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    • 5. 发明申请
    • PROCESS FOR PREPARING PEROXIDES USING MIXED ANHYDRIDES
    • 使用混合无机物制备过氧化物的方法
    • WO01027078A1
    • 2001-04-19
    • PCT/EP2000/009927
    • 2000-10-09
    • C07C407/00C07B61/00C07C68/02C07C69/96C07C409/24C07C409/34C07C409/38C08F4/32C08F4/34C08F20/00
    • C07C69/96C07C409/24C07C409/34C07C409/38C07C2601/14
    • The invention relates to a process for the preparation of a peracid, perester or diacylperoxide and is characterized in that a mixed anhydride of formula: R [C(O)OC(O)OR ]n or [R C(O)OC(O)O]pR is contacted with a hydroperoxide of formula: R [OOH]m in the presence of a base, wherein R represents a mono-, di-, tri- or tetravalent C1-C19 hydrocarbon group, optionally containing one or more hetero atoms, n is 1-4, R represents a C1-C20 hydrocarbon group, optionally containing one or more hetero atoms, R represents a C1-C19 hydrocarbon group, optionally containing one or more hetero atoms, R represents a di-, tri- or tetravalent C1-C20 hydrocarbon group, optionally containing one or more hetero atoms, p is 2-4, R represents hydrogen or a mono- or divalent C3-C18 tertiary alkyl or C2-C20 acyl group, in which the tertiary alkyl or acyl group may optionally contain one or more hetero atoms, m is 1 or 2, and if R represents hydrogen, m is 1, provided that if the hydroperoxide is an alpha , alpha -dihydroperoxyperoxide, the reaction is not carried out in an inert two-phase solvent system comprising a polar solvent and an polar solvent. The invention also relates to a hydroxyperacid, hydroxyperester, and hydroxydiacylperoxide obtainable by said process and the use of said hydroxyperoxides.
    • 本发明涉及一种制备过酸,过氧化物或二酰基过氧化物的方法,其特征在于下列结构式的混合酸酐:R 1 [C(O)OC(O)OR 2] n或[ 3 C(O)OC(O)O] p R 4在碱的存在下与式R 5 [OOH] m的氢过氧化物接触,其中R 1表示单,二 - ,三价或四价的C 1 -C 19烃基,任选地含有一个或多个杂原子,n为1-4,R 2表示任选含有一个或多个杂原子的C 1 -C 20烃基,R 3, 表示任选含有一个或多个杂原子的C 1 -C 19烃基,R 4表示二价,三价或四价C 1 -C 20烃基,任选地含有一个或多个杂原子,p为2-4,R 其中叔烷基或酰基可任选地含有一个或多个杂原子,m为1或2,并且如果R 1为氢或一或二价C 3 -C 18叔烷基或C 2 -C 20酰基, 5>表示氢,m为1,条件是如果水合 过氧化氢是α,α-二氢过氧化氢,该反应不是在包含极性溶剂和极性溶剂的惰性两相溶剂系统中进行的。 本发明还涉及通过所述方法和所述羟基过氧化物的使用可获得的羟基过酸,羟基过氧化物和羟基过氧化氢。
    • 8. 发明申请
    • PEROXYACID MANUFACTURE
    • 过氧化物制造
    • WO1990014336A1
    • 1990-11-29
    • PCT/GB1990000793
    • 1990-05-21
    • INTEROX CHEMICALS LIMITEDTROUGHTON, Nicholas, AradorCARR, GrahamJAMES, Alun, PryceWILLSON, Andrew, John
    • INTEROX CHEMICALS LIMITED
    • C07C407/00
    • C07D209/48C07C407/00C07C407/003C07C409/24C07C409/40
    • In one class of processes for making poorly soluble organic peroxyacids the corresponding carboxylic acid is reacted with hydrogen peroxide in a reaction medium containing a high concentration of sulphuric acid. The presence of such constituents in the reaction mixture and the manner of the reactants and the way in which they are brought into contact, can result in the processes being hazardous. In the present invention, hazard problems are reduced or eliminated by first dissolving the carboxylic acid in concentrated sulphuric acid, secondly forming a Caro's acid solution containing a complementary amount of sulphuric acid and hydrogen peroxide within a predetermined range, and then introducing the carboxylic acid solution at a controlled rate in the Caro's acid solution, often over a period of from about 30 to 90 minutes, with agitation and temperature control. The compositions of the two reactant solutions are precalculated relative to each other such that the A value (weight ratio of sulphuric acid to the combined weight of it and water) either increases during addition of the carboxylic acid solution or if the latter is relatively less insoluble, stays the same or increases. The solutions are preferably formulated to provide an A value at the end of the reaction period selected in the range of around 0.7 to around 0.8, at a temperature of around 20 to 45 DEG C, the more soluble tending towards the lower end of each range and the less soluble towards the upper end of each range. The process is especially suitable for making poorly soluble aliphatic mono or diperoxycarboxylic acids such as peroxynonanoic acid or diperoxydodecanedioic acid, or for aromatic group substituted peroxyacids in which the peroxydation occurs in a primarily aliphatic environment, such as phthalimidoperoxyhexanoic acid.
    • 在一类制备难溶性有机过氧酸的方法中,相应的羧酸在含有高浓度硫酸的反应介质中与过氧化氢反应。 反应混合物中这些组分的存在和反应物的方式以及它们接触的方式可导致该方法是危险的。 在本发明中,通过首先将羧酸溶解在浓硫酸中,二次形成含有互补量的硫酸和过氧化氢的Caro酸溶液在预定范围内,然后将羧酸溶液 以Caro酸溶液的控制速率,通常在约30至90分钟的时间内进行搅拌和温度控制。 两种反应物溶液的组成相对于彼此预先计算,使得A值(硫酸与其与水的总重量的重量比)在加入羧酸溶液期间增加,或者如果后者相对较不溶解 ,保持不变或增加。 优选将溶液配制成在约20至45℃的温度下在约0.7至约0.8范围内选择的反应周期结束时提供A值,对每个范围的下端的溶解度越趋向 并且朝向每个范围的上端较少溶解。 该方法特别适用于制备难溶的脂族单或二过氧羧酸如过氧壬酸或二过氧十二烷二酸,或芳族取代的过氧酸,其中过氧化在主要脂族环境中发生,例如邻苯二甲酰亚氨基过氧己酸。