• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Katalysiert man die Umesterung von Estern der Formel II mit Alkoholen der Formel III A-(OH)m durch Behandlung mit katalytischen Mengen eines organischen oder anorganischen Zinksalzes und destilliert anschliessend die erhaltene Schmelze in einer Kurzzeit-Destillationsapparatur bei bestimmten Bedingungen an, so erhält man Verbindungen der Formel worin n die Zahlen 0 bis 2, m die Zahlen 1 oder 2, A einen von einem m-wertigen aliphatischen Alkohol abgeleiteten Rest mit 2 bis 18 Kohlenstoffatomen, B Methyl oder t-Butyl und R Methyl oder Ethyl bedeuten in praktisch quantitativer Ausbeute. Die so erhaltenen Produkte enthalten keine störenden Nebenprodukte und müssen nicht zusätzlich gereinigt werden.
    公开号:SU1553010A3
    申请号:SU864027324
    申请日:1986-04-25
    公开日:1990-03-23
    发明作者:Орбан Иван
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of sterically hindered hydroxyphenylcarboxylic acid esters, namely to a process for the preparation of octadecyl-3 (3.5 di-tert-butyl-4-hydroxyphenyl) propionate, which is a stabilizer for synthetic organic polymers, animal and vegetable oils, hydrocarbons, lubricants, etc.
    The aim of the invention is to reduce environmental pollution and simplify the process.
    Example 1: 1051 g (3.6 mol) methyl-3 - (3.5 Di-tert-butyl-4-hydroxyphenyl) is introduced into the flask in which the reflux condenser heated to 80 ° C is located.
    propionate and 1001 g (3.7 mol) of stearyl alcohol and heated to 80 ps; 1.35 g (0.007 mol) of anhydrous zinc acetate are added and heated to 175 ° C under azo pressure. The resulting methanol is distilled in a sump. Then, in a flask at 1 75 ° C for 1 h, a pressure of 1-3 mbar is created in steps and the distillation is continued. Then stirring is carried out for 1 h at 175 ° C and a pressure of 1-3 mbar.
    The resulting melt, having a yellowish color, is continuously passed through a thin-film evaporator (pressure 1-3 mbar, temperature inside 240-2 / 0 ° C). At the bottom of the line is SL
    with

    cm
    The apparatus melts and cools out at 60-80 ° C. The melt is then poured onto the sheet and is crushed after solidification.
    Under certain conditions, the melt is fed directly to the granulation.
    1900 g (99.5% of theor.) Octadecyl-3 (3 5 Di-tert-butyl 1-4-hydroxyphenyl) propionate are obtained, m.p. 50-51 ° C.
    EXAMPLE 2 The method according to Example 1 is repeated, but instead of 1001 g, only 972 g (3.6 mol) of stearyl alcohol is introduced.
    1895 g (99.3% of theor.) Octadecyl-3 (3.5 di-tert-butyl-hydroxyphenyl) propionate are obtained, m.p. 50-51 ° C.
    EXAMPLE 3 A method according to example 1 was repeated, but 1.7 g (0.007 mol) of zinc acetate dihydrate was introduced as a catalyst, and after adding the catalyst, the reaction mixture was first 15 minutes at 80 ° C and pressure. 1-3 mbar is stirred (removal of hydrated water) and only then heated to 1bO ° C under normal pressure. The resulting product corresponds to the product obtained in Example 1, with the same melting point and the same yield.
    Example. In a flask equipped with a reflux condenser heated to 80 ° C, 1051 g (3.6 mol) of methyl 3 (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 1001 g (3.7 mol ) sterile alcohol and heated to 80 ° C, 0.66 g (0.0036 mol) of anhydrous zinc acetate is added, and nitrogen is heated under normal pressure to 175 ° C under atmospheric pressure. The resulting methanol is distilled from the receiver. Then, in a flask at 175 ° C for 1 h, the pressure was gradually reduced to 1-3 mbar and the distillation of methanol was continued. Finally, it is stirred for the next 3 hours at 175 ° C and a pressure of 1-3 mbar.
    The resulting melt, which has a slightly yellowish color, is continuously passed through a thin-film evaporator (pressure 1-3 mbar, temperature inside 21 0-270 ° С). At the bottom of the evaporator, the melt is cooled and exits at 60-80dC. The melt is then poured onto the sheet and, after solidification, is crushed.
    Thus, more than 99% of theoretical is obtained. Octadecyl-3- (3,5-Di-tert-butyl- -gylroxyphenyl) propionate f so pl. 50-51 C.
    Example 5: The method according to the example is repeated, but instead of 0.55 g, 3.3 g (0.018 mol) of zinc acetate are introduced as a catalyst and further stirring at 1-3 mbar is continued for only 30 minutes instead of 3 hours. A virtually quantitative yield of octadecyl 3- (3,5-di-tert-butyl -1 -1 hydroxyphenyl) propionate is obtained with the same melting point as in Example k.
    EXAMPLE 6 The method according to Example K is repeated, but the transesterification is carried out not at 175 ° C, but at 1 ° C, and 1.35 g (0.00 mol ), additional stirring at 1-3 mbar is continued for 30 minutes instead of 3 hours. The same yield of the same product is obtained with the same melting point as in Example k.

    Carrying out the process in this way eliminates the use of toxic compounds with tin. The use of zinc salts is safe for the environment, since zinc is a trace element used in biological systems.
    In addition, the proposed method reduces the time spent on the process, since there is no need for preheated filtering equipment, as well as the need to use tools such as Hyflo, while the yield of the target product is very high (99.5% of theoretical).
    权利要求:
    Claims (1)
    [1]
    1. A method for preparing octadecyl-3 (3 5-di-tert- (butyl-4-hydroxyphenyl) propionate by transesterifying methyl 3 (3.5 Di-tert-butyl-hydroxyphenyl propionate with stearyl alcohol in the presence of a catalyst with a different so that, in order to reduce environmental pollution and simplify the process, zinc acetate and its dihydrate are used as a catalyst, taken in an amount of 0.1-0.5 mol.% based on methyl- - (3, 5-di-tert-butyl-β-hydroxy phenyl) propionate, and the process is carried out at
    ib53uiuo
    pressure 1000-1 mbar, obtained by ras-2. The method according to p. 1, is characterized by distillation of the distillation apparatus and with the fact that the distillation of the short-term operation with pressure melting is carried out in the distillation apparatus 1-3. mbar and at temperatures of short-term action at 2l 0-270 C, and then granularit., 2bO ° C.
    类似技术:
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    同族专利:
    公开号 | 公开日
    KR860008967A|1986-12-19|
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    US4716244A|1987-12-29|
    CA1242214A|1988-09-20|
    JPH0714897B2|1995-02-22|
    CS311986A2|1989-01-12|
    EP0200685A2|1986-11-05|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3779945A|1961-10-30|1973-12-18|Geigy Ag J R|Mixtures of 3--propionic acid esters of alkanediols|
    BE624206A|1961-10-30|
    CH471769A|1965-08-02|1969-04-30|Geigy Ag J R|Process for the preparation of hydroxyphenyl fatty acid esters|
    JPS49132012A|1973-02-09|1974-12-18|
    US4196301A|1973-09-25|1980-04-01|Ciba-Geigy Corporation|2,4,6-Trialkyl-3-hydroxybenzylmalonate|
    JPS532197B2|1973-10-26|1978-01-26|
    US4536593A|1982-07-13|1985-08-20|Ciba-Geigy Corporation|Process for the preparation of sterically hindered hydroxphenylcarboxylic acid esters|
    JPS59222445A|1983-05-30|1984-12-14|Sumitomo Chem Co Ltd|Hindered phenol compound, production thereof and stabilizer for polyolefin containing the same as active constituent|
    US4594444A|1983-12-22|1986-06-10|Ciba-Geigy Corporation|Process for the preparation of sterically hindered hydroxyphenylcarboxylic acid esters|JPH0678278B2|1985-09-03|1994-10-05|住友化学工業株式会社|Process for producing hydroxyphenylpropionates|
    EP0300056B1|1987-02-03|1992-01-29|Yoshitomi Pharmaceutical Industries, Ltd.|Process for preparing tetrakis propionyloxymethyl)methane|
    JPH0710807B2|1987-02-03|1995-02-08|吉富製薬株式会社|Method for producing tetrakis [3-propionyloxymethyl] methane|
    TW212790B|1991-10-15|1993-09-11|Ciba Geigy Ag|
    WO1993008154A1|1991-10-18|1993-04-29|Akzo Nobel N.V.|SYNTHESIS OF α,φ-BIS ALKANE|
    DE4344180A1|1993-12-23|1995-06-29|Bayer Ag|Use of anticorrosive agents in the production of isocyanate-based foams|
    TW289752B|1994-03-11|1996-11-01|Ciba Geigy Ag|
    FR2721924B1|1994-06-30|1996-10-31|Fileco Sa|NOVEL 2,6-DI-TERT-BUTYLPHENOLS SUBSTITUTED IN POSITION 4, THE PHARMACEUTICAL COMPOSITIONS CONTAINING THEM AND THEIR PREPARATION PROCESS|
    US6800228B1|1998-09-22|2004-10-05|Albemarle Corporation|Sterically hindered phenol antioxidant granules having balanced hardness|
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    US6821456B2|1998-09-22|2004-11-23|Albemarle Corporation|Granular polymer additives and their preparation|
    US6596198B1|2000-04-28|2003-07-22|Albemarle Corporation|Additive system for polymers in pellet form which provides proportioned stabilization and internal mold release characteristics|
    DE50109215D1|2000-06-23|2006-05-11|Ciba Sc Holding Ag|PROCESS FOR PREPARING HYDROXYPHENYL CARBOXYLIC ACID ESTERS|
    TW593669B|2001-11-21|2004-06-21|Ciba Sc Holding Ag|Aqueous functional fluids with antioxidants|
    US7667066B2|2004-02-27|2010-02-23|Albemarle Corporation|Preparation of sterically hindered hydroxyphenylcarboxylic acid esters|
    CN105732713B|2014-12-11|2018-05-04|中国石油天然气股份有限公司|One kind includes hindered phenol and phosphite ester Amphi-pathic compound and its synthetic method and application|
    CN105732969B|2014-12-12|2017-10-17|中国石油天然气股份有限公司|A kind of polymer electrolyte is anti-oxidant, antistatic dual-function compound, synthetic method and its application|
    ES2688470T3|2015-03-10|2018-11-02|Evonik Degussa Gmbh|Antioxidants for the preparation of low emission PUR systems|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH187085|1985-05-02|
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