WO2017067098A1 - 芳基取代对苯二胺类物质的制备方法 - Google Patents

芳基取代对苯二胺类物质的制备方法 Download PDF

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WO2017067098A1
WO2017067098A1 PCT/CN2016/070614 CN2016070614W WO2017067098A1 WO 2017067098 A1 WO2017067098 A1 WO 2017067098A1 CN 2016070614 W CN2016070614 W CN 2016070614W WO 2017067098 A1 WO2017067098 A1 WO 2017067098A1
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Prior art keywords
raw material
phenylenediamine
catalyst
preparation
aryl
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PCT/CN2016/070614
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English (en)
French (fr)
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郭湘云
邢金国
阮晓敏
陈新民
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江苏圣奥化学科技有限公司
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Priority to EA201890804A priority Critical patent/EA035875B1/ru
Priority to RS20201591A priority patent/RS61329B1/sr
Application filed by 江苏圣奥化学科技有限公司 filed Critical 江苏圣奥化学科技有限公司
Priority to ES16856546T priority patent/ES2839423T3/es
Priority to MX2018004932A priority patent/MX2018004932A/es
Priority to AU2016343321A priority patent/AU2016343321B2/en
Priority to KR1020187014156A priority patent/KR102090115B1/ko
Priority to MYPI2018000536A priority patent/MY185374A/en
Priority to EP16856546.3A priority patent/EP3366666B1/en
Priority to BR112018007719-4A priority patent/BR112018007719B1/pt
Priority to PL16856546T priority patent/PL3366666T3/pl
Priority to CA3002688A priority patent/CA3002688C/en
Priority to JP2018540193A priority patent/JP6643496B2/ja
Priority to SG11201803239PA priority patent/SG11201803239PA/en
Publication of WO2017067098A1 publication Critical patent/WO2017067098A1/zh
Priority to IL258783A priority patent/IL258783A/en
Priority to US15/956,618 priority patent/US10793510B2/en
Priority to ZA2018/02651A priority patent/ZA201802651B/en
Priority to CONC2018/0004288A priority patent/CO2018004288A2/es

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/86—Separation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to the technical field of organic synthesis, in particular to a method for preparing an aryl substituted p-phenylenediamine.
  • the aryl-substituted p-phenylenediamines are an important class of p-phenylenediamine derivatives, which are formed by replacing the N-amino hydrogen atom and the N'-amino hydrogen atom in p-phenylenediamine with an aryl group.
  • a compound or mixture (referred to as a mixture because it is possible to contain different kinds of compounds, and these compounds have the same core structure, indicating that the substituted aryl group is different).
  • the rubber antioxidant 3100 is an important one of aryl-substituted p-phenylenediamines.
  • Rubber antioxidant 3100 chemical name N, N'-dimethylphenyl-p-phenylenediamine or diaryl-p-phenylenediamine, which contains three different structural compounds, the structural formulas of which are as follows:
  • Rubber anti-aging agent 3100 is a typical after-effect p-phenylenediamine rubber anti-aging agent, which can effectively compensate for the short-term anti-aging effect of the currently dominant p-phenylenediamine anti-aging agent 4020 and 4010NA, and is suitable for the shortcomings.
  • Synthetic rubber such as natural rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, and neoprene. It is an anti-ozone protection effect and is a variety of high-efficiency anti-aging agents for tires.
  • the main production process of the product uses hydroquinone, aniline and o-toluidine as reaction raw materials, and reacts under normal pressure or autoclave under the action of a Lewis acid (for example, anhydrous ferric chloride) catalyst to obtain a product.
  • a Lewis acid for example, anhydrous ferric chloride
  • toluene is used as a water-laden solvent to continuously carry out the water formed by the reaction out of the reaction system to promote the reaction in the direction of product formation.
  • the reaction temperature reaches about 250 °C, and the amount of water taken out is used as a sign to judge the end of the reaction.
  • the reaction is cooled by adding a saturated aqueous solution of sodium carbonate, and then the mixture is heated and vacuum-reduced to remove low-boiling substances, and then the inorganic salt is removed by hot filtration.
  • the organic phase is then washed several times to give the product.
  • the advantage of the process is that the whole process is relatively simple, and the disadvantage is that the reaction raw material used is expensive, the supply channel is not rich, and the price fluctuates greatly.
  • the Lewis acid is quenched with the alkali solution, and the product is washed away.
  • the catalyst residual metal ions will generate a large amount of waste water, and the reaction is high in temperature and corrosive to equipment under acidic medium.
  • the main object of the present invention is to provide a method for preparing an aryl-substituted p-phenylenediamine material, which has the advantages of high cost, poor environmental friendliness and high corrosiveness in synthesizing aryl substituted p-phenylenediamines in the prior art. And the problem of harsh reaction conditions.
  • R" is phenyl or o-methylphenyl, and R' is the same as or different from R";
  • the preparation method comprises the following steps: the raw material A and the raw material B react under the action of a hydrogen acceptor and a catalyst to form an aryl-substituted p-phenylenediamine; the raw material A has the structure represented by the formula I, and the raw material B is cyclohexanone and/or adjacent Methylcyclohexanone, a hydrogen acceptor that is a hydrogen acceptor capable of being converted into a raw material B by hydrogen,
  • the molar ratio between the raw material A and the raw material B is from 20:1 to 5:1, and the molar ratio between the raw material A and the hydrogen acceptor is from 1:10 to 1:2.5.
  • the hydrogen acceptor is phenol and/or o-methylphenol.
  • the aryl-substituted p-phenylenediamine is rubber anti-aging agent 3100, and the preparation method comprises the following steps: using N-phenyl-p-phenylenediamine as raw material A, cyclohexanone and/or o-methylcyclohexanone as Starting material B, phenol as a hydrogen acceptor, reacting under the action of a catalyst to obtain a first component; using N-phenyl p-phenylenediamine as a raw material A, cyclohexanone and/or o-methylcyclohexanone as a raw material B , o-methylphenol as a hydrogen acceptor, reacted under the action of a catalyst, or N-o-methylphenyl-p-phenylenediamine as a raw material A, cyclohexanone and/or o-methylcyclohexanone as a raw material B , phenol as a hydrogen acceptor, reacted under the action of a catalyst to
  • the aryl-substituted p-phenylenediamine is a rubber antioxidant 3100
  • the preparation method comprises the following steps: using a mixture of N-phenyl-p-phenylenediamine and N-o-methylphenyl-p-phenylenediamine as a raw material A Using cyclohexanone and/or o-methylcyclohexanone as the raw material B, a mixture of phenol and o-methylphenol is used as a hydrogen acceptor, and reacted under the action of a catalyst to obtain a rubber antioxidant 3100.
  • the catalyst is a noble metal supported catalyst, preferably a Pd-C and/or Pt-C noble metal supported catalyst.
  • the amount of the catalyst used is 0.1 to 2% by weight based on the amount of the raw material A.
  • the raw material A and the raw material B are reacted at a temperature of 220 to 280 ° C for a reaction time of 6 to 8 hours.
  • the preparation method further comprises: after the reaction of the raw material A and the raw material B under the action of the hydrogen acceptor and the catalyst, the reaction liquid obtained by the reaction is filtered to obtain a filtrate, and the filtrate is subjected to distillation under reduced pressure to obtain an aryl group. Substituting p-phenylenediamines.
  • the raw material A having the structure of the formula I and the cyclohexanone and/or o-methylcyclohexanone are reacted to form an aryl-substituted p-phenylenediamine.
  • both cyclohexanone and o-methylcyclohexanone can undergo a dehydrogenation reaction under the action of a catalyst, and at the same time replace a hydrogen atom on the amino group at the N' position of the starting material A to form R" as a phenyl group or an o-methyl group.
  • the aryl group of the phenyl group is substituted with the p-phenylenediamine.
  • the hydrogen acceptor in the reaction system continuously receives hydrogen desorbed by cyclohexanone and/or o-methylcyclohexanone under the action of the catalyst, and further forms the raw material B.
  • the cyclohexanone and/or o-methylcyclohexanone required for the reaction are supplied.
  • the amount of the raw material B may be added in a small amount, which is mainly used as a raw material for the reaction, and is to be reacted with the raw material A under the action of a catalyst.
  • the reaction When the reaction is carried out, hydrogen is supplied to the hydrogen acceptor, and a large amount of aryl-substituted p-phenylenediamine is formed during the continuous hydrogenation of the hydrogen acceptor and the continuous dehydrogenation of the formed compound B.
  • the preparation method has the advantages that the raw materials are cheap and easy to obtain, and the post-treatment of the reaction does not need to use a large amount of water. At the same time, the reaction conditions are mild and the reaction equipment is not corroded. Therefore, the preparation method is environmentally friendly, less polluted and can obtain better economic benefits.
  • the existing aryl substituted p-phenylenediamine synthesis processes have the problems of high cost, poor environmental friendliness, strong corrosiveness and complicated process.
  • the inventors of the present invention have provided a process for preparing an aryl-substituted p-phenylenediamine, and the structural formula of the aryl-substituted p-phenylenediamine is as follows:
  • R" is phenyl or o-methylphenyl, and R' is the same as or different from R";
  • the preparation method comprises the following steps: reacting the raw material A and the raw material B under the action of a hydrogen acceptor and a catalyst to form an aryl-substituted p-phenylenediamine;
  • the raw material A has the structure represented by the formula I
  • the raw material B is cyclohexanone and/or Or o-methylcyclohexanone, the hydrogen acceptor being a hydrogen acceptor capable of being converted into a starting material B by hydrogen;
  • the above preparation method provided by the present invention reacts with the starting material A having the structure of the formula I and the starting material B (cyclohexanone and/or o-methylcyclohexanone) to form an aryl-substituted p-phenylenediamine.
  • both cyclohexanone and o-methylcyclohexanone can undergo a dehydrogenation reaction under the action of a catalyst, and at the same time replace a hydrogen atom on the amino group at the N' position of the starting material A to form R" as a phenyl group or an o-methyl group.
  • the aryl group of the phenyl group is substituted with the p-phenylenediamine.
  • the hydrogen acceptor in the reaction system continuously receives hydrogen desorbed by cyclohexanone and/or o-methylcyclohexanone under the action of the catalyst, and further forms the raw material B.
  • the cyclohexanone and/or o-methylcyclohexanone required for the reaction are supplied.
  • the amount of the raw material B may be added in a small amount, which is mainly used as a raw material for the reaction, and is to be reacted with the raw material A under the action of a catalyst.
  • the raw materials are cheap and easy to obtain, and the post-treatment of the reaction does not require the use of a large amount of water.
  • the reaction conditions are mild and do not corrode the reaction equipment. Therefore, the preparation method is environmentally friendly, has less pollution, and can obtain better economic benefits.
  • the above-mentioned aryl-substituted p-phenylenediamines of the present invention may be a compound or a mixture.
  • the starting material A is a single structure compound and the raw material B is cyclohexanone or o-methylcyclohexanone
  • the prepared aryl-substituted p-phenylenediamine is also a single structure compound.
  • the selected raw material A and/or raw material B itself is a mixture of a plurality of compounds, the reaction can still be carried out, and the obtained aryl-substituted p-phenylenediamines have two or more kinds of the same parent core structure.
  • a mixture of different substituted aryl compounds are Specifically, those skilled in the art can choose to mix different raw materials to obtain different aryl substituted p-phenylenediamines, and details are not described herein again.
  • the amount of the raw material B can be added little, and when it is reacted with the raw material A under the action of the catalyst, the hydrogen required for the hydrogen acceptor can be supplied to the hydrogen acceptor.
  • a large amount of aryl substituted p-phenylenediamines are formed during the continuous dehydrogenation of hydrogen and the resulting compound B.
  • the molar ratio between the raw material A and the raw material B is from 20:1 to 5:1, and the molar ratio between the raw material A and the hydrogen acceptor is from 1:10 to 1:2.5.
  • the reaction rate can be more effectively ensured, and sufficient hydrogen can be maintained in the reaction system to continuously convert the hydrogen acceptor into the raw material B, thereby reacting with the raw material A. .
  • the hydrogen acceptor is phenol and/or o-methylphenol.
  • Phenol and o-methylphenol have higher conversion efficiency when converted to cyclohexanone and o-methylcyclohexanone by hydrogen.
  • the cost of these two hydrogen acceptors is lower, and the high dose in more practical industrial production. use.
  • the aryl-substituted p-phenylenediamine is rubber anti-aging agent 3100, and the preparation method comprises the following steps: using N-phenyl-p-phenylenediamine as starting material A, cyclohexanone and/or adjacent Methylcyclohexanone is used as the raw material B, and phenol is used as a hydrogen acceptor to react under the action of a catalyst to obtain a first component (as described above, the amount of the raw material B added may be small, and the raw material A and the raw material A are in the catalyst.
  • the hydrogen can be supplied to the hydrogen acceptor, and a large amount of aryl-substituted p-phenylenediamine is formed during the continuous hydrogen dehydrogenation of the hydrogen acceptor and the continuous dehydrogenation of the formed compound B.
  • N-phenyl-p-phenylene The amine is used as the starting material A, cyclohexanone and/or o-methylcyclohexanone as the starting material B, o-methylphenol as the hydrogen acceptor, reacted under the action of a catalyst, or N-o-methylphenyl-p-phenylene Amine as starting material A, cyclohexanone and / or o-methylcyclohexanone as starting material B, phenol as hydrogen
  • the reaction is carried out under the action of a catalyst to obtain a second component (same reason, although cyclohexanone and/or o-methylcyclohexanone are used as the starting material B in the process, the final product is mainly due to the small amount of addition.
  • the component is still the second component); N-o-methylphenyl-p-phenylenediamine is used as the starting material A, cyclohexanone and/or o-methylcyclohexanone as the starting material B, and o-methylphenol as the hydrogen acceptor, The reaction is carried out under the action of a catalyst to obtain a third component (Similarly, although cyclohexanone and/or o-methylcyclohexanone are used as the raw material B, the main component of the product formed in this step is still the third component); And mixing the first component, the second component, and the third component to obtain a rubber antioxidant 3100.
  • the preparation steps of the three components in the preparation method are not in order. It is well known to those skilled in the art that the rubber antioxidant 3100 itself is a mixture of three aryl-substituted p-phenylenediamine compounds, and the preparation steps of the above three components actually use a single raw material A, a raw material B and a hydrogen acceptor, respectively. These three components were prepared, and finally the three components were mixed to obtain a rubber antioxidant 3100. In the process of mixing, those skilled in the art can set the respective amounts of the three components according to the predetermined requirements of the rubber antioxidant 3100.
  • the rubber antioxidant 3100 can also be prepared in a one-step process, the preparation method comprising the steps of: N-phenyl-p-phenylenediamine and N-o-methylphenyl pair A mixture of phenylenediamine is used as the raw material A, cyclohexanone and/or o-methylcyclohexanone are used as the raw material B, and a mixture of phenol and o-methylphenol is used as a hydrogen acceptor, and reacted under the action of a catalyst to obtain a rubber anti-aging agent. Agent 3100.
  • the one-step preparation of the rubber antioxidant 3100 can further simplify the reaction process and reduce the reaction cost.
  • the catalyst to be used may have a function of dehydrogenation and hydrogenation.
  • the catalyst is a noble metal supported catalyst, preferably a Pd-C and/or Pt-C noble metal supported catalyst. These catalysts have high catalytic activity and can make the reaction conditions milder. Additionally, one skilled in the art can adjust the specific amount of catalyst. In a preferred embodiment, the catalyst is used in an amount of from 0.1 to 2% by weight based on the weight of the starting material A.
  • the synthesis conditions of the aryl-substituted p-phenylenediamines are more moderate due to the unique reaction principle and route of the present invention.
  • the raw materials A and B are reacted under the action of a hydrogen acceptor and a catalyst, and the reaction liquid obtained by the reaction is filtered to obtain a filtrate, and the filtrate is subjected to distillation under reduced pressure to obtain an aryl-substituted p-phenylene. Amines.
  • the post-treatment process is relatively simple due to the unique reaction route.
  • the raw material A and the raw material B are reacted under a nitrogen atmosphere.
  • N,N'-diphenyl-p-phenylenediamine was prepared using the same starting materials and process conditions as in Example 1, except that the amount of each raw material was different (in which N-phenyl-p-phenylenediamine was maintained). The weight does not change).
  • the specific dosage relationship and product conditions are as follows:
  • the unreacted o-cresol and cyclohexanone were removed by distillation to obtain 54.2 g of a distillation residue, and N-phenyl-N'-tolyl-p-phenylenediamine and N,N'-bis(tolyl) pair were determined by sampling.
  • the content of phenylenediamine was 47.3% and 47.2%, respectively, and the calculated yields were 93.6% and 88.8%, respectively.
  • the content of '-tolyl-p-phenylenediamine and N,N'-bis(tolyl)-p-phenylenediamine is 42.2%, 37.5% and 14.1%, respectively, and the product can be directly used as a rubber antioxidant 3100.
  • the catalyst was discharged, the catalyst was recovered by filtration, and the unreacted phenol and cyclohexanone were removed by distillation under reduced pressure to obtain 54.5 g of a distillation residue, and N,N'-diphenyl-p-phenylenediamine and N-phenyl-
  • the contents of N'-tolyl-p-phenylenediamine and N,N'-bis(tolyl)-p-phenylenediamine are 22.6%, 43.7% and 24.2%, respectively, and the product can be directly used as a rubber antioxidant 3100.
  • the preparation method In the preparation method, the raw materials are cheap and easy to obtain, and the post-treatment of the reaction does not require the use of a large amount of water. At the same time, the reaction conditions are mild and do not corrode the reaction equipment. Therefore, the preparation method is environmentally friendly, has less pollution, and can obtain better economic benefits. More specifically, by controlling the ratio of each raw material and the reaction process conditions, the product content and yield of the product can be further improved.

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Abstract

提供了芳基取代对苯二胺类物质的制备方法。该芳基取代对苯二胺类物质的结构式如式（I'）：其中，R"为苯基或邻甲基苯基，R'与R"相同或不同；制备方法包括：原料A和原料B在氢受体和催化剂的作用下反应，形成芳基取代对苯二胺类物质；原料A的结构式为式（I），原料B为环己酮和/或邻甲基环己酮，氢受体为能够受氢转化为原料B的氢受体。该制备方法，原料便宜易获取，反应的后处理无需使用大量的水。同时，反应条件较温和，且不会腐蚀反应设备。因此该制备方法环保、污染少且能获得好的经济效益。

Description

芳基取代对苯二胺类物质的制备方法 技术领域
本发明涉及有机合成技术领域，具体而言，涉及一种芳基取代对苯二胺类物质的制备方法。
背景技术
芳基取代对苯二胺类物质是对苯二胺衍生物中重要的一类物质，其是对苯二胺中的N-氨基氢原子和N’-氨基氢原子经芳基取代后形成的化合物或混合物(称其混合物是由于其有可能包含不同种化合物，且这些化合物具有相同的母核结构，指示取代的芳基不同而已)。其中，橡胶防老剂3100是芳基取代对苯二胺类物质中重要的一种。
橡胶防老剂3100，化学名称N,N’-二甲苯基对苯二胺或二芳基对苯二胺，其包含了三种不同结构的化合物，这三种化合物的结构式分别如下：
Figure PCTCN2016070614-appb-000001
橡胶防老剂3100是典型的后效型对苯二胺类橡胶防老剂，可以有效地弥补目前主导的对苯二胺类防老剂4020和4010NA早期抗老化效果好而后期略差的缺点，适应于天然橡胶、顺丁橡胶、丁苯橡胶、丁腈橡胶、氯丁橡胶等合成橡胶。属于抗臭氧防护效果极佳，是轮胎用高效防老剂的品种。
目前产品的主要生产工艺以对苯二酚、苯胺、邻甲苯胺为反应原料，在路易斯酸(例如无水三氯化铁)催化剂作用下在常压或高压釜中反应得到产物。过程中以甲苯为带水溶剂不断将反应生成的水带出反应体系以促进反应向生成产物的方向进行。反应温度达到250℃左右，以带出的水量作为衡量反应结束的标志，反应结束后降温加入饱和碳酸钠水溶液淬灭反应，然后再升温减压蒸馏除去低沸物，然后趁热过滤除去无机盐后再对有机相多次洗涤后得到产物。该工艺优点是：整个工艺流程比较简单，缺点是：所用的反应原料对苯二酚价格昂贵、供应渠道不丰富且价格波动较大，反应后要用碱液淬灭路易斯酸、洗去产品中的催化剂残留金属离子都会产生大量的废水，反应中高温且在酸性介质下对设备的腐蚀性强。
类似于橡胶防老剂3100，目前芳基取代对苯二胺类物质的合成工艺中均存在成本高、环保性差、腐蚀性强及反应条件苛刻的问题。因此，有必要提供一种用于制备芳基取代对苯二胺类物质的，具有成本低、环保性好、反应条件温和且对反应设备腐蚀性较弱等特性的绿色制备工艺。
发明内容
本发明的主要目的在于提供一种芳基取代对苯二胺类物质的制备方法，以解决现有技术中合成芳基取代对苯二胺类物质时存在的成本高、环保性差、腐蚀性强及反应条件苛刻的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种芳基取代对苯二胺类物质的制备方法，该芳基取代对苯二胺类物质的结构式如下：
Figure PCTCN2016070614-appb-000002
其中，R”为苯基或邻甲基苯基，R’与R”相同或不同；
制备方法包括：原料A和原料B在氢受体和催化剂的作用下反应，形成芳基取代对苯二胺类物质；原料A具有式I所示结构，原料B为环己酮和/或邻甲基环己酮，氢受体为能够受氢转化为原料B的氢受体，
Figure PCTCN2016070614-appb-000003
进一步地，原料A和原料B之间的摩尔比为20:1～5:1，原料A和氢受体之间的摩尔比为1:10～1:2.5。
进一步地，氢受体为苯酚和/或邻甲基苯酚。
进一步地，芳基取代对苯二胺类物质为橡胶防老剂3100，制备方法包括以下步骤：将N-苯基对苯二胺作为原料A，环己酮和/或邻甲基环己酮作为原料B，苯酚作为氢受体，在催化剂的作用下反应，得到第一组份；将N-苯基对苯二胺作为原料A，环己酮和/或邻甲基环己酮作为原料B，邻甲基苯酚作为氢受体，在催化剂的作用下反应，或者，将N-邻甲基苯基对苯二胺作为原料A，环己酮和/或邻甲基环己酮作为原料B，苯酚作为氢受体，在催化剂的作用下反应，得到第二组份；将N-邻甲基苯基对苯二胺作为原料A，环己酮和/或邻甲基环己酮作为原料B，邻甲基苯酚作为氢受体，在催化剂的作用下反应，得到第三组份；以及混合第一组份、第二组份和第三组份，得到橡胶防老剂3100。
进一步地，芳基取代对苯二胺类物质为橡胶防老剂3100，制备方法包括以下步骤：将N-苯基对苯二胺和N-邻甲基苯基对苯二胺的混合物作为原料A，将环己酮和/或邻甲基环己酮作为原料B，将苯酚和邻甲基苯酚的混合物作为氢受体，在催化剂的作用下反应，得到橡胶防老剂3100。
进一步地，催化剂为贵金属负载型催化剂，优选为Pd-C和/或Pt-C贵金属负载型催化剂。
进一步地，催化剂的用量为原料A重量的0.1～2％。
进一步地，原料A和原料B在220～280℃温度条件下进行反应，反应时间为6～8h。
进一步地，制备方法在原料A和原料B在氢受体和催化剂的作用下反应完毕后还包括：将反应得到的反应液进行过滤，得到滤液，并将滤液进行减压蒸馏后，得到芳基取代对苯二胺类物质。
进一步地，原料A和原料B在氮气气氛下进行反应。
应用本发明的技术方案，以具有式I结构的原料A和环己酮和/或邻甲基环己酮进行反应生成芳基取代对苯二胺类物质。具体地，环己酮和邻甲基环己酮均能够在催化剂的作用下发生脱氢反应，同时取代原料A中N’位置氨基上的一个氢原子，形成R”为苯基或邻甲基苯基的芳基取代对苯二胺类物质。同时，反应体系中的氢受体在催化剂的作用下不断接受环己酮和/或邻甲基环己酮脱出的氢，进一步形成原料B以供应反应所需要的环己酮和/或邻甲基环己酮。该制备方法中，原料B的加入量可以很少，其主要是作为反应的引子原料，待与原料A在催化剂的作用下进行反应时，便能向氢受体提供所需要的氢，在氢受体不断的受氢和所生成的化合物B不断的脱氢过程中形成大量的芳基取代对苯二胺类物质。该制备方法，原料便宜易获取，反应的后处理无需使用大量的水。同时，反应条件较温和，且不会腐蚀反应设备。因此该制备方法环保、污染少且能获得更好的经济效益。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术部分所描述的，现有的芳基取代对苯二胺类物质的合成工艺中均存在成本高、环保性差、腐蚀性强及工艺复杂的问题。为了解决这一问题，本发明发明人提供了一种芳基取代对苯二胺类物质的制备方法，该芳基取代对苯二胺类物质的结构式如下：
Figure PCTCN2016070614-appb-000004
其中，R”为苯基或邻甲基苯基，R’与R”相同或不同；
该制备方法包括：以原料A和原料B在氢受体和催化剂的作用下反应，形成芳基取代对苯二胺类物质；原料A具有式I所示结构，原料B为环己酮和/或邻甲基环己酮，氢受体为能够受氢转化为原料B的氢受体；
Figure PCTCN2016070614-appb-000005
本发明提供的上述制备方法以具有式I结构的原料A和原料B(环己酮和/或邻甲基环己酮)进行反应生成芳基取代对苯二胺类物质。具体地，环己酮和邻甲基环己酮均能够在催化剂的作用下发生脱氢反应，同时取代原料A中N’位置氨基上的一个氢原子，形成R”为苯基或邻甲基苯基的芳基取代对苯二胺类物质。同时，反应体系中的氢受体在催化剂的作用下不断接受环己酮和/或邻甲基环己酮脱出的氢，进一步形成原料B以供应反应所需要的环己酮和/或邻甲基环己酮。该制备方法中，原料B的加入量可以很少，其主要是作为反应的引子原料，待与原料A在催化剂的作用下进行反应时，便能向氢受体提供所需要的氢，在氢受体不断的受氢和所生成的原料B不断的脱氢过程中形成大量的芳基取代对苯二胺类物质。
本发明提供的该制备方法，原料便宜易获取，反应的后处理无需使用大量的水。同时，反应条件较温和，且不会腐蚀反应设备。因此该制备方法环保、污染少且能获得更好的经济效益。
需要说明的是，本发明上述的芳基取代对苯二胺类物质可以是化合物，也可以是混合物。当选用的原料A为单一结构的化合物、原料B为环己酮或邻甲基环己酮时，制备得到的芳基取代对苯二胺类物质亦为单一结构的化合物。而当选用的原料A和/或原料B本身是多种化合物的混合物时，该反应仍旧能够进行，且得到的芳基取代对苯二胺类物质为两种或两种以上具有相同母核结构不同取代芳基的化合物所形成的混合物。具体地，本领域技术人员能够选择搭配不同的原料以获得不同的芳基取代对苯二胺类物质，在此不再赘述。
如前文所述，该制备方法中，原料B的加入量可以很少，待其与原料A在催化剂的作用下进行反应时，便能向氢受体提供所需要的氢，在氢受体不断的受氢和所生成的化合物B不断的脱氢过程中形成大量的芳基取代对苯二胺类物质。在一种优选的实施方式中，原料A和原料B之间的摩尔比为20:1～5:1，原料A和氢受体之间的摩尔比为1:10～1:2.5。将各原料之间的用量关系控制在上述范围内，能够更有效地保证反应的速率，使反应体系中保持充分的氢，以使氢受体不断地转化为原料B，进而与原料A进行反应。同时，能够进一步节约成本较高的原料B，是制备方法具有更好的经济性。
在一种优选的实施方式中，氢受体为苯酚和/或邻甲基苯酚。苯酚和邻甲基苯酚在受氢转化为环己酮和邻甲基环己酮时具有更高的转化效率，同时，这两种氢受体的成本较低，更实用工业化生产中的大剂量使用。
只要采用本发明提供的上述制备方法，就能够制得特定结构的芳基取代对苯二胺类物质。在一种优选的实施方式中，芳基取代对苯二胺类物质为橡胶防老剂3100，制备方法包括以下步骤：将N-苯基对苯二胺作为原料A，环己酮和/或邻甲基环己酮作为原料B，苯酚作为氢受体，在催化剂的作用下反应，得到第一组份(如前文所述，原料B的加入量可以很少，待其与原料A在催化剂的作用下进行反应时，便能向氢受体提供所需要的氢，在氢受体不断的受氢和所生成的化合物B不断的脱氢过程中形成大量的芳基取代对苯二胺类物质。该过程中尽管以环己酮和/或邻甲基环己酮作为原料B，但由于加入量较小，最终的产物主要成分仍旧是第一组分)；将N-苯基对苯二胺作为原料A，环己酮和/或邻甲基环己酮作为原料B，邻甲基苯酚作为氢受体，在催化剂的作用下反应，或者，将N-邻甲基苯基对苯二胺作为原料A，环己酮和/或邻甲基环己酮作为原料B，苯酚作为氢受体，在催化剂的作用下反应，得到第二组份(同理，该过程中尽管以环己酮和/或邻甲基环己酮作为原料B，但由于加入量较小，最终的产物主要成分仍旧是第二组分)；将N-邻甲基苯基对苯二胺作为原料A，环己酮和/或邻甲基环己酮作为原料B，邻甲基苯酚作为氢受体，在催化剂的作用下反应，得到第三组份(同理，尽管以环己酮和/或邻甲基环己酮作为原料B，该步骤生成的产物主要组分仍旧为第三组分)；以及混合第一组份、第二组份和第三组份，得到橡胶防老剂3100。
该制备方法中三种组份的制备步骤并不分先后顺序。本领域技术人员公知，橡胶防老剂3100本身是三种芳基取代对苯二胺类化合物的混合物，上述三种组份的制备步骤中其实是分别采用单一的原料A、原料B和氢受体制备了这三种成分，最后将这三种成分混合即可得到橡胶防老剂3100。在混合的过程中，本领域技术人员只要按照橡胶防老剂3100的既定要求设定三种成分各自的用量即可。
当然，除了上述分步骤制备橡胶防老剂3100之外，还可以采用一步法制备橡胶防老剂3100，该制备方法包括以下步骤：将N-苯基对苯二胺和N-邻甲基苯基对苯二胺的混合物作为原料A，将环己酮和/或邻甲基环己酮作为原料B，将苯酚和邻甲基苯酚的混合物作为氢受体，在催化剂的作用下反应，得到橡胶防老剂3100。这种一步法制备橡胶防老剂3100能够进一步简化反应工序，降低反应成本。
本发明提供的上述制备方法中，采用的催化剂只要具有脱氢和加氢的功能即可。在一种优选的实施方式中，催化剂为贵金属负载型催化剂，优选为Pd-C和/或Pt-C贵金属负载型催化剂。这些催化剂具有较高的催化活性，能够使反应条件更加温和。此外，本领域技术人员可以调整催化剂的具体用量。在一种优选的实施方式中，上述催化剂的用量为原料A重量的0.1～2％。
如前文所述，正因为本发明中独特的反应原理和路线，使得芳基取代对苯二胺类物质的合成条件更加温和。在一种优选的实施方式中，原料A和原料B在220～280℃温度条件下进行反应，反应时间为6～8h。将反应体系的温度和时间控制在上述范围内，除了能够提高反应＝转化率和速率外，还有利于降低反应的副反应利率，是产物具有更高的纯度。
更优选地，待原料A和原料B在氢受体和催化剂的作用下反应完毕，将反应得到的反应液进行过滤，得到滤液，并将滤液进行减压蒸馏后，得到芳基取代对苯二胺类物质。该反应中由于独特的反应路线，后期的后处理过程较为简单。进一步优选地，原料A和原料B在氮气气氛下进行反应。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
向500mL高压釜中加入36.8g(0.2mol)N-苯基对苯二胺、94.1g(1mol)苯酚、2.0g(0.02mol)环己酮和1.3g干Pd/C(含5wt％Pd)催化剂；开启搅拌，氮气置换3次后加热升温至220℃，保温反应6h后降至室温出料，过滤回收催化剂，滤液减压蒸馏脱除未反应的苯酚和环己酮，得到蒸馏残液51.7g，取样测得N,N′-二苯基对苯二胺含量为94.1％，经计算收率为93.6％。
实施例2至5
采用与实施例1中相同的原料和工艺条件制备N,N′-二苯基对苯二胺，不同之处在于各原料之间的用量关系不同(其中保持N-苯基对苯二胺的重量不变)。具体的用量关系和产物情况如下：
Figure PCTCN2016070614-appb-000006
实施例6
向500mL高压釜中加入36.8g(0.2mol)N-苯基对苯二胺、108.1g(1mol)邻甲苯酚、2.0g(0.02mol)环己酮和1.3g干Pt/C(含5％Pt)催化剂；开启搅拌，氮气置换3次后加热升温至250℃，保温反应6h后降至室温出料，过滤回收催化剂，滤液减压蒸馏脱除未反应的邻甲苯酚和环己酮，得到蒸馏残液49.7g，取样测得N-苯基-N′-甲苯基对苯二胺含量为68％，经计算收率为90.8％。
实施例7
向500mL高压釜中加入39.6g(0.2mol)N-甲苯基对苯二胺、94.1g(1mol)苯酚、2.0g(0.02mol)环己酮和1.3g干Pd/C(含5％Pd)催化剂；开启搅拌，氮气置换3次后加热升温至250℃，保 温反应6h后降至室温出料，过滤回收催化剂，滤液减压蒸馏脱除未反应的苯酚和环己酮，得到蒸馏残液53.7g，取样测得N-苯基-N′-甲苯基对苯二胺含量为93.8％，经计算收率为91.9％。
实施例8
向500mL高压釜中加入39.6g(0.2mol)N-甲苯基对苯二胺、108.1g(1mol)邻甲苯酚、2.0g(0.02mol)环己酮和1.3g干Pd/C(含5％Pd)催化剂；开启搅拌，氮气置换3次后加热升温至270℃，保温反应6h后降至室温出料，过滤回收催化剂，滤液减压蒸馏脱除未反应的邻甲苯酚和环己酮，得到蒸馏残液56.6g，取样测得N,N′-二(甲苯基)对苯二胺含量为93.4％，经计算收率为91.8％。
实施例9
向500mL高压釜中加入18.4g(0.1mol)N-苯基对苯二胺、19.8g(0.1mol)N-甲苯基对苯二胺、94.1g(1mol)苯酚、2.0g(0.02mol)环己酮和1.3g干Pd/C(含5％Pd)催化剂；开启搅拌，氮气置换3次后加热升温至250℃，保温反应6h后降至室温出料，过滤回收催化剂，滤液减压蒸馏脱除未反应的苯酚和环己酮，得到蒸馏残液52g，取样测得N,N′-二苯基对苯二胺和N-苯基-N′-甲苯基对苯二胺的含量分别为47.2％和46.8％，经计算收率分别为94.4％和88.8％。
实施例10
向500mL高压釜中加入18.4g(0.1mol)N-苯基对苯二胺、19.8g(0.1mol)N-甲苯基对苯二胺、108.1g(1mol)邻甲苯酚、2.0g(0.02mol)环己酮和1.3g干Pd/C(含5％Pd)催化剂；开启搅拌，氮气置换3次后加热升温至270℃，保温反应8h后降至室温出料，过滤回收催化剂，滤液减压蒸馏脱除未反应的邻甲苯酚和环己酮，得到蒸馏残液54.2g，取样测得N-苯基-N′-甲苯基对苯二胺和N,N′-二(甲苯基)对苯二胺的含量分别为47.3％和47.2％，经计算收率分别为93.6％和88.8％。
实施例11
向500mL高压釜中加入18.4g(0.1mol)N-苯基对苯二胺、19.8g(0.1mol)N-甲苯基对苯二胺、47.1g(0.5mol)苯酚、54.1g(0.5mol)邻甲苯酚、2.0g(0.02mol)环己酮和1.3g干Pd/C(含5％Pd)催化剂；开启搅拌，氮气置换3次后加热升温至270℃，保温反应8h后降至室温出料，过滤回收催化剂，滤液减压蒸馏脱除未反应的酚和环己酮，得到蒸馏残液53.4g，取样测得N,N′-二苯基对苯二胺、N-苯基-N′-甲苯基对苯二胺和N,N′-二(甲苯基)对苯二胺的含量依次为42.2％、37.5％和14.1％，该产品可以直接作为橡胶防老剂3100。
实施例12
向500mL高压釜中加入27.6g(0.15mol)N-苯基对苯二胺、9.9g(0.05mol)N-甲苯基对苯二胺、23.5(0.25mol)苯酚、81.1g(0.75mol)邻甲苯酚、2.0g(0.02mol)环己酮和1.3g干Pd/C(含5％Pd)催化剂；开启搅拌，氮气置换3次后加热升温至280℃，保温反应8h后降至室温 出料，过滤回收催化剂，滤液减压蒸馏脱除未反应的酚和环己酮，得到蒸馏残液54.5g，取样测得N,N′-二苯基对苯二胺、N-苯基-N′-甲苯基对苯二胺和N,N′-二(甲苯基)对苯二胺的含量依次为22.6％、43.7％和24.2％，该产品可以直接作为橡胶防老剂3100。
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
该制备方法，原料便宜易获取，反应的后处理无需使用大量的水。同时，反应条件较温和，且不会腐蚀反应设备。因此该制备方法环保、污染少且能获得更好的经济效益。更为特别地，通过控制各原料的比例及反应工艺条件，能够进一步提高产物的产品含量和收率。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种芳基取代对苯二胺类物质的制备方法，其特征在于，所述芳基取代对苯二胺类物质的结构式如下：
    Figure PCTCN2016070614-appb-100001
    其中，所述R”为苯基或邻甲基苯基，所述R’与所述R”相同或不同；
    所述制备方法包括：原料A和原料B在氢受体和催化剂的作用下反应，形成所述芳基取代对苯二胺类物质；所述原料A具有式I所示结构，所述原料B为环己酮和/或邻甲基环己酮，所述氢受体为能够受氢转化为所述原料B的氢受体，
    Figure PCTCN2016070614-appb-100002
  2. 根据权利要求1所述的制备方法，其特征在于，所述原料A和所述原料B之间的摩尔比为20:1～5:1，所述原料A和所述氢受体之间的摩尔比为1:10～1:2.5。
  3. 根据权利要求2所述的制备方法，其特征在于，所述氢受体为苯酚和/或邻甲基苯酚。
  4. 根据权利要求3所述的制备方法，其特征在于，所述芳基取代对苯二胺类物质为橡胶防老剂3100，所述制备方法包括以下步骤：
    将N-苯基对苯二胺作为所述原料A，环己酮和/或邻甲基环己酮作为所述原料B，苯酚作为所述氢受体，在所述催化剂的作用下反应，得到第一组份；
    将N-苯基对苯二胺作为所述原料A，环己酮和/或邻甲基环己酮作为所述原料B，邻甲基苯酚作为所述氢受体，在所述催化剂的作用下反应，或者，将N-邻甲基苯基对苯二胺作为所述原料A，环己酮和/或邻甲基环己酮作为所述原料B，苯酚作为所述氢受体，在所述催化剂的作用下反应，得到第二组份；
    将N-邻甲基苯基对苯二胺作为所述原料A，环己酮和/或邻甲基环己酮作为所述原料B，邻甲基苯酚作为所述氢受体，在所述催化剂的作用下反应，得到第三组份；以及
    混合所述第一组份、所述第二组份和所述第三组份，得到所述橡胶防老剂3100。
  5. 根据权利要求3所述的制备方法，其特征在于，所述芳基取代对苯二胺类物质为橡胶防老剂3100，所述制备方法包括以下步骤：
    将N-苯基对苯二胺和N-邻甲基苯基对苯二胺的混合物作为所述原料A，将环己酮和/或邻甲基环己酮作为所述原料B，将苯酚和邻甲基苯酚的混合物作为所述氢受体，在所述催化剂的作用下反应，得到所述橡胶防老剂3100。
  6. 根据权利要求1至5中任一项所述的制备方法，其特征在于，所述催化剂为贵金属负载型催化剂，优选为Pd-C和/或Pt-C贵金属负载型催化剂。
  7. 根据权利要求6所述的制备方法，其特征在于，所述催化剂的用量为所述原料A重量的0.1～2％。
  8. 根据权利要求1至5中任一项所述的制备方法，其特征在于，所述原料A和所述原料B在220～280℃温度条件下进行反应，反应时间为6～8h。
  9. 根据权利要求8所述的制备方法，其特征在于，所述制备方法在所述原料A和所述原料B在所述氢受体和所述催化剂的作用下反应完毕后还包括：将反应得到的反应液进行过滤，得到滤液；并将所述滤液进行减压蒸馏后，得到所述芳基取代对苯二胺类物质。
  10. 根据权利要求8所述的制备方法，其特征在于，所述原料A和所述原料B在氮气气氛下进行反应。
PCT/CN2016/070614 2015-10-21 2016-01-11 芳基取代对苯二胺类物质的制备方法 WO2017067098A1 (zh)

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