Succinic acid from ethylene

Other microbial plastics are polymers from lactic acid, succinic acid, poly(ethylene) ethylene from ethanol and its polymer poly-(ethylene), 1,3-propanediol, as weU as poly(p-phenylene) (23). 

Succinic acid diesters are also obtained by one-step hydrogenation (over Pd on charcoal) and esterification of maleic anhydride dissolved in alcohols (40) carbonylation of acrylates in the presence of alcohols and Co complex catalysts (41—43) carbonylation of ethylene in alcohol in the presence of Pd or Pd—Cu catalysts (44—50) hydroformylation of acetylene with Mo and W complexes in the presence of butanol (51) and a biochemical process from dextrose/com steep Hquor, using Jinaerobiumspirillum succiniciproducens as a bacterium (52). 

The principles set forth above account reasonably well for the course of bifunctional condensations under ordinary conditions and for the relative difficulty of ring formation with units of less than five or more than seven members. They do not explain the formation of cyclic monomers from five-atom units to the total exclusion of linear polymers. Thus 7-hydroxy acids condense exclusively to lactones such as I, 7-amino acids give the lactams II, succinic acid yields the cyclic anhydride III, and ethylene carbonate and ethylene formal occur only in the cyclic forms IV and V. 

Starting from the commercially available aldehyde (12), styrene (13) was prepared by a straightforward synthetic sequence (Scheme 11.3). Subsequent esterification of the phenol with succinate-derivatized poly(ethylene glycol) monomethyl ether (MeO-PEG) appended the styrene unit to approximately 50% of the free acid groups in (14). The loading in (15) was estimated by 500 MHz NMR spectroscopy to be about 0.1 mmol g . In a final step, the polymer-bound catalyst was ob-... 

Chemical/Physical. Gaseous products formed from the reaction of cyclohexene with ozone were (% yield) formic acid (12), carbon monoxide (18), carbon dioxide (42), ethylene (1), and valeraldehyde (17) (Hatakeyama et al., 1987). In a smog chamber experiment conducted in the dark at 25 °C, cyclohexane reacted with ozone. The following products and their respective molar yields were oxalic acid (6.16%), malonic acid (6.88%), succinic acid (0.63%), glutaric acid (5.89%), adipic acid (2.20%), 4-hydroxybutanal (2.60%), hydroxypentanoic acid (1.02%), hydroxyglutaric acid (2.33%), hydroxyadipic acid (1.19%), 4-oxobutanoic acid (6.90%), 4-oxopentanoic acid (4.52%), 6-oxohexanoic acid (4.16%), 1,4-butandial (0.53%), 1,5-pentanedial (0.44%), 1,6-hexanedial (1.64%), and pentanal (17.05%). 

Chemical/Physical. Gaseous products formed from the reaction of cyclopentene with ozone were (% yield) formic acid (11), carbon monoxide (35), carbon dioxide (42), ethylene (12), formaldehyde (13), and butanal (11). Particulate products identified include succinic acid, glutaraldehyde, 5-oxopentanoic acid, and glutaric acid (Hatakeyama et al., 1987). 

Scope of oxidative carbonylation has been studied [83]. The synthesis of acrylic acid or its ester (116) from ethylene has been investigated in AcOH from the standpoint of its commercial production [84]. The carbonylation of styrene is a promising commercial process for cinnamate (117) [80,85,86]. Succinate formation occurs at room temperature and 1 atm of CO using Pd on carbon as a catalyst in the presence of an excess of CuCl2, although the reaction is slow (100% conversion after 9 days) [87],... 

Synthesis from Ethylene Bromide.—Such an acid is known as a commonly occurring substance in nature and is called succinic acid. It has the composition C4H6O4 and is plainly isomeric with methyl malonic acid. Its constitution as given above is, however, proven by the following syntheses Ethylene bromide, or symmetrical di-brom ethane, which is made by the addition of bromine to ethylene gas, yields by treatment with potassium cyanide a symmetrical di-... 

The unsaturated dibasic acids bear the same relation to the saturated dibasic acids, just considered, as the unsaturated mono-basic acids, acrylic acid, crotonic acid, etc. (p. 172), do to the saturated monobasic acids, acetic acid, etc. They are also the oxidation products of the unsaturated hydrocarbons, alcohols, and aldehydes just as oxalic and succinic acids are of the corresponding saturated compounds. As the simplest dibasic acid containing an ethylene unsaturated group will contain two carboxyl groups and also two doubly linked carbon atoms there must be at least four carbons in the compound. This compound will therefore correspond to succinic acid of the saturated series. Now succinic acid may be derived from either butane by oxidation or from ethane by substitution. Similarly the corresponding unsaturated acid may be derived from butene by oxidation or from ethene by substitution. All of these general relationships may be represented as follows ... 

Deposits may also be formed from additives used in the process, e.g. defoamers, sizing agents and wax dispersants. Typical components that can be found in deposits originating from this source are fatty alcohols (defoamer), ethylene bisstearamide (BBS) wax (defoamer), calcium salt of alkenyl succinic acid (ASA sizing agent) and paraffin wax (from wax dispersions). Other additives although by themselves not depositable, such as talc, may often be found incorporated into a deposit with mixed composition. 

Figure 21.11 Degradation of ester bonds by different enzymes. Poly(L-lactic acid) (L-PLA), poly[D,L-lactic acid) (DL-PLA), poly(caprolactone) [PCL), poly[butylene succinate adipate) (PBSA), polyfbutylene succinate) [PBS), poly[propiolactone) (PPL), poly[3-hydroxybutyrate) [DL-PHB), poly[4-hydroxybu-tyrate) (4-PHB), poly[ethylene succinate) (PES), poly[ethylene adipate) [PEA) and poly[3R-3-hydroxybutyrate) [D-PHB). Adapted from [110].

If the number of polar groups becomes very large relative to the number of CH2 groups, as for instance in the polyester from ethylene glycol and succinic acid, the interaction of the polar groups in adjacent chains (and perhaps also in the same chain) becomes so considerable as to cause the structure to seek an other more favour-... 

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