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    • 2. 发明授权
    • Process for producing unsaturated carboxylic esters
    • 不饱和羧酸酯的制备方法
    • US4356316A
    • 1982-10-26
    • US236956
    • 1981-02-23
    • Atsushi AoshimaToshiaki Murofushi
    • Atsushi AoshimaToshiaki Murofushi
    • C07C45/35C07C67/39
    • C07C45/35C07C67/39
    • A process for producing an ester of acrylic or methacrylic acid by oxidizing propylene or isobutylene in the liquid phase in the presence of a straight chain lower alcohol and molecular oxygen, characterized by carrying out the reaction in the presence of:(1) a catalyst consisting of palladium and at least one metal selected from the group consisting of lead, bismuth, thallium, tellurium and mercury, preferably an intermetallic compound of palladium and said metal;(2) at least one compound selected from the group consisting of mineral acids, heteropoly-acids, heteropoly-acid salts, molybdic acid and organic sulfonic acids, preferably heteropoly-acids or their salts; and(3) optionally, at least one compound selected from the group consisting of alkali metal compounds and alkaline earth metal compounds.According to this process, the activity of catalyst is high even in a reaction at low temperatures, the amount of by-product is small and the objective ester can be produced with a high selectivity.
    • 一种通过在直链低级醇和分子氧的存在下,在液相中氧化丙烯或异丁烯来生产丙烯酸或甲基丙烯酸酯的方法,其特征在于在下列存在下进行反应:(1) 的钯和选自铅,铋,铊,碲和汞的至少一种金属,优选钯和所述金属的金属间化合物; (2)至少一种选自无机酸,杂多酸,杂多酸盐,钼酸和有机磺酸的化合物,优选杂多酸或其盐; 和(3)任选的至少一种选自碱金属化合物和碱土金属化合物的化合物。 根据该方法,即使在低温下的反应中,催化剂的活性也高,副产物的量少,能以高选择性生产目的酯。
    • 3. 发明授权
    • Process for preparing an ether having tertiary alkyl group
    • 制备具有叔烷基的醚的方法
    • US4376219A
    • 1983-03-08
    • US340668
    • 1982-01-19
    • Toshiaki MurofushiAtsushi Aoshima
    • Toshiaki MurofushiAtsushi Aoshima
    • B01J21/00B01J23/00B01J23/24B01J27/00C07B61/00C07C41/00C07C41/05C07C41/06C07C43/04C07C67/00
    • B01J23/24C07C41/06
    • In a process for preparing an ether having a tertiary alkyl group by the reaction of a primary or secondary alcohol with the tertiary olefin in a tertiary olefin-containing mixed hydrocarbon, said reaction is carried out in the presence of an adduct of the starting alcohol with a heteropoly acid or salt thereof containing at least one member selected from the group consisting of P, Si, B, Ge, As, Se, Ti, Zr, Mn, F, U, Ce and Th as a central element, at least Mo and/or W as a coordinating element and at least one member selected from the group consisting of H, Li, Na, K, Rb, Cs, NR.sup.4 R.sup.5 R.sup.6 R.sup.7 wherein R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are hydrogen atoms or alkyl groups, Mg, Ca, Ba, Zr, Cr, Mn, Fe, Co, Mi, Cu, Ag, Zn, Cd, Hg, Al, Pb and Bi as cations, the ratio of the number of the coordinating elements to the number of the central elements being 2.5 to 12, said adduct being substantially in the solid phase, under a pressure higher than the pressure at which said mixed hydrocarbon containing the tertiary olefin is kept in the liquid phase. The reaction under the above conditions enables the extreme reduction of the degree of excess of the alcohol and the enhancement of the conversion of said tertiary olefin.
    • 在通过伯醇或仲醇与叔烯烃在含叔烯烃的混合烃中反应制备具有叔烷基的醚的方法中,所述反应在起始醇加合物与 含有选自P,Si,B,Ge,As,Se,Ti,Zr,Mn,F,U,Ce和Th中的至少一种的杂多酸或其盐作为中心元素,至少Mo 和/或W作为配位元素和选自H,Li,Na,K,Rb,Cs,NR4R5R6R7中的至少一种,其中R4,R5,R6和R7是氢原子或烷基,Mg,Ca ,Ba,Zr,Cr,Mn,Fe,Co,Mi,Cu,Ag,Zn,Cd,Hg,Al,Pb和Bi作为阳离子,协调元素数与中心元素数之比为 2.5至12,所述加合物基本上处于固相中,在高于含有叔烯烃的混合烃的压力 翅片保持液相。 在上述条件下的反应使得醇的过量度极度降低,并且提高了所述叔烯烃的转化率。