces a C9 carhocation which may further react with another propene molecule and eventually produce propylene tetramer. 

The product is a mixmre of dimers, trimers, tetramers, and pentamers having an average RON (Research Octane Number) = 95. Table 3-14 shows the analysis of feed and products from dimerization of propylene. ... 

Steam cracking of various petroleum fractions is gaining widespread use for the production of olefins. These olefins are produced essentially for use as feed stock for numerous petrochemical processes, but the by-product butylenes and propylenes are sometimes used as feed stock for aviation and motor alkylation units. Ethylene is the most important of the olefins produced from this type of cracking, and propylene is second in importance. These two olefins are normally charged to either alkylation or polymerization units for the production of petrochemicals or petrochemical intermediates. Polyethylene and propylene dimers, trimers, tetramers, and penta-mers are some of the more important polymers produced, while ethybenzene, dodecylbenzene, cumene, diisopropylbenzene, and alkylated... 

Some propylene polymerization units are operating for production of motor polymer only. This now is becoming uncommon because many refiners have changed their operations to make tetramer, and others fractionate some tetramer, trimer, or dimer out of the polymer leaving very little, if any, motor gasoline. 

Commercial polymerization was once used only for converting the olefins from cracked gases into motor fuel. However, it is rapidly becoming very important in the production of such petrochemicals as heptene, propylene dimer, trimer, tetramer and pentamer and the alkylated aromatics such as ethylbenzene, isopropylbenzene, cymene, and butyl-benzenes. This list may be expected to grow as new uses are found for the heavier olefins. 

When propylene oxide is polymerized by trimethyl aluminum at 0 °C, cyclic tetramer together with some cyclic dimer and trimer is formed in the first stages of the polymerization (5). 

Evidence of oligomers appears at short contact time. Figure 3 shows plateaus corresponding to the trimer, tetramer and penta-mer of propylene at conditions of 2.7 WHSV, 400°F, 500 psig at which propylene conversion if 67%. This contrasts with the smooth curve at 0.4 WHSV, 98% propylene conversion. 

Apart from the isooctanol and isononanol discussed above, isodecanol can be produced from the trimer of propylene and isotridecanoi from its tetramer. Alcohols with 8... 

Propylene was polymerized by means of this catalyst to trimers to be blended with gasoline, and to tetramers to be used in the manufacture of detergents. 

The first one includes the catalysts which oligomerize ethylene, propylene, higher olefins with internal or terminal double bond (e.g. 1- or 2-butene) into a mixture of dimers, trimers, tetramers. .. of various structures (head-to-head, head-to-tail, tail-to-tail). They readily catalyse the shift of the double bond in reactants and products. Tri-, tetra-, pentamers form at the same time by parallel (growing chain) and consecutive reactions. 

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