Propylene with butadiene

Thermal Reactions of Olefins with Butadiene. The rate constant of the reaction of ethylene with butadiene was reported by Rowley and Steiner (18), whereas that of propylene or butenes with butadiene has not been reported. Tarasenkova (22) reported that the thermal reaction of propylene with butadiene at 600°C gave toluene, the yield of which was twice as large as the yield of benzene plus xylenes. Moreover, the thermal reactions of 1-butene with butadiene and 2-butene with butadiene at 500° — 550°C gave as main products ethylbenzene and o-xylene, respectively. The ratio of ethylbenzene to total xylenes was close to the ratio of 1-butene to 2-butene in the feed. 

Cooligomerization of propylene with butadiene gives two derivatives of CIS, rra/15-cyclodecatriene 76% 73 and 24% 74. 

Elastomers. Ethylene—propylene terpolymer (diene monomer) elastomers (EPDM) use a variety of third monomers during polymerization (see Elastomers, ethyiene-propylene-diene rubber). Ethyhdenenorbomene (ENB) is the most important of these monomers and requires dicyclopentadiene as a precursor. ENB is synthesized in a two step preparation, ie, a Diels-Alder reaction of CPD (via cracking of DCPD) with butadiene to yield 5-vinylbicyclo[2.2.1]-hept-2-ene [3048-64-4] (7) where the external double bond is then isomerized catalyticaHy toward the ring yielding 5-ethyhdenebicyclo[2.2.1]-hept-2-ene [16219-75-3] (ENB) (8) (60). 

Type 3A sieves. A crystalline potassium aluminosilicate with a pore size of about 3 Angstroms. This type of molecular sieves is suitable for drying liquids such as acetone, acetonitrile, methanol, ethanol and 2-propanol, and drying gases such as acetylene, carbon dioxide, ammonia, propylene and butadiene. The material is supplied as beads or pellets. 

Propane cracking is similar to ethane except for the furnace temperature, which is relatively lower (longer chain hydrocarbons crack easier). However, more by-products are formed than with ethane, and the separation section is more complex. Propane gives lower ethylene yield, higher propylene and butadiene yields, and significantly more aromatic pyrolysis gasoline. Residual gas (mainly H2 and methane) is about two and half times that produced when ethane is used. Increasing the severity... 

Aryloxyphosphazene copolymers can also confer fireproof properties to flammable materials when blended. Dieck [591] have used the copolymers III, and IV containing small amounts of reactive unsaturated groups to prepare blends with compatible organic polymers crosslinkable by the same mechanism which crosslinks the polyphosphazene, e.g. ethylene-propylene and butadiene-acrylonitrile copolymers, poly(vinyl chloride), unsaturated urethane rubber. These blends were used to prepare foams exhibiting excellent fire retardance and producing low smoke levels or no smoke when heated in an open flame. Oxygen index values of 27-56 were obtained. 

Petroleum is rarely used in the form produced at the well, but is converted in refineries into a wide range of products, such as gasoline, kerosene, diesel fuel, jet fuel, and domestic and industrial fuel oils, together with petrochemical feedstocks such as ethylene, propylene, butene, butadiene, and isoprene. Petroleum is refined, that is, it is separated into useful products (Figure 1.1 Chapter 3). 

Monomer. A molecule of relatively simple structure and low molecular weight that is capable of being polymerized with itself or other monomers into polymers, synthetic resins, or elastomers such as ethylene, propylene, styrene, butadiene, or vinyl chloride. 

Selective modification of polyols such as ethylene glycol, 1,3-propylene glycol, or glycerol with butadiene (1) has been studied [7-10]. The monosubstituted compounds are preferred due to their potential applications as surfactants, PVC plasticizers, or even in cosmetics. The telomerization of 1 with ethylene glycol yields a complex mixture including linear and branched mono- and ditelomers, as well as 1,3,7-octatriene and vinyl cyclohexene (Fig. 2) [11]. 

Scheme 9 A proposed mechanism for co-polymerization of propylene and butadiene to form isotactic polypropylenes with pendant vinyl groups.

Some Available Data. A brief list of extractive distillation processes of actual or potential commercial value is in Table 13.7 the column of remarks explains why this mode of separation is adopted. The leading applications are to the separation of close-boiling aromatic, naphthenic, and aliphatic hydrocarbons and of olefins from diolefins such as butadiene and isoprene. Miscellaneous separations include propane from propylene with acrylonitrile as solvent (DuPont, U.S. Pat. 2,980,727) and ethanol from propanol with water as solvent [Fig. 13.24(b)],... 

The first free radical initiated copolymerization was described by Brubakerl) in a patent. A variety of peroxides and hydroperoxides, as well as, 02, were used as initiators. Olefins that were copolymerized with CO included ethylene, propylene, butadiene, CH2=CHX (X—Cl, OAc, CN) and tetrafluoroethylene. A similar procedure was also used to form terpolymers which incorporated CO, C2H4 and a second olefin such as propylene, isobutylene, butadiene, vinyl acetate, tetrafluoroethylene and diethyl maleate. In a subsequent paper, Brubaker 2), Coffman and Hoehn described in detail their procedure for the free radical initiated copolymerization of CO and C2H4. Di(tert-butyl)peroxide was the typical initiator. Combined gas pressures of up to 103 MPa (= 15,000 psi) and reaction temperatures of 120—165 °C were employed. Copolymers of molecular weight up to 8000 were obtained. The percentage of CO present in the C2H4—CO copolymer was dependent on several factors which included reaction temperature, pressure and composition of reaction mixture. Close to 50 mol % incorporation of CO in the copolymer may be achieved by using a monomer mixture that is >70 mol% CO. Other related procedures for the free radical... 

Terpolymers made from two different olefins and CO are known. They were first described in Brubaker s initial patent and involved the free radical initiated terpolymerization of CO and C2H with another olefin such as propylene, isobutylene, butadiene, vinyl acetate, diethyl maleate or tetrafluoroethylene More recently, in another patent, Hammer has described the free radical initiated terpolymerization of CO and C2H with vinyl esters, vinyl ethers or methyl methacrylate 26Reaction temperatures of 180-200 °C and a combined pressure of 186 MPa were employed. Typically a CO QH4 olefin molar ratio of 10 65 25 was observed in the terpolymers. In other patents, Hammer 27,28) has described the formation of copolymers with pendant epoxy groups by the free radical initiated polymerization of CO, QH4, vinyl acetate and glycidyl methacrylate. Reaction conditions similar to those stated above were employed, and a typical CO C2H vinyl acetate glycidyl methacrylate molar ratio of 10 65 20 5 was observed in the product polymer. 

The in situ regeneration of Pd(II) from Pd(0) should not be counted as being an easy process, and the appropriate solvents, reaction conditions, and oxidants should be selected to carry out smooth catalytic reactions. In many cases, an efficient catalytic cycle is not easy to achieve, and stoichiometric reactions are tolerable only for the synthesis of rather expensive organic compounds in limited quantities. This is a serious limitation of synthetic applications of oxidation reactions involving Pd(II). However it should be pointed out that some Pd(II)-promoted reactions have been developed as commercial processes, in which supported Pd catalysts are used. For example, vinyl acetate, allyl acetate and 1,4-diacetoxy-2-butene are commercially produced by oxidative acetoxylation of ethylene, propylene and butadiene in gas or liquid phases using Pd supported on silica. It is likely that Pd(OAc)2 is generated on the surface of the catalyst by the oxidation of Pd with AcOH and 02, and reacts with alkenes. 

Acrylonitrile (CH2=CH-CN) was made from acetylene and HCN until the 1960s. Today it is made by direct ammoxidation of propylene. Its major use is in making polyacrylonitrile, which is mainly converted to fibers (Orion). It is also copolymerized with butadiene and styrene to produce high impact plastics. 

A detailed study of the oxidation of alkenes by O on MgO at 300 K indicated a stoichiometry of one alkene reacted for each O ion (114). With all three alkenes, the initial reaction appears to be the abstraction of a hydrogen atom by the O ion in line with the gas-phase data (100). The reaction of ethylene and propylene with O" gave no gaseous products at 25°C, but heating the sample above 450°C gave mainly methane. Reaction of 1-butene with O gives butadiene as the main product on thermal desorption, and the formation of alkoxide ions was proposed as the intermediate step. The reaction of ethylene is assumed to go through the intermediate H2C=C HO which reacts further with surface oxide ions to form carboxylate ions in Eq. (23),... 

Another contrarian, DSM in the Netherlands, had been a state-owned company before it became privatized, a process that began in 1989 and was completed in 1996. From its past it had inherited positions in fertilizers, industrial chemicals, and such intermediates as melamine and caprolactam as well as polyolefins, with access to basic olefins through its own crackers in Geleen, Netherlands. In 1997 DSM acquired the polyethylene and polypropylene operations of FIuls (VEBA) with the Gelsenkirchen site. The company had also diversified into elastomers, having purchased in the United States the Copolymer Rubber and Chemical Corporation, which contributed to DSM s expansion into the fields of ethylene propylene, styrene butadiene, and nitrile rubbers. DSM is also a supplier of industrial resins and engineering... 

In the triplet benzene photosensitization, the yield of 1,3-butadiene was about eight times the yield of propylene (with acrolein). ... 

In general, with decreasing hydrocarbon partial pressure, unsaturated components such as acetylene, ethylene, propylene, and butadiene increase whereas BTX, pyrolysis fuel oil, and saturated components such as methane, ethane, and propane decrease. Low hydrocarbon partial pressure can be attained either by high steam dilution or by low absolute pressure in the cracking coil, which is determined by furnace outlet pressure and pressure drop in the cracking coil. For each specific case there is an optimum steam dilution. Reduction of steam dilution influences yields, utilities, running times and, in the case of a new ethylene plant, of course, investment costs—but in different ways, either positive or negative. Thus, an optimization has to be carried out to identify the most economic steam dilution. 

Experiments with ethylene, acetylene, propylene, and butadiene were made using a 1.27 cm i.d. tubular reactor such as used by Tsai and Albright (14) or Brown and Albright (15). This reactor was inserted in a horizontal position in an electrical resistance furnace. 

Formation of the relatively unstable complexes (olefin)M(C0)5 and (olefin)2M(C0)4 (M = Mo or W) with propylene and butadiene has been accomplished (559) by UV irradiation of M(CO)o with olefin in w-hexane. From W(CO)e, the complexes (cis-2-butene)W(CO)6, (fmws-2-butene)-W(CO)5, and (cis-2-butene)2W(CO)4 have been produced similarly. As with the corresponding ethylene complexes, the olefin ligands in the bis-olefin complexes are in trans positions. Although, in these complexes, the butadiene molecule is coordinated at only one double bond, upon lengthy irradiation of (butadiene)2Mo(CO)4 (559), the previously reported (268) complex (butadiene)2Mo(CO)2 involving chelated butadiene molecules is produced. 

The rhodium-catalyzed addition of ethylene to 1,3-butadiene to yield 1,4-hexadiene (5a, 151) proceeds via a similar mechanism (151) with the exception that, upon formation of the alkylrhodium(III) species, the hexadiene synthesis proceeds without further change in the oxidation state of the metal. In these reactions with butadiene the coordinated alkyl groups are either chelate or 7r-allyl structures which appear to stabilize Rh(III) (151). The addition of propylene to butadiene and isoprene to produce [Pg.297]

Note Ethylene may be copolymerized with varying percentages of other materials, e.g., 2-butene or acrylic acid a crystalline product results from copolymerization of ethylene and propylene. When butadiene is added to the copolymer blend, a vulcan-izable elastomer is obtained. 

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