• 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:
    Aryldialkyl in the presence of an accelerator which may be an alkali metal borate (e.g. borax), an alkali metal salt of a polymer (e.g. acrylic polymer) or an alkali reagent (e.g. borax) mixed with a certain proportion of added or hydrated water. Methane (eg cumene) is converted to the corresponding hydroperoxide by reaction with oxygen. In particular when the promoter comprises water, high yields of hydroperoxide are obtained.
    公开号:KR19990063137A
    申请号:KR1019980055510
    申请日:1998-12-16
    公开日:1999-07-26
    发明作者:사라다 고피나탄；존 윌리암 풀머；찬가람폰나트 고피나탄；존 크리스토퍼 슈미트하우저
    申请人:제이 엘. 차스킨, 버나드 스나이더, 아더엠. 킹；제너럴 일렉트릭 캄파니；
    IPC主号:
    专利说明:

    Process for producing hydroperoxide by oxidation
    The present invention relates to the preparation of hydroperoxides, more particularly by their improved oxidation methods.
    Hydroperoxides of aryldialkylmethanes such as cumene are useful intermediates for organic chemicals. Cumene hydroperoxide (hereinafter often CHP) can be converted to phenol and acetone, for example, by acid treatment, both of which have numerous utility in the chemical industry. For example, these two compounds can react with each other to form 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), which is the monomer precursor of polycarbonate and other polymers.
    It has long been known that hydroperoxides of aryldialkylmethanes can be prepared by treating the precursor compound with oxygen. Oxidation reactions typically occur in the presence of a promoter, which is usually an aqueous alkaline compound, such as sodium hydroxide, sodium carbonate, or an alkyl metal salt of carboxylic acid or cumene hydroperoxide.
    Many known methods for the oxidation of aryldialkylmethanes lack such points as yield, reaction rate and tendency to form byproducts. Therefore, it is important to develop new promoters and methods of treating previously used promoters to improve their properties and efficiency.
    The present invention is based on numerous discoveries, including the discovery of novel promoters for oxidation reactions, and the discovery of levels of water content in promoters that substantially improve yield.
    Accordingly, the present invention provides a method of hydrolyzing aryldialkylmethane, comprising contacting aryldialkylmethane with oxygen at a temperature in the range of about 70 to 125 ° C. in the presence of an oxidation promoting amount of one of the following (I) and (II): Oxidation to loperoxide is:
    At least one promoter selected from the group consisting of (I) hydrates of alkali metal borate and (B) alkali metal salts of carboxylic acid-substituted polymers; And
    (II) Alkali reagent as an accelerator mixed with added water or hydrated water, wherein the proportion of water is about 80 to 120% by weight based on the alkaline reagent.
    The aryldialkylmethanes used as reactants according to the invention are of the general formula Wherein A is an aromatic radical and R 1 and R 2 are each alkyl radicals. These are hydrocarbons or substituted hydrocarbons, including those in which the aromatic ring contains alkyl substituents. Phenyl radicals are preferred.
    R 1 and R 2 are alkyl radicals, usually C 1 to C 4 primary alkyl radicals. Methyl radicals are preferred. Thus, a particularly preferred aryldialkylmethane is cumene (isopropylbenzene). Although often mentioned later for cumene, it should be contemplated that other compounds having the above general formula may optionally replace cumene.
    Substantially pure or industrial grade cumene may be used. It is also possible to use cumene streams containing material recycled from previous oxygen runs. Generally, a reactant stream containing about 90% by weight, preferably about 95% by weight cumene, is advantageously used.
    Oxygen is another essential reactant in the process of the invention. It can be used in the form of pure oxygen, but more often exists as a component of a gas mixture such as air.
    According to embodiment I of the present invention, two classes of materials can be used as promoters. For each class, it is often desirable if the promoter is heterogeneous, ie it is not otherwise inherently the promoter is a solid in another liquid-gas reaction mixture.
    Class A consists of hydrates of alkali metal borates. Exemplary and preferred compounds include borax; Sodium tetraborate dicarhydrate (Na 2 B 4 O 7 .10H 2 O).
    Class B consists of alkali metal salts of carboxylic acid-substituted polymers, in particular sodium and potassium, preferably sodium salts. These include, for example, acrylic polymers; That is, acrylic acid homopolymers and copolymers. They may also be polymers of carboxylated styrene, for example. Copolymers of acrylic acid and acrylamide are particularly preferred.
    In embodiment II, any alkaline reagents known in the art or known in the art for being effective as promoters in oxidation reactions are used in admixture with the above amounts of water. Alkali reagents useful as promoters in this embodiment include alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates such as sodium carbonate, and alkali metal borates of the types described above such as borax.
    The amount of promoter used in the process of the invention is typically in the range of about 1 to 10% by weight, based on cumene. The amount of water used in embodiment II, which is important in embodiment II, is about 80 to 120 weight based on alkaline reagents in anhydride form. This amount is present as water added in admixture with anhydrous alkaline reagent. Alternatively, this amount may be present as hydrated water, such as in borax, containing 10 molecules of hydrated water per mole, for a total water content of 90% based on sodium tetraborate.
    If present, this proportion of water results in a substantially higher conversion to CHP than when other amounts of water are present or absent. As used herein, conversion to CHP is the weight of cumene hydroperoxide found to be present in the product by analysis (eg, by titration) divided by the weight of cumene as the reactant, expressed as%.
    The reaction mixture preferably also contains small amounts of cumene hydroperoxide as co-promoter. Its amount is typically in the range of about 0.5 to 10.0% by weight, based on cumene. The conversion of cumene to cumene hydroperoxide is calculated excluding the amount of hydroperoxide added as co-promoter.
    The process of the present invention simply comprises cumene, accelerator, water (if used) and optionally cumene hydroperoxide in an oxygen-containing gas at temperatures ranging from about 70 to 125 ° C., preferably from 70 to 110 ° C., in the presence of a facilitating substance. Is performed by contact with Contact can be accomplished by simply aeration of the gas through the liquid mixture. For example, an input device in which gas enters through a glass filter can be used.
    When the reaction proceeds to the desired degree, cumene hydroperoxide product can be separated by known techniques. Alternatively, also preferably, the organic phase of the reaction mixture can be washed to remove alkali promoters and other impurities and used directly for the synthesis of phenols and acetone.
    The invention is illustrated by the following examples. All parts and percentages are by weight.
    Examples 1 and 2
    A vertical tube reactor containing a glass filter plate near the bottom and an air inlet tube under the filter plate, and a reflux condenser connected to an ice trap to collect volatile impurities were used. Into the reactor was added pure (99 wt% or more) cumene, CHP (82% purity) as promoter and borax aqueous solution as promoter. It was heated to 100 ° C. and air was passed through the mixture at a rate of 67 ml / min for about 6 hours. At the end of this, the mixture was analyzed for cumene hydroperoxide by titration.
    The results are given in Table 1 compared to the control without borax. % Of borax, CHP and water are based on cumene reactants. Selectivity is the ratio of CHP as% of total product formed.
    Example 1Example 2Control Borax,%2.52.5--- Water,%5047.5--- CHP,%4.1105 Conversion rate to CHP,%6.156.523.30 Selectivity,%92.4786.3084.64
    The use of aqueous borax solution yields cumene hydroperoxide at about twice the conversion obtained when no accelerator is used and selectivity comparable to the control, so it is clear that aqueous borax solution is an effective catalyst.
    Examples 3 and 4
    In a 300 ml stainless steel autoclave 100 g cumene, 2 g 82% pure cumene hydroperoxide and 5% by weight of two acrylic polymers (Example 3-poly (acrylamide-acrylic acid), 40% acid group, Sodium salt: Example 4-polymer of Example 3 mixed with 0.5% water).
    The mixture was heated to 115 ° C. and air was passed through at a pressure of 482.7 KPa. After 3 hours, analysis of the mixture showed conversion to 22.3% CHP in Example 3 and conversion to 28.2% CHP in Example 4. The control without the acrylic polymer yielded a conversion of 16.1%.
    Example 5
    The procedure of Example 1 or 2 was repeated and a promoter containing 2% amount of CHP and 1.25% solid sodium carbonate and 1.25% water was used. The air flow rate was 64 ml / min and the temperature was 100 ° C. After 16 hours, the conversion to CHP was 43.34% and the selectivity was 91.04%.
    A control using 2.5% sodium carbonate and 47.5% water as promoter mixture yielded only 15.52% conversion to CHP and 92.62% selectivity. Thus, the advantages of the water used in the amounts described above for embodiment II are evident.
    Examples 6-9
    The procedure of Example 1 or 2 was repeated and solid borax (ie sodium tetraborate dicarhydrate) was used with pure and regenerated (purity of about 98%) cumene as catalyst. As co-promoter, cumene hydroperoxide was introduced at 2%. The results are given in Table 2.
    Example 6Example 7Example 8Example 9 Cumene usedPure thingRegeneratedRegeneratedPure thing Borax,%2.55.02.52.5 Air flow rate, ml / min65656570 Conversion rate to CHP,%43.0957.8233.4649.79 Selectivity,%91.2787.8892.1591.80
    It will be appreciated that the conversion to CHP was much higher in Examples 6-9 with the ratio of water defined according to embodiment II than in Examples 1 and 2 where water was used at higher ratios. Selectivity was equivalent.
    According to the present invention, the aryldialkylmethane is reacted with oxygen in the presence of a promoter to obtain a hydroperoxide in a higher yield than without the promoter, and especially when a specific amount of water is included, To obtain.
    权利要求:
    Claims (17)
    [1" claim-type="Currently amended] Oxidizing aryldialkylmethane to hydroperoxide, comprising contacting aryldialkylmethane with oxygen at a temperature in the range of about 70 to 125 ° C. in the presence of an oxidation promoting amount of one of (I) and (II) Way:
    At least one promoter selected from the group consisting of (I) hydrates of alkali metal borate and (B) alkali metal salts of carboxylic acid-substituted polymers; And
    (II) Alkali reagent as an accelerator mixed with added water or hydrated water, wherein the proportion of water is about 80 to 120% by weight based on the alkaline reagent.
    [2" claim-type="Currently amended] Oxygen dialkylmethane is oxygenated at a temperature in the range of about 70 to 125 ° C. in the presence of an oxidation promoting amount of at least one promoter selected from the group consisting of (A) a hydrate of an alkali metal borate and (B) an alkali metal salt of a carboxylic acid-substituted polymer. A method of oxidizing aryldialkylmethane to hydroperoxide, comprising contacting with a.
    [3" claim-type="Currently amended] The method of claim 2,
    Wherein aryldialkylmethane is cumene.
    [4" claim-type="Currently amended] The method of claim 3, wherein
    The promoter is a hydrate of an alkali metal borate.
    [5" claim-type="Currently amended] The method of claim 4, wherein
    The promoter is borax.
    [6" claim-type="Currently amended] The method of claim 3, wherein
    The promoter is an alkali metal salt of an acrylic polymer.
    [7" claim-type="Currently amended] The method of claim 6,
    The acrylic polymer is an acrylic acid-acrylamide copolymer.
    [8" claim-type="Currently amended] Aryldialkyl at a temperature in the range of about 70 to 125 ° C. in the presence of an accelerated amount of oxidation of the solid alkaline reagent as an accelerator mixed with added water or hydrated water, wherein the proportion of water is about 80 to 120 wt% based on the alkali reagent. Oxidizing aryldialkylmethane to hydroperoxide, comprising contacting methane with oxygen.
    [9" claim-type="Currently amended] The method of claim 8,
    Wherein aryldialkylmethane is cumene.
    [10" claim-type="Currently amended] The method of claim 9,
    The alkali reagent is an alkali metal hydroxide, carbonate or borate.
    [11" claim-type="Currently amended] The method of claim 10,
    The alkaline reagent is sodium carbonate.
    [12" claim-type="Currently amended] The method of claim 10,
    The promoter-water mixture is borax.
    [13" claim-type="Currently amended] The method of claim 1,
    Wherein cumene hydroperoxide is present as co-promoter.
    [14" claim-type="Currently amended] The method of claim 13,
    Wherein the proportion of cumene hydroperoxide ranges from about 0.5 to 10.0 weight percent based on cumene.
    [15" claim-type="Currently amended] The method of claim 1,
    Wherein the amount of promoter is about 1 to 10 weight percent based on aryldialkylmethane.
    [16" claim-type="Currently amended] The method of claim 1,
    Providing oxygen as air.
    [17" claim-type="Currently amended] The method of claim 1,
    The reaction temperature is about 70 to 110 ° C.
    类似技术:
    公开号 | 公开日 | 专利标题
    KR101748068B1|2017-06-15|Processes for producing phenol
    KR100395987B1|2003-11-14|Process for preparation of allyl ether, thioether and amine compounds
    EP0738698B1|2000-08-23|Process for decomposition of cumene hydroperoxide
    KR100653589B1|2006-12-05|Catalytic method of producing alkyl mercaptans by adding hydrogen sulphide to an olefin
    CN101389586B|2012-06-27|Selective oxidation of alkylbenzenes
    Sharpless et al.1976|Osmium-catalyzed vicinal oxyamination of olefins by Chloramine-T
    KR101257988B1|2013-04-24|Oxidation of hydrocarbons
    CN1886196B|2010-09-15|Functionalized zeolite compositions and methods for their preparation and use
    CN1210242C|2005-07-13|Method for making bisphenol A
    US8247593B2|2012-08-21|Process for preparing substituted 7-cyano quinone methides
    US8487138B2|2013-07-16|Oxidation of hydrocarbons
    ES2381859T3|2012-06-01|Process for the preparation of | alkyl acrylates
    US6620974B2|2003-09-16|Method and system for manufacturing cumene hydroperoxide
    TWI310027B|2009-05-21|Co-production of phenol, acetone, alpha-methylstyrene and propylene oxide, and catalyst therefor
    KR910003252B1|1991-05-25|Process for preparing bis phenola
    Aresta et al.2002|Carbon dioxide as building block for the synthesis of organic carbonates: behavior of homogeneous and heterogeneous catalysts in the oxidative carboxylation of olefins
    US6720462B2|2004-04-13|Method for producing aromatic alcohols, especially phenol
    CN100558689C|2009-11-11|Be used to produce the method for phenol and methyl ethyl ketone
    US5908962A|1999-06-01|Cumene oxidation process
    Varagnat1976|Hydroquinone and pyrocatechol production by direct oxidation of phenol
    US5241106A|1993-08-31|Process for producing ethyl acetate
    Rust et al.1949|Oxidation of hydrocarbons catalyzed by hydrogen bromide-Summary
    CN1039803A|1990-02-21|The method for preparing internal olefin sulphonates
    JP2002255880A|2002-09-11|Method for bisphenol a production
    EP1188735B1|2005-07-27|Process for producing carbonyl or hydroxy compound
    同族专利:
    公开号 | 公开日
    SG71875A1|2000-04-18|
    CA2255484A1|1999-06-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-12-17|Priority to IN2390CA1997
    1997-12-17|Priority to IN2390/CAL/97
    1998-12-16|Application filed by 제이 엘. 차스킨, 버나드 스나이더, 아더엠. 킹, 제너럴 일렉트릭 캄파니
    1999-07-26|Publication of KR19990063137A
    优先权:
    申请号 | 申请日 | 专利标题
    IN2390CA1997|1997-12-17|
    IN2390/CAL/97|1997-12-17|
    [返回顶部]