| 摘要 |
Plasticizers comprise esters of dibasic acids such as phthalic, adipic, sebacic, and pimelic with alcohols obtained by reduction of OXO aldehydes produced from C6-C9 mono-olefins made by polymerizing propylene or mixtures thereof with butenes or pentenes (see Group IV (b)). In examples dialkyl esters of phthalic acid with C10 and C8 alcohols obtained from propylene trimer and propylene-butenes copolymer respectively are incorporated in polyvinyl chloride mixes of the composition: P.V.C. 100, plasticizer 50, white lead 7, and stearic acid 0.25 parts by weight. The plastics are milled at 140 and pressed for 3 mins. at 150 DEG C.ALSO:Aldehydes are produced by Oxo synthesis from a feedstock comprising a mono-olefin of 6-9 carbon atoms formed by polymerizing propylene alone or admixed with a butene or pentene, carbon monoxide and hydrogen in the presence of a cobalt carbonyl (including carbonyl hydride), catalyst, the synthesis zone being operated at 50-250 atm. without the introduction, before or during the reaction, of cobalt compounds in the solid phase, said catalyst and feedstock being separately introduced into said zone. Preferred synthesis conditions are 100-180 DEG C., and 100-200 atm. The weight of cobalt, as metal, may be .01-5 per cent. of the olefin feed. This may be introduced by passing part of the water gas feed over reduced cobalt oxide usually at 140-200 DEG C. and about 3000 p.s.i. The products are reduced to alcohols and used for making ester plasticizers. Production of catalysts, and conditions for reaction, product separation, and recovery stages may be as described in Specifications 702,191, 702,192, 702,195, 702,196, 702,197, 702,203, 702,204, 702,221, 702,222, 702,241 and 702,242. The olefin polymerization may be effected with, e.g. supported phosphoric acid or phosphates or metals such as cobalt and nickel, or silicaalumina, a C6-C9 fraction being separated. A fraction boiling at 30-150, especially 55-120 DEG C., obtained from propylene polymerization with phosphoric acid on kieselguhr is particularly suitable. Sulphur is preferably removed by extractive or azeotropic distillation. The Oxo product is freed from carbonyl as by heating to 150-250 DEG C., and fractionated, in presence or absence of the cobalt compounds produced. Unreacted olefins separated from the aldehyde product may be recycled. The aldehyde may be hydrogenated with nickel or cobalt at up to 200 DEG C. and 200 atm or more or with copper at about atmospheric pressure. The alcohols are esterified with dibasic acids such as phthalic, adipic, sebacic or pimelic. Thus, phthalic anhydride is reacted with excess alcohol using an acid catalyst and a water entrainer. Alternatively an ester interchange reaction with dimethyl phthalate is used. In examples (1), (2) a propylene polymer fraction boiling at 120-150 DEG C. is treated, the product hydrogenated, and a C10 alcohol fraction recovered, esterified with phthalic anhydride, and incorporated in a P.V.C./plasticizer mix; (3) polymer gasoline (propylene-mixed butenes copolymer) is fractionated into narrow fractions which are oxonated separately using dicobalt octacarbonyl as catalyst, the corresponding alcohols being separately esterified and used in P.V.C./plasticizer mixes. Specification 659,712, also is referred to. The Provisional Specification comprises the use of C6-C9 olefins from any source including cracked and reformed petroleum fractions, synthesis products, and butene polymers, and includes examples using fractions obtained by cracking wax, by reforming, and by copolymerizing n-butene and isobutene, and wherein the catalyst is introduced in the feedstock. |
