Production from butadiene

An attractive alternative to building a world scale adipic acid plant is to construct a specialty smaller volume oxycarbonylation plant which is capable of exclusively producing the more valuable precursors for pelargonic and sebacic acid. Oxycarbonylation process conditions can be controlled to give methyl, 4-pentadienoate which is the product from butadiene mono-carbonylation(39,40). Methyl, 4-pentadienoate can react in a subsequent step with butadiene to give an unsaturated pelargonic acid precursor in high yield(41). Methyl, 4-pentadienoate... 

Palladium-catalyzed addition of phenylsulfinic acid to butadiene and isoprene gave mainly 1,2-addition products. From butadiene, a 4 1 ratio of 1,2- to 1,4-addition product was obtained in high yield [Eq.(ll)] [27]. It was later shown that the 1,2-addition product is the kinetic product and that prolonged reaction time increased the amount of 1,4-addition product [27b]. 

Other related cyclic olefins, 1,3-cyclohexadiene and vinylcyclohexene, are reported to be formed as main products from butadiene over tungsten oxide catalysts [24]. Under the reaction conditions, hexatriene, resulting from the intermolecular metathesis of butadiene, underwent subsequent cyclization to 1,3-cyclohexa-diene ... 

Figure 12.8 Ozonolysis products from butadiene containing 11% vinyl structures A succinaldehyde B 3-formyl-l,6-hexanedial C 4-octene-l,8-dial.

Example 4.4 Butadiene sulfone (or 3-sulfolene) is an intermediate used for the production of solvents. It can be produced from butadiene and sulfur dioxide according to the reaction ... 

Thus, to name just a few examples, a nucleophilic aliphatic substitution such as the reaction of the bromide 3.5 with sodium iodide (Figure 3-21a) can lead to a range of stereochemical products, from a l l mbrture of 3.6 and 3.7 (racemization) to only 3.7 (inversion) depending on the groups a, b, and c that are bonded to the central carbon atom. The ring closure of the 1,3-butadiene, 3.8, to cyclobutene... 

It is possible to prepare 1-acetoxy-4-chloro-2-alkenes from conjugated dienes with high selectivity. In the presence of stoichiometric amounts of LiOAc and LiCl, l-acetoxy-4-chloro-2-hutene (358) is obtained from butadiene[307], and cw-l-acetoxy-4-chloro-2-cyclohexene (360) is obtained from 1.3-cyclohexa-diene with 99% selectivity[308]. Neither the 1.4-dichloride nor 1.4-diacetate is formed. Good stereocontrol is also observed with acyclic diene.s[309]. The chloride and acetoxy groups have different reactivities. The Pd-catalyzed selective displacement of the chloride in 358 with diethylamine gives 359 without attacking allylic acetate, and the chloride in 360 is displaced with malonate with retention of the stereochemistry to give 361, while the uncatalyzed reaction affords the inversion product 362. 

Recall from Section 7 13 that a stereospecific reaction is one in which each stereoiso mer of a particular starting material yields a different stereoisomeric form of the reaction product In the ex amples shown the product from Diels-Alder cycloaddi tion of 1 3 butadiene to as cinnamic acid is a stereo isomer of the product from trans cinnamic acid Each product although chiral is formed as a racemic mixture... 

It has been known since the early 1950s that butadiene reacts with CO to form aldehydes and ketones that could be treated further to give adipic acid (131). Processes for producing adipic acid from butadiene and carbon monoxide [630-08-0] have been explored since around 1970 by a number of companies, especially ARCO, Asahi, BASF, British Petroleum, Du Pont, Monsanto, and Shell. BASF has developed a process sufficiendy advanced to consider commercialization (132). There are two main variations, one a carboalkoxylation and the other a hydrocarboxylation. These differ in whether an alcohol, such as methanol [67-56-1is used to produce intermediate pentenoates (133), or water is used for the production of intermediate pentenoic acids (134). The former is a two-step process which uses high pressure, >31 MPa (306 atm), and moderate temperatures (100—150°C) (132—135). Butadiene,... 

Dehydrogenation. Dehydrogenation of / -butane was once used to make 1,3-butadiene, a precursor for synthetic mbber. There are currently no on-purpose butadiene plants operating in the United States butadiene is usually obtained as a by-product from catalytic cracking units. 

Nylon-12. Laurolactam [947-04-6] is the usual commercial monomer for nylon-12 [24937-16-4] manufacture. Its production begins with the mixture of cyclododecanol and cyclododecanone which is formed in the production of dodecanedioic acid starting from butadiene. The mixture is then converted quantitatively to cyclododecanone via dehydrogenation of the alcohol at 230—245°C and atmospheric pressure. The conversion to the lactam by the rearrangement of the oxime is similar to that for caprolactam manufacture. There are several other, less widely used commercial routes to laurolactam (171). 

Production of ethylbenzene from butadiene has been iavestigated by many researchers. It consists of two steps cyclodimerization of 1,3-butadiene to 4-vinylcyclohexene and dehydrogenation of the vinylcyclohexene to ethylbenzene. 

Oiganometallic usage is shown in the piepaiation of titanium- oi vanadium-containing catalysts foi the polymerisation of styrene or butadiene by the reaction of dimethyl sulfate with the metal chloride (145). Free-radical activity is proposed for the quaternary product from dimethylaruline and dimethyl sulfate and for the product from l,l,4,4-tetramethyl-2-tetra2ene and dimethyl sulfate (146,147). 

By-products from EDC pyrolysis typically include acetjiene, ethylene, methyl chloride, ethyl chloride, 1,3-butadiene, vinylacetylene, benzene, chloroprene, vinyUdene chloride, 1,1-dichloroethane, chloroform, carbon tetrachloride, 1,1,1-trichloroethane [71-55-6] and other chlorinated hydrocarbons (78). Most of these impurities remain with the unconverted EDC, and are subsequendy removed in EDC purification as light and heavy ends. The lightest compounds, ethylene and acetylene, are taken off with the HCl and end up in the oxychlorination reactor feed. The acetylene can be selectively hydrogenated to ethylene. The compounds that have boiling points near that of vinyl chloride, ie, methyl chloride and 1,3-butadiene, will codistiU with the vinyl chloride product. Chlorine or carbon tetrachloride addition to the pyrolysis reactor feed has been used to suppress methyl chloride formation, whereas 1,3-butadiene, which interferes with PVC polymerization, can be removed by treatment with chlorine or HCl, or by selective hydrogenation. 

The manufacture of hexamethylenediamine [124-09-4] a key comonomer in nylon-6,6 production proceeds by a two-step HCN addition reaction to produce adiponittile [111-69-3] NCCH2CH2CH2CH2CN. The adiponittile is then hydrogenated to produce the desired diamine. The other half of nylon-6,6, adipic acid (qv), can also be produced from butadiene by means of either of two similar routes involving the addition of CO. Reaction between the diamine and adipic acid [124-04-5] produces nylon-6,6. 

Diels-Alder Reactions. The important dimerization between 1,3-dienes and a wide variety of dienoplules to produce cyclohexene derivatives was discovered in 1928 by Otto Diels and Kurt Alder. In 1950 they won the Nobel prize for their pioneering work. Butadiene has to be in the j -cis form in order to participate in these concerted reactions. Typical examples of reaction products from the reaction between butadiene and maleic anhydride (1), or cyclopentadiene (2), or itself (3), are <7 -1,2,3,6-tetrahydrophthaHc anhydride [27813-21 -4] 5-vinyl-2-norbomene [3048-64-4], and 4-vinyl-1-cyclohexene [100-40-3], respectively. 

ABS (acrylonitrile—butadiene-styrene) resins are two-phase blends. These are prepared by emulsion polymerization or suspension grafting polymerization. Products from the former process contain 20—22% butadiene those from the latter, 12—16%. 

The pattern of commercial production of 1,3-butadiene parallels the overall development of the petrochemical industry. Since its discovery via pyrolysis of various organic materials, butadiene has been manufactured from acetylene as weU as ethanol, both via butanediols (1,3- and 1,4-) as intermediates (see Acetylene-DERIVED chemicals). On a global basis, the importance of these processes has decreased substantially because of the increasing production of butadiene from petroleum sources. China and India stiU convert ethanol to butadiene using the two-step process while Poland and the former USSR use a one-step process (229,230). In the past butadiene also was produced by the dehydrogenation of / -butane and oxydehydrogenation of / -butenes. However, butadiene is now primarily produced as a by-product in the steam cracking of hydrocarbon streams to produce ethylene. Except under market dislocation situations, butadiene is almost exclusively manufactured by this process in the United States, Western Europe, and Japan. 

Since the bulk of butadiene is recovered from steam crackers, its economics is very sensitive to the selection of feedstocks, operating conditions, and demand patterns. Butadiene supply and, ultimately, its price are strongly influenced by the demand for ethylene, the primary product from steam cracking. Currently there is a worldwide surplus of butadiene. Announcements of a number of new ethylene plants will likely result in additional butadiene production, more than enough to meet worldwide demand for polymers and other chemicals. When butadiene is in excess supply, ethylene manufacturers can recycle the butadiene as a feedstock for ethylene manufacture. 

Significant products from a typical steam cracker are ethylene, propylene, butadiene, and pyrolysis gasoline. Typical wt % yields for butylenes from a steam cracker for different feedstocks are ethane, 0.3 propane, 1.2 50% ethane/50% propane mixture, 0.8 butane, 2.8 hill-range naphtha, 7.3 light gas oil, 4.3. A typical steam cracking plant cracks a mixture of feedstocks that results in butylenes yields of about 1% to 4%. These yields can be increased by almost 50% if cracking severity is lowered to maximize propylene production instead of ethylene. 

Chloroprene (2-chloro-1,3-butadiene), [126-99-8] was first obtained as a by-product from tbe synthesis of divinylacetylene (1). Wben a mbbery polymer was found to form spontaneously, investigations were begun tbat prompdy defined tbe two methods of synthesis that have since been the basis of commercial production (2), and the first successbil synthetic elastomer. Neoprene, or DuPrene as it was first called, was introduced in 1932. Production of chloroprene today is completely dependent on the production of the polymer. The only other use accounting for significant volume is the synthesis of 2,3-dichloro-l,3-butadiene, which is used as a monomer in selected copolymerizations with chloroprene. 

The vinylacetylene [689-97-4] route to chloroprene has been described elsewhere (14). It is no longer practical because of costs except where inexpensive by-product acetylene and existing equipment ate available (see Acetylene-DERIVED chemicals). In the production of chloroprene from butadiene [106-99-0], there are three essential steps, chlorination, isomerization, and caustic dehydrochlorination of the 3,3-dichloro-l-butene, as shown by the following equations Chlorination... 

During World War II, production of butadiene (qv) from ethanol was of great importance. About 60% of the butadiene produced in the United States during that time was obtained by a two-step process utilizing a 3 1 mixture of ethanol and acetaldehyde at atmospheric pressure and a catalyst of tantalum oxide and siHca gel at 325—350°C (393—397). Extensive catalytic studies were reported (398—401) including a fluidized process (402). However, because of later developments in the manufacture of butadiene by the dehydrogenation of butane and butenes, and by naphtha cracking, the use of ethanol as a raw material for this purpose has all but disappeared. 

In 1942 the Japanese overran Malaya and the then Dutch East Indies to cut off the main sources of natural rubber for the United States and the British Commonwealth. Because of this the US Government initiated a crash programme for the installation of plants for the manufacture of a rubber from butadiene and styrene. This product, then known as GR-S (Government Rubber-Styrene), provided at that time an inferior substitute for natural rubber but, with a renewed availability of natural rubber at the end of the war, the demand for GR-S slumped considerably. (Today the demand for SBR (as GR-S is now known) has increased with the great improvements in quality that have been made and SBR is today the principal synthetic rubber). 

Temperature-dependent phase behavior was first applied to separate products from an ionic liquid/catalyst solution by de Souza and Dupont in the telomerization of butadiene and water [34]. This concept is especially attractive if one of the substrates shows limited solubility in the ionic liquid solvent. 

Butadiene is obtained mainly as a coproduct with other light olefins from steam cracking units for ethylene production. Other sources of butadiene are the catalytic dehydrogenation of butanes and butenes, and dehydration of 1,4-butanediol. Butadiene is a colorless gas with a mild aromatic odor. Its specific gravity is 0.6211 at 20°C and its boiling temperature is -4.4°C. The U.S. production of butadiene reached 4.1 billion pounds in 1997 and it was the 36th highest-volume chemical. ... 

Butadiene is obtained as a by-product from ethylene production. It is then separated from the C4 fraction by extractive distillation using furfural. 

Butadiene is mainly obtained as a byproduct from the steam cracking of hydrocarbons and from catalytic cracking. These two sources account for over 90% of butadiene demand. The remainder comes from dehydrogenation of n-butane or n-butene streams (Chapter 3). The 1998 U.S. production of butadiene was approximately 4 billion pounds, and it was the 36th highest-volume chemical. Worldwide butadiene capacity was nearly 20 billion pounds. 

The production of adiponitrile from butadiene starts by a free radical chlorination, which produces a mixture of 1,4-dichloro-2-butene and 3,4-dichloro -1-butene ... 

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