[go: up one dir, main page]

CN101717339A - Double quaternary ammonium base compound and preparation method as well as application thereof - Google Patents

Double quaternary ammonium base compound and preparation method as well as application thereof Download PDF

Info

Publication number
CN101717339A
CN101717339A CN200910250203A CN200910250203A CN101717339A CN 101717339 A CN101717339 A CN 101717339A CN 200910250203 A CN200910250203 A CN 200910250203A CN 200910250203 A CN200910250203 A CN 200910250203A CN 101717339 A CN101717339 A CN 101717339A
Authority
CN
China
Prior art keywords
bis
quaternary ammonium
reaction
hydroxide
ethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN200910250203A
Other languages
Chinese (zh)
Inventor
丁克鸿
史雪芳
程晓曦
王秋萍
顾克军
许金来
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
YANGZHOU FUYUAN CHEMICAL TECHNOLOGY Co Ltd
Jiangsu Yangnong Chemical Group Co Ltd
Original Assignee
YANGZHOU FUYUAN CHEMICAL TECHNOLOGY Co Ltd
Jiangsu Yangnong Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by YANGZHOU FUYUAN CHEMICAL TECHNOLOGY Co Ltd, Jiangsu Yangnong Chemical Group Co Ltd filed Critical YANGZHOU FUYUAN CHEMICAL TECHNOLOGY Co Ltd
Priority to CN200910250203A priority Critical patent/CN101717339A/en
Priority to PCT/CN2009/076245 priority patent/WO2011069309A1/en
Publication of CN101717339A publication Critical patent/CN101717339A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/42—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having etherified hydroxy groups and at least two amino groups bound to the carbon skeleton

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention describes a double quaternary ammonium base compound with a general expression I, wherein in the general expression, R1 and R2 are mutually independent alkyls of C1-C18; R3, R4, R5 and R6 are mutually independent alkyls of a linear chain or a branch chain of C1-C6; and R7 is an alkylene of C2-C6 or alkoxy-substituted alkylene of C2-C6. The preparation method of the double quaternary ammonium base compound comprises the following steps: firstly, synthesizing double quaternary ammonium salt, and then, substituting the quaternary ammonium salt by the precipitation method to obtain the double quaternary ammonium base. The double quaternary ammonium base of the invention has the characteristics of novel structure, convenient preparation, low cost, and the like. The compound can be used as a condensation catalyst for condensation and hydrogenation of nitrobenzene and aniline to synthesize an intermediate 4-aminodiphenylamine of a rubber antioxidant. Compared with the common single quaternary ammonium base tetramethyl ammonium hydroxide, the compound of the invention has the advantages of convenient sources of raw materials, low cost, simple and convenient preparation processes, good heat stability, and the like.

Description

Biquaternary ammonium base compound and preparation method and application thereof
Technical Field
The invention relates to a diquaternary ammonium base compound, in particular to a diquaternary ammonium base compound suitable for a condensation catalyst for preparing 4-aminodiphenylamine by an aniline nitrobenzene method and a preparation method thereof.
Background
P-aminodiphenylamine (4-aminodiphenylamine), also known as RT base, is mainly used for producing p-phenylenediamine rubber anti-aging agents 4010NA, 4020 and the like. The production of p-aminodiphenylamine by aniline nitrobenzene method is a green production process successfully developed at home and abroad in nearly ten years, i.e. nitrobenzene and aniline are condensed in the presence of alkali catalyst to produce 4-nitrodiphenylamine and 4-nitrosodiphenylamine, and then the 4-aminodiphenylamine is obtained by hydrogenation reduction in the presence of catalyst. See US5117063A, US5453541A, US5451702A of Monsanto, fleisches America (Flexsys America l.p.), US7504539A, US7183439B2, US6583320B2, US6395933B1, US5977411A, US5623088A, US5608111A, CN1735587A, CN1307556A, CN1545497A, etc., in which the catalyst and solvent can be reused, the atom utilization rate is high, and "three wastes" are less. As the condensation reaction base catalyst, tetraalkylammonium hydroxide, particularly tetramethylammonium hydroxide (TMAOH), is used.
The tetramethylammonium hydroxide is high in market price, thermal decomposition is caused due to improper control of the ratio of heating to alkaline water in the condensation and hydrogenation reaction processes, the self-prepared tetramethylammonium chloride and chloromethane are inconvenient to source, and excessive chloromethane is not easy to recover, so that the search for a catalyst for condensation of nitrobenzene and aniline which is easier to prepare has important significance in reducing the consumption of the catalyst.
Disclosure of Invention
The invention aims to provide a condensation alkali catalyst which has the advantages of convenient raw material source, low cost, simple and convenient preparation process and good thermal stability.
The excellent performance of the prior bis-quaternary ammonium hydroxide is gradually known, but the synthesis and application research of the bis-quaternary ammonium hydroxide is still in a starting stage, mainly because the synthesis research of the raw material bis-quaternary ammonium salt prepared by the bis-quaternary ammonium hydroxide is lagged, and the raw material cost and the industrial operation are not considered enough, so that the bis-quaternary ammonium salt is still in a laboratory research stage, and the industrial large-scale production is not realized. The present inventors have diligently studied and have found that bis-quaternary ammonium bases having a bis-hydrophobic group and a bis-hydrophilic group of the general formula I can achieve this object.
Figure G2009102502035D0000021
The compound is named as N, N, N, N ', N ', N ' -hexahydrocarbyl-substituted (alkoxy substituent-containing) alkylene diammonium hydroxide.
Wherein R is1And R2Independently of one another, a hydrocarbon radical from C1 to C18, preferably a hydrocarbon radical from C1 to C12, more preferably an alkyl or alkenyl radical from C1 to C4, most preferably methyl, ethyl, n-propyl, isopropyl, allyl or butyl;
R3、R4、R5and R6Independently of one another, a linear or branched hydrocarbon radical from C1 to C6, preferably from C1 to C3; more preferably a linear hydrocarbon group of C1 to C3, most preferably a methyl group, an ethyl group or a propyl group;
R7is C2-C6 alkylene or alkoxy substituted C2-C6 alkylene; C2-C4 alkylene groups or alkoxy-substituted C2-C4 alkylene groups are preferred. The alkoxy is methoxy, ethoxy, propoxy, isopropoxy, - (OCH)2CH2)nOH or- (OCH (CH)3)CH2)nAnd OH, wherein n is 1-6, preferably n is 1-2. R7Most preferred is ethylene, propylene, butylene, 2-methoxypropylene, 2-ethoxypropylene or 2-hydroxyethoxypropylene.
Table 1 lists R1And R2Is methyl, ethyl, n-propyl, isopropyl, allyl, butyl or dodecyl, R3、R4、R5And R6Is methyl, ethyl or propyl, and R7Examples of compounds which are ethylene, propylene, 2-methoxypropylene, 2-ethoxypropylene or butylene, whose preparation is described in detail in the preparation examples.
TABLE 1 examples of bis-quaternary ammonium base compounds
Serial number R1、R2 R3～R6 R7 Name of Compound
1# Methyl radical Methyl radical Ethylene radical Ethyl-alpha, beta-bis (trimethylammonium hydroxide)
2# Ethyl radical Methyl radical Ethylene radical Ethyl-alpha, beta-bis (ethyldimethylammonium hydroxide)
3# N-propyl radical Methyl radical Ethylene radical Ethyl-alpha, beta-bis (propyldimethylammonium hydroxide)
4# Isopropyl group Methyl radical Ethylene radical Ethyl-alpha, beta-bis (isopropyl dimethyl ammonium hydroxide)
5# Allyl radical Methyl radical Ethylene radical Ethyl-alpha, beta-bis (allyldimethylammonium hydroxide)
6# Dodecyl radical Methyl radical Ethylene radical Ethyl-alpha, beta-bis (dodecyl dimethyl ammonium hydroxide)
7# Methyl radical Ethyl radical Ethylene radical Ethyl-alpha, beta-bis (methyldiethylammonium hydroxide)
8# Ethyl radical Ethyl radical Ethylene radical Ethyl-alpha, beta-bis (triethylammonium hydroxide)
9# N-propyl radical Ethyl radical Ethylene radical Ethyl-alpha, beta-bis (propyldiethylammonium hydroxide)
10# Methyl radical Methyl radical Propylene radical Propyl-alpha, gamma-bis (trimethylammonium hydroxide)
11# Ethyl radical Methyl radical Propylene radical Propyl-alpha, gamma-bis (ethyldimethylammonium hydroxide)
12# N-propyl radical Methyl radical Propylene radical Propyl-alpha, gamma-bis (propyldimethylammonium hydroxide)
13# Isopropyl group Methyl radical Propylene radical Propyl-alpha, gamma-bis (isopropyl dimethyl ammonium hydroxide)
14# Allyl radical Methyl radical Propylene radical Propyl-alpha, gamma-bis (allyldimethylammonium hydroxide)
15# N-butyl Methyl radical Propylene radical Propyl-alpha, gamma-bis (butyldimethylammonium hydroxide)
16# Dodecyl radical Methyl radical Propylene radical Propyl-alpha, gamma-bis (dodecyl dimethyl ammonium hydroxide)
17# Methyl radical Ethyl radical Propylene radical Propyl-alpha, gamma-bis (methyl diethyl ammonium hydroxide)
18# Ethyl radical Ethyl radical Propylene radical Propyl-alpha, gamma-bis (triethylammonium hydroxide)
19# N-propyl radical Ethyl radical Propylene radical Propyl-alpha, gamma-bis (propyldiethylammonium hydroxide)
Serial number R1、R2 R3～R6 R7 Name of Compound
20# Methyl radical Propyl radical Propylene radical Propyl-alpha, gamma-bis (methyl dipropyl ammonium hydroxide)
21# Ethyl radical Propyl radical Propylene radical Propyl-alpha, gamma-bis (ethyl dipropyl ammonium hydroxide)
22# N-propyl radical Propyl radical Propylene radical Propyl-alpha, gamma-bis (tripropylammonium hydroxide)
23# Methyl radical Methyl radical 2-methoxypropylidene Beta-methoxypropyl-alpha, gamma-Bis (trimethyl ammonium hydroxide)
24# Ethyl radical Methyl radical 2-ethoxypropylene radical Beta-ethoxypropyl-alpha, gamma-bis (ethyldimethylammonium hydroxide)
25# Methyl radical Methyl radical Butylene group Butyl-alpha, delta-bis (trimethylammonium hydroxide)
26# Ethyl radical Methyl radical Butylene group Butyl-alpha, delta-bis (ethyldimethylammonium hydroxide)
27# N-propyl radical Methyl radical Butylene group Butyl-alpha, delta-bis (propyldimethylammonium hydroxide)
28# Isopropyl group Methyl radical Butylene group Butyl-alpha, delta-bis (isopropyl dimethyl ammonium hydroxide)
29# Allyl radical Methyl radical Butylene group Butyl-alpha, delta-bis (allyldimethylammonium hydroxide)
30# N-butyl Methyl radical Butylene group Butyl-alpha, delta-bis (butyldimethylammonium hydroxide)
31# Dodecyl radical Methyl radical Butylene group Butyl-alpha, delta-bis (dodecyl dimethyl ammonium hydroxide)
32# Methyl radical Ethyl radical Butylene group Butyl-alpha, delta-bis (methyldiethylammonium hydroxide)
33# Ethyl radical Ethyl radical Butylene group Butyl-alpha, delta-bis (triethylammonium hydroxide)
34# N-propyl radical Ethyl radical Butylene group Butyl-alpha, delta-bis (propyldiethylammonium hydroxide)
35# Allyl radical Ethyl radical Butylene group Butyl-alpha, delta-bis (allyldiethylammonium hydroxide)
Another object of the present invention is to provide a process for preparing the bis-quaternary ammonium base compound of formula I.
The preparation method of the quaternary ammonium base mainly comprises the following steps: a quaternary ammonium salt electrolysis method, an ion exchange resin method, a substitution method (classified into a calcium hydroxide method, a potassium hydroxide method, and a silver oxide method depending on the kind of anion to be substituted), and the like.
The preparation method of the bis-quaternary ammonium base shown in the formula I comprises the following steps: the double quaternary ammonium salt compound shown in the formula II is used as a raw material and is subjected to ion exchange with hydroxide or oxide of alkali metal or alkaline earth metal in the presence of a solvent to prepare the double quaternary ammonium salt compound. Generally, the diquaternary ammonium base will contain minor amounts of diquaternary ammonium salts and alkali metal or alkaline earth metal hydroxides or oxides.
Figure G2009102502035D0000041
In the formula II, R1And R2Independently of one another, a C1-C18 hydrocarbon group, preferably a C1-C12 hydrocarbon group, more preferably a C1-C4 alkyl or alkenyl group, most preferably methylAlkyl, ethyl, n-propyl, isopropyl, allyl, or butyl;
R3、R4、R5and R6Independently of one another, a linear or branched hydrocarbon radical from C1 to C6, preferably from C1 to C3; more preferably a linear hydrocarbon group of C1 to C3, most preferably a methyl group, an ethyl group or a propyl group;
R7is C2-C6 alkylene or alkoxy substituted C2-C6 alkylene; C2-C4 alkylene groups or alkoxy-substituted C2-C4 alkylene groups are preferred. The alkoxy is methoxy, ethoxy, propoxy, isopropoxy, - (OCH)2CH2)nOH or- (OCH (CH)3)CH2)nAnd OH, wherein n is 1-6, preferably n is 1-2. R7Most preferably ethylene, propylene, butylene, 2-methoxypropylene, 2-ethoxypropylene or 2-hydroxyethoxypropylene;
x-is halide, sulfate, bisulfate, carbonate, bicarbonate, oxalate, phosphate, carboxylate, alkyl-substituted sulfate, carbonate or oxalate. The halide is chloride, bromide or iodide, and the carboxylate is formate, acetate or propionate. Preferably chloride, bromide, sulphate, carbonate or oxalate. The alkyl-substituted sulfates, carbonates or oxalates here are preferably C1-C2 alkyl-substituted sulfates, carbonates or oxalates, such as methyl sulfate (CH)3SO4 -) Ethyl sulfate radical (C)2H5SO4 -) Methyl Carbonate (CH)3OCOO-) Ethylcarbonate (C)2H5OCOO-) Methyl oxalate (CH)3OOCCOO-) Ethyl oxalate (C)2H5OOCCOO-)。
The alkali metal or alkaline earth metal hydroxide used is a hydroxide of lithium, sodium, potassium, cesium, magnesium, calcium or barium, preferably sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide. The oxide of an alkali metal or alkaline earth metal is sodium oxide, potassium oxide, cesium oxide, calcium oxide or barium oxide, preferably sodium oxide, potassium oxide, calcium oxide or barium oxide.
The solvent is C1-C4 straight chain and/or branched chain alcohol, preferably one or more of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
The preparation process conditions of the bis-quaternary ammonium base are as follows: the molar ratio of the biquaternary ammonium salt to the hydroxide or oxide of the alkali metal or the alkaline earth metal is 1: 1.0-4.0, preferably 1: 1.8-2.5; the dosage of the solvent is 1-15 times of the weight of the biquaternary ammonium salt, preferably 3-10 times; the reaction temperature is 20-150 ℃, and preferably 30-100 ℃; the reaction time is 1-10 h, preferably 1.5-6 h; the reaction can be carried out under normal pressure or under increased pressure, and is preferably carried out under normal pressure.
In the preparation method of the bis-quaternary ammonium base compound, the used raw material bis-quaternary ammonium salt can be prepared by the following three methods.
The method comprises the following steps: using dihalogenated hydrocarbon and dialkyl amine as raw materials to synthesize N, N, N ', N' -tetraalkyl alkylene diamine, and then adding the N, N, N ', N' -tetraalkyl alkylene diamine with halogenated hydrocarbon to obtain biquaternary ammonium salt;
the method 2 comprises the following steps: using dihalogenated hydrocarbon and trialkylamine as raw materials to synthesize biquaternary ammonium salt;
the method 3 comprises the following steps: n, N, N ', N' -tetraalkyl alkylene diamine and dibasic acid dimethyl or ethyl ester are used as raw materials to synthesize biquaternary ammonium salt;
the dihalo-hydrocarbon as the raw material used in the above production method means: the hydrocarbon molecules may or may not contain, in addition to two halogen substitutions, halogen, hydroxyl, alkoxy, double bonds, and the substituents may not be on the same carbon atom.
In the above method 2, bis-quaternary ammonium salt can be prepared by adding hydroxy-substituted dihalo-hydrocarbon and trialkylamine, and then subjecting the resulting mixture to hydroxy etherification with dibasic acid dimethyl or ethyl ester or halogenated hydrocarbon.
In a preferred embodiment, the process for preparing the bis-quaternary ammonium salt of formula II comprises the steps of:
(1) firstly, dihalohydrocarbon reacts with dialkyl amine in the presence of solvent to generate N, N, N ', N' -tetraalkyl alkylene diamine; the molar ratio of the dihalogenated hydrocarbon to the dialkylamine is 1: 1.0-4.0, preferably 1: 1.8-2.5, the reaction temperature is 10-200 ℃, preferably 30-120 ℃, the reaction time is 2-20 h, preferably 2-12, and the reaction pressure is 0-2 MPa, preferably 0-1.0 MPa;
(2) adding halogenated hydrocarbon into the N, N, N ', N' -tetraalkyl alkylene diamine obtained by the reaction, and carrying out addition reaction in the presence of a solvent to obtain biquaternary ammonium salt; the molar ratio of the N, N, N ', N' -tetraalkylalkylene diamine to the halogenated hydrocarbon is 1: 1.0-4.0, preferably 1: 1.8-2.5, the reaction temperature is 30-200 ℃, preferably 40-150 ℃, the reaction time is 3-20 hours, preferably 4-12 hours, and the reaction pressure is 0-1.5 MPa, preferably 0-1.0 MPa;
the dihalo-hydrocarbon used is 1, 2-dichloroethane, 1, 2-dibromoethane, 1-chloro-2-bromoethane, 1, 3-dichloropropane, 1, 3-dichloro-2-propanol, 1, 3-dichloro-2-methoxypropane, 1, 4-dibromobutane, 1, 4-dichlorobutane, 1, 4-dichloro-2-butene or 1, 4-dibromo-2-butene;
the dialkylamine used is dimethylamine, diethylamine, dipropylamine or dibutylamine;
the halogenated hydrocarbon used is methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, allyl chloride, allyl bromide, butyl chloride, butyl bromide, 1-chloro-2-butene, 1-bromo-2-butene or dodecyl bromide;
the solvent is one or more of water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol, preferably one or more of water, methanol, ethanol and propanol.
In the step (1), the molar ratio of the dihalohydrocarbon to the dialkylamine is appropriate. If the proportion of the dialkylamine is too large, the dialkylamine is excessive in a reaction system, so that the operation of a subsequent process is difficult and the environment is polluted; if the proportion of dialkylamine is too small, the dihalohydrocarbon is substituted for only one halogen group or is excessive, and the purity of the obtained product is low.
In the step (1), the reaction may be carried out under normal pressure or under pressure. In order to prevent the dialkyl amine with low boiling point from escaping, the normal pressure reaction selects lower temperature and has long reaction time; the pressurized reaction can be carried out at a higher temperature and the reaction time is short. Under the condition of normal pressure reaction, directly dripping concentrated alkali aqueous solution or alcohol solution; under the condition of pressurized reaction, pumping concentrated alkali aqueous solution or alcohol solution by using a high-pressure pump; the formed dialkylamine hydrogen halide salt is liberated to the dialkylamine for continued reaction with the dihalohydrocarbon while forming a halogenated salt of an alkali or alkaline earth metal.
In another preferred embodiment, the process for preparing the bis-quaternary ammonium salt of formula II comprises the steps of:
dihalogenated hydrocarbon and trialkylamine are used as raw materials and react in the presence of a solvent to prepare biquaternary ammonium salt; the molar ratio of the dihalogenated hydrocarbon to the trialkylamine is 1: 1.0-1: 4.0, preferably 1: 1.8-1: 2.5, the reaction temperature is 10-180 ℃, preferably 30-120 ℃, the reaction time is 1-20 hours, preferably 3-12 hours, and the reaction pressure is 0-3 MPa, preferably 0-1.5 MPa;
the dihalo-hydrocarbon is 1, 2-dichloroethane, 1, 2-dibromoethane, 1-chloro-2-bromoethane, 1, 3-dichloropropane, 1, 3-dichloro-2-propanol, 1, 3-dichloro-2-methoxypropane, 1, 4-dibromobutane, 1, 4-dichlorobutane, 1, 4-dichloro-2-butene, 1, 4-dibromo-2-butene;
the trialkylamine used is trimethylamine, dodecyldimethylamine, hexadecyldimethylamine, triethylamine, dodecyldiethylamine, hexadecyldiethylamine, tripropylamine, dodecyldipropylamine, hexadecyldipropylamine or tributylamine;
the reaction solvent is one or more of water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol, preferably one or more of water, methanol, ethanol and isopropanol.
In the above reaction steps, the trialkylamine which is gaseous at normal temperature can be prepared into aqueous solution or alcoholic solution of trialkylamine for convenient use, and the trialkylamine which is liquid at normal temperature can be directly weighed and fed. The reaction can be carried out under normal pressure or under pressure, and in order to prevent the escape of the trialkylamine with low boiling point, the normal pressure reaction generally selects lower temperature and has long reaction time; the pressurized reaction can be carried out at a higher temperature, and the reaction time is shortened.
In another preferred embodiment, the process for preparing the bis-quaternary ammonium salt of formula II comprises the steps of:
reacting N, N, N ', N' -tetraalkyl alkylene diamine and dibasic acid dimethyl or ethyl ester in a solvent to prepare biquaternary ammonium salt; the molar ratio of the tetraalkylalkylene diamine to the dibasic acid dimethyl or ethyl ester is 1: 1.0-1: 4.0, preferably 1: 1.8-1: 2.5; the reaction temperature is 10-200 ℃, preferably 50-150 ℃; the reaction time is 2-20 h, preferably 3-12 h; the reaction pressure is 0-3 MPa, preferably 0.1-2.0 MPa;
the dibasic acid dimethyl or ethyl ester is dimethyl sulfate, diethyl sulfate, dimethyl carbonate, diethyl carbonate, dimethyl oxalate, diethyl oxalate, dimethyl phosphate or diethyl phosphate;
the solvent is one or more selected from water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol, preferably one or more selected from water, methanol, ethanol and isopropanol.
In the above reaction step, generally, the pressure is closely related to the selected temperature, the type and the amount of the solvent, i.e., the less the amount of the solvent, the higher the system pressure; the higher the temperature, the higher the pressure.
Further, after the crude product of the biquaternary ammonium salt compound is obtained by the three preparation methods, the following post-treatment steps can be adopted:
dissolving the crude product by using a benign solvent, dropwise adding a poor solvent until the solution is turbid, heating to dissolve, naturally cooling, filtering to obtain a product, repeating for 1-3 times to obtain white particles, and performing vacuum drying at 50-60 ℃ for 6-10 hours to obtain the target product, namely the bis-quaternary ammonium salt.
The benign solvent is polar solvent such as methanol, ethanol, acetone, acetonitrile, DMF and the like; the poor solvent is a weak polar or non-polar solvent such as n-propanol, n-butanol, ethyl acetate, n-butyl acetate, n-propyl acetate, dichloroethane, chloroform, chlorobutane, n-hexane, etc.
The double quaternary ammonium base has the characteristics of novel structure, convenient preparation, low price and the like. The compound is particularly suitable to be used as a condensation catalyst for synthesizing rubber antioxidant intermediate p-aminodiphenylamine by condensation and hydrogenation of nitrobenzene and aniline.
As a novel base catalyst for catalyzing the condensation of nitrobenzene and aniline, compared with the common mono-quaternary ammonium base tetramethyl ammonium hydroxide, the catalyst has the advantages of good stability, high selectivity of target products, high speed of subsequent hydrogenation reaction and the like. The double quaternary ammonium base catalyst has high stability, the molar ratio of water to alkali is high after the condensation reaction process is finished (the condensation reaction needs to continuously bring water to promote the nitrobenzene to be converted completely, the double quaternary ammonium base is used as the catalyst, and when the water content in the system is higher after the reaction is finished, the satisfactory nitrobenzene conversion rate can be obtained, and the water content in the later period of the reaction is less, the dehydration efficiency is lower.
In addition, in the process of using the bis-quaternary ammonium base compound as a condensation catalyst, bis-quaternary ammonium carbonate or sulfite is easily formed with carbon dioxide, sulfur dioxide and the like in air and hydrogen used in a hydrogenation process, so that the basicity is weakened and the deactivation is gradual, which is shown in that the conversion rate of nitrobenzene is reduced and the selectivity of 4-nitrodiphenylamine and/or 4-nitrosodiphenylamine is reduced. In order to solve the above problems, the catalyst with poor activity can be partially or completely extracted, and alkali metal or alkaline earth metal hydroxide and/or oxide such as lithium hydroxide, calcium hydroxide, barium hydroxide, calcium oxide or barium oxide is added, and carbonate or sulfate is removed by precipitation, so that the bis-quaternary ammonium salt is converted into bis-quaternary ammonium base to restore the catalytic activity.
Drawings
FIG. 1 shows the IR diagram of the bis-quaternary ammonium base ethyl-alpha, beta-bis (trimethylammonium hydroxide) prepared according to the present invention. Wherein, 1060.8cm-1C-N stretching vibration; 1374.5cm-1、1450.0cm-1C-H bending vibration; 3019.6cm-1C-H stretching vibration; 3100-3200 cm-1Stretching vibration of OH.
FIG. 2 shows the IR of the quaternary ammonium monobasic tetramethylammonium hydroxide as a comparative example. Wherein, 1060.8cm-1C-N stretching vibration; 1373.5cm-1、1520.0cm-1C-H bending vibration; 3019.6cm-1C-H stretching vibration; 3100-3200 cm-1Stretching vibration of OH.
FIG. 3 shows a TG/DSC of the bis-quaternary ammonium base ethyl-alpha, beta-bis (trimethylammonium hydroxide) prepared according to the present invention. Wherein the weight of the sample is 15.47mg, and the temperature is 5 ℃/min to 800 ℃.
FIG. 4 shows a TG/DSC of a quaternary ammonium monobasic tetramethylammonium hydroxide as a comparative example. Wherein the weight of the sample is 13.35mg, and the temperature is 5 ℃/min to 300 ℃.
FIG. 5 shows a DSC of the bis-quaternary ammonium base ethyl-alpha, beta-bis (trimethylammonium hydroxide) prepared according to the present invention. Wherein the weight of the sample is 19.24mg, and the temperature is 5 ℃/min to 500 ℃.
FIG. 6 shows a DSC of quaternary ammonium monobasic tetramethylammonium hydroxide as a comparative example. Wherein the weight of the sample is 13.01mg, and the temperature is 5 ℃/min to 400 ℃.
Detailed Description
The present invention is further explained below by way of examples, but the present invention is not limited to these examples. In the above description, "%" is "% by mass" unless otherwise specified.
The preparation examples of the bis-quaternary ammonium base of the invention are as follows:
example 1
Preparation of bis-quaternary ammonium base 1# ethyl-alpha, beta-bis (trimethyl ammonium hydroxide)
Synthesizing N, N, N ', N' -tetramethyl-alpha, beta-ethylenediamine by using 1, 2-dichloroethane and dimethylamine, then adding the N, N, N ', N' -tetramethyl-alpha, beta-ethylenediamine and methyl bromide to obtain ethyl-alpha, beta-bis (trimethyl ammonium bromide), and finally performing ion exchange to obtain ethyl-alpha, beta-bis (trimethyl ammonium hydroxide).
The synthesis reaction formula is as follows:
Figure G2009102502035D0000101
operation step 1: pressure reaction
Adding 100g of methanol into a 500mL four-mouth bottle, stirring, cooling to below 0 ℃, introducing dimethylamine gas until the weight of the material is increased by about 108g (2.4mol), stopping introducing the dimethylamine gas, and refrigerating for later use. Adding 99g (1mol) of 1, 2-dichloroethane into a 1L autoclave, quickly pouring the prepared dimethylamine methanol solution into the autoclave, sealing the autoclave, heating to 80 ℃, and keeping the temperature at 80-90 ℃ for 1h, wherein the pressure of the autoclave is 0.03-0.08 MPa. Then, pumping 432g of 25% sodium methoxide methanol solution into the reaction kettle by using a column pump within 30-60 min, controlling the reaction temperature to be 80-90 ℃, keeping the temperature for 1h after dropwise adding, cooling to room temperature by introducing cooling water after keeping the temperature, opening an air outlet valve to exhaust, and absorbing redundant dimethylamine by using methanol; the feed liquid is filtered, the filter cake is washed twice with 100mL of methanol and drained, and the filter cake weighs 138 g. Pouring the filtrate into a 1L four-mouth bottle, heating, refluxing for 0.5h to remove excessive dimethylamine gas, and absorbing with cooled methanol. The reflux device is a distillation device, and front cut fraction and main cut fraction are respectively collected, wherein the front cut fraction is 165g of dimethylamine methanol solution, the main cut fraction is N, N, N ', N' -tetramethyl-alpha, beta-ethylenediamine (TMEDA for short) methanol solution, the weight is 486g, and the content of the detected TMEDA is 23.6%.
And 2, operation step:
300g of methanol was added to a 500mL four-necked flask, and then stirred and cooled to 0 ℃ or lower, 191.9g (99%, 2mol) of methyl bromide stored in a freezer was added thereto, and the mixture was sealed and refrigerated for further use. 486g of TMEDA methanol solution is poured into a 1.5L high-pressure autoclave, the prepared methanol-methyl bromide mixed solution is quickly added, and the autoclave is sealed. Stirring and heating to 80 ℃, maintaining the temperature at 80-90 ℃, and the pressure of the reaction kettle at 0.01-0.05 MPa, reacting for 4 hours, and cooling to obtain 976g of ethyl-alpha, beta-bis (trimethyl ammonium bromide) methanol solution, wherein the content of bromine ions is analyzed to be 16.0%, and the yield is 97.6%.
Operation step 3:
383g of methanol solution containing 21% NaOH (containing 2mol of NaOH) is added into a 2L four-mouth bottle, 976g of ethyl-alpha, beta-bis (trimethyl ammonium bromide) methanol solution is dripped at 50 ℃, the temperature is maintained at 50-60 ℃, and the temperature is kept for 2 hours at about 55 ℃ after dripping. After the heat preservation, the temperature is reduced to the room temperature. Suction filtration, filter cake with 150g x 2 methanol washing 2 times, filter cake weighing 257.5g, analysis of bromide ion content of 59%. Removing methanol from the filtrate under the negative pressure of-0.055 MPa to the liquid temperature of 78 ℃, reducing the temperature, adding 400g of deionized water, continuously removing methanol from the filtrate under the negative pressure of-0.085 MPa and adding water to the liquid temperature of 78 ℃, and analyzing the content of ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) to be 34.9 percent and the content of bromide to be 0.98 percent in 475g of residual liquid in the kettle. The aqueous solution of diquaternary ammonium base is used for condensing nitrobenzene and aniline.
Ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) is purified and then subjected to conventional analysis such as crystal water, melting point, decomposition temperature, carbon dioxide absorption, water absorption, element analysis and the like; the spectra of the product can be shown in figures 1, 3 and 5.
And (3) crystal water determination: (CH)3)3NCH2CH2N(CH3)3(OH)2·xH2O x＝10。
And (3) melting point determination: 56-66 ℃.
Decomposition temperature: the initial decomposition temperature was 115 ℃ and the decomposition temperature was 173.9 ℃.
Carbon dioxide absorption test: taking 10g of the double quaternary ammonium hydroxide, placing the double quaternary ammonium hydroxide in a watch glass, flatly paving the watch glass into a thickness of 2-3 mm, placing the watch glass in air for 12 hours, and then adding ethyl-alpha, beta-bis (trimethyl ammonium bicarbonate) DTMAHCO3The mass content of (A) is increased from 1.61% to 5.16%; after 24h, the total amount reaches 8.88 percent, which shows that the bis-quaternary ammonium hydroxide is very easy to absorb CO2。
Water absorption test: 10g of the double quaternary ammonium hydroxide is placed in a watch glass and spread to form a thickness of 2-3 mm, after the double quaternary ammonium hydroxide is placed in the air for 10 hours, the water content is increased from 5.8% to 14.2%, and the double quaternary ammonium hydroxide is easy to absorb water.
Elemental analysis: (CH)3)3NCH2CH2N(CH3)3(OH)2·10H2O，C8H44N2O12M is 360, calculated: c, H, N and O are 26.67 percent, 12.22 percent, 7.78 percent and 53.33 percent; measured value: c, H, N and O are respectively 26.01 percent, 12.06 percent, 7.45 percent and 54.48 percent; the measured value and the calculated value are better matched.
The bis-quaternary ammonium base describes: colorless crystals (normally containing 10 crystal waters) have a melting point of 56-66 ℃, are easy to absorb moisture, can quickly absorb carbon dioxide in air, start to decompose at 110 ℃, and decompose to a maximum value at 175 ℃ into trimethylamine, tetramethylethylenediamine, methanol and the like.
Examples 2 to 6
Preparation of bis-quaternary ammonium base 2# to 6#
Operation step 1: n, N' -tetramethyl- α, β -ethylenediamine was prepared in the same manner as in operation 1 of example 1.
And 2, operation step: in the operation step 2 of example 1, the addition of bromomethane was changed to the addition of bromoethane, bromopropane, isopropyl bromide, chloropropene and bromododecane, respectively, in an amount of 2mol, and the rest operations were the same.
Operation step 3: same as in operation step 3 of example 1.
The obtained quaternary ammonium bases 2# to 6# are respectively:
ethyl-alpha, beta-bis (ethyldimethylammonium hydroxide),
ethyl-alpha, beta-bis (propyldimethylammonium hydroxide),
ethyl-alpha, beta-bis (isopropyldimethylammonium hydroxide),
ethyl-alpha, beta-bis (allyldimethylammonium hydroxide),
ethyl-alpha, beta-bis (dodecyl dimethyl ammonium hydroxide).
Examples 7 to 9
Preparation of diquaternary ammonium base 7# to 9#
Operation step 1: reaction under normal pressure
200g of ethanol and 177g (99%, 2.4mol, the boiling point of diethylamine is 55 ℃ under normal pressure) of diethylamine are added into a 1L four-mouth reaction bottle, the mixture is directly weighed, 99g (1mol) of 1, 2-dichloroethane is dripped into the reaction bottle at 50-55 ℃ within 30-60 min, and the temperature is kept for 1 h. 486g of 28% sodium ethoxide solution is dripped within 30-60 min, and after the dripping is finished, the temperature is slowly increased and is kept at 75-85 ℃ for 1 h. The reaction mixture was cooled to room temperature, filtered off with suction, and the filter cake was washed twice with 100mL of ethanol and weighed 133 g. 885g of the filtrate is poured into a four-mouth bottle for distillation, and the front fraction weighs 600g and is a diethylamine ethanol solution; the main fraction weighed 257g and was 65% ethanol solution containing N, N, N ', N' -tetraethylethylenediamine.
And 2, operation step:
the halogenated hydrocarbons were methyl chloride, ethyl bromide and propyl bromide, respectively, in an amount of 2mol, and the procedure was repeated in the same manner as in 2. sup. th step of example 1.
Operation step 3: same as in operation step 3 of example 1.
The obtained quaternary ammonium bases 7# to 9# are respectively:
ethyl-alpha, beta-bis (methyldiethylammonium hydroxide),
ethyl-alpha, beta-bis (triethylammonium hydroxide),
ethyl-alpha, beta-bis (propyldiethylammonium hydroxide).
Examples 10 to 16
Preparation of diquaternary ammonium base 10# to 16#
Operation step 1: in the operation step 1 of example 1, 2-dichloroethane was changed to 1, 3-dibromopropane, the charge amount was 1mol, and the rest of the operations were the same, thereby obtaining N, N, N ', N' -tetramethyl- α, γ -propanediamine.
And 2, operation step: the halogenated hydrocarbon was methyl bromide, ethyl bromide, propyl bromide, isopropyl bromide, allyl chloride, butyl bromide and dodecyl bromide, each added in an amount of 2mol, and the rest was the same as in operation 2 of example 1.
Operation step 3: same as in operation step 3 of example 1.
The obtained quaternary ammonium hydroxide 10# to 16# are respectively as follows:
propyl- α, γ -bis (trimethylammonium hydroxide);
propyl- α, γ -bis (ethyldimethylammonium hydroxide);
propyl- α, γ -bis (propyldimethylammonium hydroxide);
propyl- α, γ -bis (isopropyl dimethyl ammonium hydroxide);
propyl- α, γ -bis (allyldimethylammonium hydroxide);
propyl- α, γ -bis (butyldimethylammonium hydroxide);
propyl-alpha, gamma-bis (dodecyl dimethyl ammonium hydroxide).
Examples 17 to 19
Preparation of bis-quaternary ammonium base No. 17-19 #
Operation step 1: in the operation step 1 of example 7-9, 1, 2-dichloroethane was changed to 1, 3-dibromopropane, the charge amount was still 1mol, and the other operations were the same, to obtain N, N' -tetraethyl- α, γ -propanediamine.
And 2, operation step: the halogenated hydrocarbon was methyl bromide, ethyl bromide and propyl bromide, respectively, in an amount of 2mol, and the rest was the same as in operation 2 of example 1.
Operation step 3: same as example 1, step 3 was conducted.
The obtained quaternary ammonium hydroxide 17# to 19# are respectively:
propyl- α, γ -bis (methyldiethylammonium hydroxide);
propyl- α, γ -bis (triethylammonium hydroxide);
propyl- α, γ -bis (propyldiethylammonium hydroxide).
Examples 20 to 22
Preparation of diquaternary ammonium base 20# to 22#
Operation step 1: in the operation step 1 of examples 7 to 9, 1, 2-dichloroethane was changed to 1, 3-dibromopropane, the charge amount was 1mol, diethylamine was changed to dipropylamine, and dipropylamine was directly weighed and still 2.4mol, so as to obtain N, N' -tetrapropyl- α, γ -propanediamine.
And 2, operation step: the halogenated hydrocarbons were methyl chloride, ethyl bromide and propyl bromide, respectively, in an amount of 2mol, and the procedure was repeated in the same manner as in 2. sup. th step of example 1.
Operation step 3: same as in operation step 3 of example 1.
The obtained quaternary ammonium hydroxide 20# to 22# are respectively:
propyl- α, γ -bis (methyldipropylammonium hydroxide);
propyl- α, γ -bis (ethyldipropylammonium hydroxide);
propyl-alpha, gamma-bis (tripropylammonium hydroxide).
Example 23
Preparation of bis-quaternary ammonium base 23# beta-methoxypropyl-alpha, gamma-bis (trimethylammonium hydroxide)
Synthesizing trimethylamine and 1, 3-dichloro-2-propanol to obtain beta-hydroxy-alpha, gamma-bis (trimethylammonium chloride), etherifying with dimethyl sulfate to obtain beta-methoxy-alpha, gamma-bis (trimethylammonium chloride), and finally performing alkali exchange to obtain beta-methoxy-alpha, gamma-bis (trimethylammonium hydroxide).
The synthesis reaction formula is as follows:
Figure G2009102502035D0000151
operation step 1:
adding 300g of methanol into a 1L four-mouth bottle, stirring, cooling to below 0 ℃, introducing trimethylamine gas, weighing, stopping introducing the gas when the weight of the material is increased by about 147.5g (2.5mol), and refrigerating for later use. Adding 130.3g (1mol) of 1, 3-dichloro-2-propanol and the trimethylamine methanol solution into a 1L autoclave, sealing the autoclave, heating to 70-80 ℃, preserving heat for 1.5-2 h, heating to 90-100 ℃, preserving heat for 2-2.5 h, and cooling to 20 ℃ after heat preservation. And opening an air outlet valve to exhaust air, recovering excessive trimethylamine, and opening the kettle to obtain 560g of beta-hydroxypropyl-alpha, gamma-bis (trimethyl ammonium chloride) methanol solution, wherein the detected chloride ion content is 12.48 percent, and the conversion rate is 98.4 percent.
And 2, operation step:
putting the beta-hydroxypropyl-alpha, gamma-bis (trimethyl ammonium chloride) methanol solution into a 1L four-mouth bottle, weighing 128.6g (1mol) of dimethyl sulfate, dropwise adding the dimethyl sulfate at 40-50 ℃ for 1.5-2 h, heating and refluxing for 2h after the dropwise adding is finished, cooling to about 40 ℃ to obtain 688.6g of beta-methoxypropyl-alpha, gamma-bis (trimethyl ammonium chloride) methanol solution, and directly carrying out the next reaction without post-treatment.
Operation step 3:
adding 811g of a prepared methanol solution containing 29% KOH (containing 4.2mol of KOH) into a 2L four-mouth bottle, dropwise adding the beta-methoxypropyl-alpha, gamma-bis (trimethyl ammonium chloride) at 50 ℃, maintaining the temperature at 50-60 ℃, dropwise adding for 1-2 h, and then preserving the heat at 50-60 ℃ for 2 h. After the heat preservation, the temperature is naturally reduced, the filtration is carried out, a filter cake is washed twice by 250g of methanol, and 403.8g is weighed. Pouring the filtrate into a 2L four-mouth bottle, removing methanol to 78 ℃ under negative pressure of-0.055 MPa, cooling, adding 450g of deionized water, and continuously removing methanol to 78 ℃ under negative pressure of-0.085 MPa; 560g of aqueous bis-quaternary ammonium hydroxide solution was obtained, and it was analyzed that the content of β -methoxypropyl- α, γ -bis (trimethylammonium hydroxide) was 36.6% and that the chloride ion content was 0.33%.
Example 24
Preparation of bis-quaternary ammonium base 24# beta-ethoxypropyl-alpha, gamma-bis (ethyldimethylammonium hydroxide)
Operation step 1:
adding 100g of methanol into a 500mL four-mouth bottle, stirring, cooling to below 0 ℃, introducing dimethylamine gas until the weight of the material is increased by about 99g (2.2mol), stopping introducing the dimethylamine gas, and refrigerating for later use. Adding 130.3g (1mol) of 1, 3-dichloro-2-propanol into a 1L autoclave, quickly pouring the prepared dimethylamine methanol solution into a kettle, sealing the kettle, stirring, heating to 70-80 ℃, and preserving heat for 1 h. Pumping 360g of 30% sodium methoxide methanol solution by using a column pump within 30-60 min, controlling the reaction temperature to be 80-90 ℃, keeping the temperature for 1h after dropwise adding, introducing cooling water to cool to about 20 ℃ after keeping the temperature, opening an air outlet valve to exhaust, and absorbing redundant dimethylamine by using methanol; the feed liquid is poured out and filtered, and the filter cake is washed twice by 100mL of methanol to obtain 142g of filter cake. The filtrate is 620g of N, N, N ', N' -tetramethyl-beta-hydroxy-alpha, gamma-propane diamine (TMHPDA for short) methanol solution, the content of the TMHPDA is detected to be 23.2%, and the yield is more than or equal to 98.6%.
And 2, operation step:
transferring the TMHPDA methanol solution into a 2L four-port bottle, dropwise adding 327g (3mol) of bromoethane, dropwise adding for 1.5h, and heating and refluxing for 2 h. And then adding 560g of methanol solution containing 30% KOH (containing 3mol of KOH) dropwise at the temperature of 50-60 ℃, adding 1-2 h dropwise, and then preserving heat at the temperature of 50-60 ℃ for 2 h. After the heat preservation, the temperature is naturally reduced, the filtration is carried out, and the filter cake is washed by methanol with the weight of 200g multiplied by 2. Removing methanol from the filtrate under negative pressure of-0.055 MPa to liquid temperature of 78 deg.C, cooling, adding 900g deionized water, and continuously removing methanol from the filtrate under negative pressure of-0.085 MPa to liquid temperature of 78 deg.C; 840g of aqueous bis-quaternary ammonium base was obtained, and the analyzed content of β -ethoxypropyl- α, γ -bis (ethyldimethylammonium hydroxide) was 29.4%.
Example 25
Preparation of bis-quaternary ammonium base 25# butyl-alpha, delta-bis (trimethylammonium hydroxide)
Trimethylamine reacts with 1, 4-dichlorobutane to obtain butyl-alpha, delta-bis (trimethyl ammonium chloride), and the butyl-alpha, delta-bis (trimethyl ammonium hydroxide) is obtained by alkali exchange with potassium hydroxide.
The synthesis reaction formula is as follows:
Figure G2009102502035D0000171
operation step 1:
adding 300g of methanol into a 1L four-mouth bottle, stirring, cooling to below 0 ℃, starting to introduce trimethylamine gas, keeping the temperature at about 0 ℃, weighing, stopping introducing the gas when the weight of the material is increased by about 148g (2.5mol), and refrigerating and standing for later use. Adding 127g (1mol) of 1, 4-dichlorobutane into a 1L autoclave, quickly pouring the prepared trimethylamine/methanol solution into the autoclave, sealing the autoclave, heating to 80 ℃, keeping the temperature for 1.5-2 h, heating to 90-100 ℃, keeping the temperature for 3-4 h, and cooling to 20 ℃ after the temperature is kept. The vent valve was opened to vent the gas, and the kettle was opened to obtain a butyl- α, δ -bis (trimethylammonium chloride) methanol solution weighing 553.6g, with a free chlorine content of 12.6% as measured.
And 2, operation step:
adding 373g (containing 2mol KOH) of methanol solution containing 30% KOH into a 1L four-mouth bottle, dropwise adding 553.6g of the butyl-alpha, delta-bis (trimethyl ammonium chloride) methanol solution, maintaining the temperature at 50-60 ℃, and preserving the temperature for 2h at 50-55 ℃ after dropwise adding. And after the heat preservation is finished, naturally cooling to room temperature, then cooling to 10-15 ℃ with ice water, carrying out suction filtration, washing the filter cake twice with 80g multiplied by 2 methanol, wherein the wet weight of the filter cake potassium chloride is 187g, and the content of analyzed chloride ions is 37.2%. 827g of filtrate is put into a 1L four-mouth bottle in two batches, methanol is removed under negative pressure of-0.07 MPa until the liquid temperature reaches 70 ℃, 550g of deionized water is added after slight temperature reduction, methanol and water are continuously removed under negative pressure of-0.088 MPa until the liquid temperature reaches 75 ℃, 597.5g of residual butyl-alpha, delta-bis (trimethyl ammonium hydroxide) aqueous solution is left in the kettle, and the content of butyl-alpha, delta-bis (trimethyl ammonium hydroxide) is analyzed to be 33.06 percent and the content of chloride ions is 0.3 percent.
Examples 26 to 31
Preparation of diquaternary ammonium base 26# to 31#
Operation step 1:
adding 100g of methanol into a 500mL four-mouth bottle, stirring, cooling to below 0 ℃, introducing dimethylamine gas until the weight of the material is increased by about 99g (2.2mol), stopping introducing the dimethylamine gas, and refrigerating for later use. Adding 127g (1mol) of 1, 4-dichlorobutane into a 1L autoclave, quickly pouring the prepared dimethylamine methanol solution into the autoclave, sealing the autoclave, stirring and heating to 70-80 ℃, and preserving heat for 1 h. Pumping 360g of 30% sodium methoxide solution by using a column pump within 30-60 min, controlling the reaction temperature to be 80-90 ℃, keeping the temperature for 1h after dropwise adding, introducing cooling water to cool to about 20 ℃ after keeping the temperature, opening an air outlet valve to exhaust, and absorbing redundant dimethylamine by using methanol; the feed liquid is poured out and filtered, and the filter cake is washed twice by 100mL of methanol to obtain 145g of filter cake. The filtrate was a methanol solution of N, N, N ', N' -tetramethyl-alpha, delta-butanediamine (abbreviated as TMBDA) weighing 563 g.
And 2, operation step:
adding the TMBDA methanol solution into a 1L four-mouth bottle, respectively dropwise adding bromoethane, bromopropane, isopropyl bromide, allyl chloride, bromobutane and bromododecane (all 2mol), dropwise adding for 1.5h, and heating and refluxing for 2 h. So as to respectively obtain the corresponding butyl-alpha, delta-bis (tri-substituted quaternary ammonium bromide).
Operation step 3:
and (3) respectively dripping 285.7g (2mol) of 28% NaOH methanol solution into the butyl-alpha, delta-bis (tri-substituted quaternary ammonium bromide) at the temperature of 50-60 ℃, dripping for 1-2 h, and then preserving heat for 2h at the temperature of 50-60 ℃. After the temperature preservation, the mixture is naturally cooled, filtered and the filter cake is washed by methanol with the weight of 150g multiplied by 2. Removing methanol from the filtrate under negative pressure of-0.055 MPa to liquid temperature of 78 deg.C, cooling, adding deionized water, and continuously removing methanol from the filtrate under negative pressure of-0.085 MPa to liquid temperature of 78 deg.C; to obtain the corresponding aqueous base solution of diquaternary ammonium.
The obtained quaternary ammonium hydroxide 26# to 31# are respectively:
butyl- α, δ -bis (ethyldimethylammonium hydroxide);
butyl- α, δ -bis (propyldimethylammonium hydroxide);
butyl- α, δ -bis (isopropyl dimethyl ammonium hydroxide);
butyl- α, δ -bis (allyldimethylammonium hydroxide);
butyl- α, δ -bis (butyldimethylammonium hydroxide);
butyl- α, δ -bis (dodecyl dimethyl ammonium hydroxide).
Examples 32 to 35
Preparation of diquaternary ammonium base 32# to 35#
Operation step 1:
100g of methanol and 168g (2.3mol) of diethylamine are added into a 1L four-neck flask, stirred and heated to 50 ℃, 127g (1mol) of 1, 4-dichlorobutane is dripped in 30-45 min, and the temperature is kept for 1h after dripping. 386g (2mol) of 28% sodium methoxide methanol solution is dropwise added within 1h, the reflux and the heat preservation are carried out for 1.5h after the dropwise addition, the temperature is reduced to the room temperature, the filtration is carried out, the filter cake is washed twice by 100mL of methanol, and 139g of the filter cake is weighed. The filtrate was a methanol solution of N, N, N ', N' -tetraethyl-alpha, delta-butanediamine (TEBDA for short) weighing 556g and containing 35.2% of TEBDA by analysis.
And 2, operation step:
556g of the TEBDA methanol solution is added into a 1L four-mouth bottle, methyl bromide, ethyl bromide, propyl bromide and allyl chloride (all 2mol) are respectively dropwise added for 1.5h, and the temperature is increased and the reflux is carried out for 2 h. So as to respectively obtain the corresponding butyl-alpha, delta-bis (tri-substituted quaternary ammonium bromide).
Operation step 3:
respectively dripping 448g (containing 2mol of KOH) of 25% KOH methanol solution into the butyl-alpha, delta-bis (tri-substituted quaternary ammonium bromide) at the temperature of 50-60 ℃, dripping for 1-2 h, and then preserving the heat for 2h at the temperature of 50-60 ℃. After the temperature preservation is finished, the temperature is naturally reduced, the filtration is carried out, and the filter cake is washed by ethanol with the weight of 150g multiplied by 2. Dealcoholizing the filtrate under the negative pressure of-0.055 MPa to the liquid temperature of 78 ℃, cooling, adding deionized water, and continuously removing methanol water under the negative pressure of-0.085 MPa to the liquid temperature of 78 ℃ to obtain the corresponding aqueous solution of the diquaternary ammonium base.
The obtained quaternary ammonium hydroxide 32# to 35# are respectively:
butyl- α, δ -bis (methyldiethylammonium hydroxide);
butyl- α, δ -bis (triethylammonium hydroxide);
butyl- α, δ -bis (propyldiethylammonium hydroxide);
butyl- α, δ -bis (allyldiethylammonium hydroxide).
Example 36
Preparation of bis-quaternary ammonium base 1# ethyl-alpha, beta-bis (trimethyl ammonium hydroxide)
Synthesizing trimethylamine and dichloroethane to obtain ethyl-alpha, beta-bis (trimethyl ammonium chloride) bis-quaternary ammonium, and then performing ion exchange with potassium hydroxide to obtain ethyl-alpha, beta-bis (trimethyl ammonium hydroxide).
The synthesis reaction formula is as follows:
Figure G2009102502035D0000201
adding 200g of methanol into a 1L four-mouth bottle, stirring, cooling to 0 ℃, introducing trimethylamine gas, weighing, stopping introducing gas when the weight of the material is increased by about 142g (2.4mol), refrigerating and standing for later use. Putting 99g (1mol) of dichloroethane into a 1L autoclave, quickly pouring the prepared trimethylamine methanol solution, sealing the autoclave, stirring, heating to 80 ℃, preserving heat for 1.5-2 h, keeping the pressure in the autoclave to 0.5-1.0 MPa, heating to 90-100 ℃, preserving heat for 3-3.5 h, cooling to 20 ℃ after heat preservation. And opening an air outlet valve to exhaust, recovering excessive trimethylamine by using cold methanol, opening the kettle, filtering a small amount of black solid, wherein the filtrate is ethyl-alpha, beta-bis (trimethyl ammonium chloride) methanol solution, the weight is about 429g, and the content of free chlorine is determined to be 16.3%.
Adding 448g of methanol solution (containing 2mol KOH) containing 25% KOH into a 1L four-mouth bottle, dropwise adding 429g of ethyl-alpha, beta-bis (trimethyl ammonium chloride) methanol solution at the dropwise adding temperature of 50-55 ℃ for 1h, and keeping the temperature at 50-60 ℃ for 2h after dropwise adding. After the temperature preservation is finished, naturally cooling to the room temperature. Suction filtration was carried out, and the filter cake was washed twice with 150g of methanol, wet weight 187g, and analyzed chloride ion content was 36.8%. And (3) removing methanol from the filtrate under the negative pressure of-0.07 MPa to the liquid temperature of 70 ℃, slightly cooling, adding 600g of deionized water, continuously removing methanol and water under the negative pressure of-0.085 MPa to the liquid temperature of 75 ℃, and analyzing the residual ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) aqueous solution 504g to obtain the ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) with the content of 34.2 percent and the chloride ion content of 0.3 percent.
Example 37
Preparation of bis-quaternary ammonium base 1# ethyl-alpha, beta-bis (trimethyl ammonium hydroxide)
Firstly, N, N, N ', N' -tetramethyl-alpha, beta-ethylenediamine and dimethyl sulfate are used for synthesizing biquaternary ammonium salt, and then ion exchange is carried out to obtain the biquaternary ammonium base.
The synthesis reaction formula is as follows:
Figure G2009102502035D0000211
adding 117.2g (99 percent and 1mol) of N, N, N ', N' -tetramethyl-alpha, beta-ethylenediamine and 300g of methanol into a 1L four-neck bottle, dropwise adding 257.1g (98 percent and 2mol) of dimethyl sulfate at 40-50 ℃, dropwise adding for 2-2.5 h, after dropwise adding, heating to 60-65 ℃ for reaction for 2h, evaporating partial methanol, adding 200g of N-butyl alcohol, heating to about 80 ℃, naturally cooling for crystallization, filtering, washing a filter cake with 100g of multiplied by 2 cold propanol to obtain 460g of white or light yellow crystal ethyl-alpha, beta-bis (trimethyl monoammonium sulfate), and drying for 364 g.
592g (3.7mol) of methanol solution containing 25 percent NaOH is added into a 2L four-mouth bottle, a mixed solution of 364g of ethyl-alpha, beta-bis (trimethyl ammonium monomethyl sulfate) and 600g of methanol is dripped, the temperature is maintained at 40-50 ℃, and after the dripping is finished, the temperature is raised and the reflux is carried out for 3-4 h. After the heat preservation, the mixture is naturally cooled and crystallized, and is filtered, a filter cake is washed by methanol with the weight of 100g multiplied by 2, and 355g is weighed. 48g (0.15mol) of barium hydroxide octahydrate is added into the filtrate, the temperature is increased, the reflux is carried out, the temperature is reduced, the filtration is carried out, and 50g of filter cake is obtained. And (3) removing methanol from the filtrate under the negative pressure of-0.055 MPa to the liquid temperature of 75 ℃, cooling, adding 500g of deionized water, continuously removing methanol from the filtrate under the negative pressure of-0.087 MPa and adding water to the liquid temperature of 78 ℃, and analyzing 480g of residual ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) aqueous solution to obtain an ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) content of 35.5 percent and sulfate radicals of less than or equal to 0.1 percent.
Example 38
Preparation of bis-quaternary ammonium base 1# ethyl-alpha, beta-bis (trimethyl ammonium hydroxide)
Firstly, synthesizing N, N, N ', N' -tetramethyl-alpha, beta-ethylenediamine and dimethyl carbonate to obtain ethyl-alpha, beta-bis (trimethyl ammonium monomethyl carbonate), and then carrying out ion exchange to obtain the bis-quaternary ammonium base.
The synthesis reaction formula is as follows:
Figure G2009102502035D0000221
adding 190g (2.1mol) of dimethyl carbonate, 116g (1mol) of N, N, N ', N' -tetramethyl-alpha, beta-ethylenediamine and 640g of methanol into a 2L autoclave, sealing the autoclave, stirring and heating, carrying out heat preservation reaction for 4-6 h at 140-150 ℃ and 1.0-1.5 MPa, cooling and discharging into a 2L four-neck flask, dropwise adding 672g (4.2mol) of a methanol solution containing 25% of NaOH, stirring and reacting, controlling the temperature to be 50-60 ℃ and the reaction time to be 4 h. Naturally cooling, crystallizing, filtering, removing methanol to liquid temperature of 78 ℃ under the negative pressure of-0.055 MPa, cooling, adding 500g of deionized water, continuing to remove methanol to liquid temperature of 78 ℃ under the negative pressure of-0.085 MPa, and obtaining residual ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) aqueous solution 487g, wherein the content of ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) is analyzed to be 35.8%, and the yield is 96.9%.
Example 39
Preparation of bis-quaternary ammonium base 25# butyl-alpha, delta-bis (trimethylammonium hydroxide)
Adding 100g of methanol into a 500mL four-mouth bottle, stirring, cooling to below 0 ℃, introducing dimethylamine gas until the weight of the material is increased by about 99g (2.2mol), stopping introducing the dimethylamine gas, and refrigerating for later use. Adding 127g (1mol) of 1, 4-dichlorobutane into a 1L autoclave, quickly pouring the prepared dimethylamine methanol solution into the autoclave, sealing the autoclave, stirring and heating to 70-80 ℃, and preserving heat for 1 h. Pumping 360g of 30% sodium methoxide methanol solution by using a column pump within 30-60 min, controlling the reaction temperature to be 80-90 ℃, keeping the temperature for 1h after dropwise adding, introducing cooling water to cool to about 20 ℃ after keeping the temperature, opening an air outlet valve to exhaust, and absorbing redundant dimethylamine by using methanol; the feed liquid is poured out and filtered, and the filter cake is washed twice by 100mL of methanol to obtain 145g of filter cake. The filtrate was a methanol solution of N, N, N ', N' -tetramethyl-alpha, delta-butanediamine (abbreviated as TMBDA) weighing 563 g. Adding the mixture into a 1.5L autoclave, quickly adding 326g of methyl chloride methanol solution (containing 126.3g of chloromethane and 2.5mol) prepared by cooling in advance, introducing nitrogen to enable the pressure to reach 0.5MPa, stirring and heating to 80 ℃, reacting for 2h, heating to 90-100 ℃ again, reacting for 3h, cooling to room temperature, slowly opening an exhaust port, discharging and collecting excessive methyl chloride, wherein the reaction solution is butyl-alpha, delta-bis (trimethyl ammonium chloride) methanol solution.
And (3) dripping 285.7g (containing 2mol of NaOH) of 28% NaOH methanol solution into the butyl-alpha, delta-bis (trimethyl ammonium chloride) methanol solution at the temperature of 50-60 ℃, dripping for 1-2 h, and then preserving the heat for 2h at the temperature of 50-60 ℃. After the temperature preservation, the mixture is naturally cooled, filtered and the filter cake is washed by methanol with the weight of 150g multiplied by 2. Removing methanol from the filtrate under the negative pressure of-0.055 MPa to the liquid temperature of 75 ℃, cooling, adding 650g of deionized water, continuously removing methanol from the filtrate under the negative pressure of-0.085 MPa to dissolve water until the liquid temperature reaches 78 ℃, and obtaining 708g of aqueous solution of butyl-alpha, delta-bis (trimethyl ammonium hydroxide), wherein the content of the aqueous solution is 28.2%.
The following examples are intended to illustrate that the bis-quaternary ammonium hydroxide catalyst is used for the condensation of nitrobenzene and aniline, and has the advantages of high catalytic activity, low consumption, high product selectivity, fast subsequent hydrogenation, easy oil-water separation, and the like, but the invention is not further limited.
In the bis-quaternary ammonium hydroxide application examples, the condensation conversion is calculated based on the amount of unreacted nitrobenzene remaining in the final condensation reaction. If no nitrobenzene is detected, the conversion is assumed to be 100%.
NB conversion ═ mass content of NB in condensation liquid x mass of condensation liquid ÷ initial NB input amount x 100%
Selectivity ═ 4-NODPA mass +4-NDPA mass ÷ (4-NODPA mass +4-NDPA mass + AZO mass + PHZ mass) × 100%
Wherein: NB represents nitrobenzene; 4-NDPA represents 4-nitrodiphenylamine; 4-NODPA represents 4-nitrosodiphenylamine; AZO represents azobenzene; PHZ represents phenazine.
In the examples described below, 4-ADPA represents 4-aminodiphenylamine; BA represents aniline; "other" refers to aniline and nitrobenzene condensation by-products, primarily 4-phenylazo-diphenylamine, ortho (ortho) nitrodiphenylamine and other unidentified materials.
Application example 1
Bis-quaternary ammonium base ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) is used for catalyzing condensation of nitrobenzene and aniline and subsequent hydrogenation reaction to generate 4-aminodiphenylamine
Adding 359g of ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) aqueous solution (the content of bis-quaternary ammonium base is 30.1 percent, the mole of bis-quaternary ammonium base is 0.6 mole, the mole of hydroxyl is 1.2 mole) and 558g of aniline (6 mole) into a 1L four-mouth bottle with a stirring device, a thermometer and a negative pressure distillation device, adjusting the absolute pressure to 40mmHg, heating the solution by using a hot water bath at 70-90 ℃, heating the reaction system to 60-70 ℃, distilling and dehydrating, reacting the bis-quaternary ammonium base and the aniline to generate bis-quaternary ammonium aniline salt, determining the reaction end point by measuring the water yield, and stopping the reaction when 142.4g of water is removed. Adjusting the absolute pressure of the system to 60mmHg, heating to 70-75 ℃, slowly dripping 123g (1mol) of nitrobenzene, continuously taking out water in the dripping process, dripping for 2 hours, and keeping the temperature for 1 hour at 75 ℃ after dripping. The separated material was poured into a separatory funnel for separation into 99.7g of an upper aqueous layer and 14.5g of a lower oil layer. The oil layer was returned to the condensation liquid to 796.4g in total.
The contents of the liquid spectrum analysis are as follows: BA 56.95%, NB 0.1%, 4-NODPA 22.93%, 4-NDPA 1.43%, PHZ 0.19%, AZO 1.07%. The conversion of NB was 99.4%, the selectivity of 4-NDPA and 4-NODPA was 95.1%, and the mass ratio of 4-NODPA to 4-NDPA was 16.03.
796.4g of the condensation liquid is put into a 2L first-stage hydrogenation autoclave, 275g of water (242.1 g of water recovered in the process of alkali concentration salt formation and condensation, the rest 32.9g of deionized water) and 2g of a self-made 0.8 percent Pd/C catalyst are added at the same time, and N is used2And H2Respectively replacing for 4 times, introducing hydrogen, controlling the pressure of the reaction kettle to be 2.0MPa and the temperature to be 85 ℃, and finishing the reaction when the reaction does not absorb hydrogen; after the temperature is reduced to room temperature, the reaction solution is subjected to nitrogen pressure filtration, and the catalyst is recovered and reused; standing the filtrate for layering, and adding 65g of ethanol2 the oil layer is washed by deionized water for 2 times until the oil layer is neutral, the washing water and the separated water layer are combined and then extracted by 75g multiplied by 3 toluene for 3 times, the extracted water layer is applied to a condensation reaction, 602.6g of the recovered water layer is recovered, the alkali content is 17.4 percent, and the recovery rate of the condensation catalyst is 97.1 percent. 642g of a first-stage hydrogenation oil layer was obtained, and 248.5g of extracted toluene (containing 23.3g of BA and 1.1g of 4-ADPA) was obtained. Analyzing the content by liquid chromatography: 70.56% of BA, 27.1% of 4-ADPA, 0.24% of PHZ and 1.3% of AZO.
642g of the first-stage hydrogenation oil layer is put into a 1L second-stage hydrogenation high-pressure kettle, 3g of skeletal nickel catalyst is added at the same time, the kettle is sealed and replaced, the pressure of the reaction kettle is controlled to be 0.8MPa, the temperature is controlled to be 90 ℃, and the reaction is finished when hydrogen is not absorbed. To obtain 639g of a two-stage hydrogenation oil layer. Analyzing the liquid spectrum content: BA 70.8%, 4-ADPA 27.8% and PHZ 0.25%.
And putting 639g of the second-stage hydrogenation solution into a 1L four-neck flask, vacuumizing to 5mmHg, slowly heating to remove aniline, water and front fraction in the hydrogenation solution, switching to collect main fraction when the kettle bottom temperature is 220 ℃ and almost no solvent is distilled out, and cooling to below 40 ℃ after the rectification is finished to break the vacuum. 442g of BA, 4-ADPA and 1.4g of PHZ in the front cut fraction, and 16.7g of separated water; main fraction 170.4g, content by liquid chromatography: BA 0.1%, 4-ADPA 99.51%, PHZ 0.23%; 5.0g of residue. The yield of the main fraction was 92.15%, and the total yield was 94.86%.
Application of comparative example 1 Change of BiQuaternary ammonium base to MonoQuaternary ammonium base
Condensation of nitrobenzene and aniline under catalysis of tetramethyl ammonium hydroxide and subsequent hydrogenation reaction to generate 4-aminodiphenylamine
Adding 362.8g (30.1 percent and 1.2mol) of tetramethylammonium hydroxide aqueous solution and 558g (6mol) of aniline into a 1L four-mouth bottle with a stirring, thermometer and negative pressure distillation device, adjusting the absolute pressure to 40mmHg, heating by using a hot water bath at 70-90 ℃, heating the reaction system to 60-70 ℃, distilling and dehydrating, reacting the diquaternary ammonium base and the aniline to generate diquaternary ammonium aniline salt, determining the reaction end point by measuring the water yield, and stopping the reaction when 145.6g of water is removed. Adjusting the absolute pressure of the system to 60mmHg, heating to 70-75 ℃, slowly dripping 123g (1mol) of nitrobenzene, continuously taking out water in the dripping process, dripping for 2 hours, and keeping the temperature for 1 hour at 75 ℃ after dripping. The separated material was poured into a separatory funnel and separated into layers, an upper aqueous layer of 109g and a lower oil layer of 18.5 g. The oil layer was returned to the condensation liquid for a total of 778 g.
Analyzing the content by liquid chromatography: 58.3% of BA, 0.34% of NB, 22.8% of 4-NODPA, 2.44% of 4-NDPA, 0.39% of PHZ and 2.01% of AZO. The conversion of NB was 97.8%, the selectivity of 4-NDPA and 4-NODPA was 91.4%, and the mass ratio of 4-NODPA to 4-NDPA was 9.3.
778g of the condensation liquid is put into a 2L first-stage hydrogenation high-pressure kettle, 275g of water (254.6 g of water recovered in the process of alkali condensation and salt formation and condensation, and the rest 20.4g of deionized water) and 2g of a self-made 0.8 percent Pd/C catalyst are added, and the reaction is carried out at 2.0MPa/85 ℃ until no hydrogen is absorbed; cooling, suction filtering, standing and layering the filtrate, washing the oil layer, and recovering 94.8% of the condensation catalyst. Obtaining 640g of a first-stage hydrogenation oil layer, and analyzing the content by liquid chromatography: 67.3 percent of BA, 26.3 percent of 4-ADPA, 0.46 percent of PHZ and 2.27 percent of AZO.
And (3) putting 640g of the first-stage hydrogenation oil layer into a second-stage hydrogenation high-pressure kettle, simultaneously adding 3g of a skeleton nickel catalyst, sealing the kettle, replacing, controlling the pressure of the reaction kettle to be 0.8MPa and the temperature to be 90 ℃, and finishing the reaction when the reaction is carried out until hydrogen is not absorbed. 635g of a second-stage hydrogenation oil layer is obtained. Analyzing the liquid spectrum content: 69.3 percent of BA, 26.4 percent of 4-ADPA and 0.54 percent of PHZ.
Adding 635g of the second-stage hydrogenation liquid into a 1L four-neck flask, vacuumizing to 5mmHg, slowly heating, removing aniline, water and front fraction in the hydrogenation liquid, switching to collect main fraction when the temperature of the kettle bottom is 220 ℃ and almost no solvent is distilled off, cooling after the rectification is finished, and breaking the empty space. 438g of BA, 4-ADPA and PHZ in the front cut fraction, and 19.7g of separated water; main fraction 162.4g, content by liquid chromatography: BA 0.1%, 4-ADPA 99.24%, PHZ 0.34%; 8.0g of residue was collected. The yield of the main fraction was 87.59%, and the total yield was 89.87%.
The overall performance of the single and double quaternary ammonium base catalysis under the same use conditions was compared by repeating the experiment of application example 1 and application comparative example 1 in 20 batches, and the results are shown in table 2.
TABLE 2 Overall comparison of catalytic Performance of Mono-and BiQuaternary ammonium bases under the same service conditions
Comparing items Ethyl-alpha, beta-bis (trimethylammonium hydroxide) Tetramethyl ammonium hydroxide
Conversion/% of condensed nitrobenzene 98～100 97～100
4-NDPA and 4-NODPA Selectivity/% 92～97 89～94
Phenazine content/%) 0.1～0.5 0.3～0.7
Mass ratio of 4-NODPA to 4-NDPA 14～22 8～16
Ratio of hydrogenation time 0.95 1
Ratio of subsequent hydrogen consumption 0.95 1
Oil-water separation time/min after hydrogenation 25～30 35～40
Alkali recovery% 97～99 95～98
Application example 2
Continuous condensation reaction of nitrobenzene and aniline catalyzed by bis-quaternary ammonium base ethyl-alpha, beta-bis (trimethyl ammonium hydroxide)
The experimental device is formed by connecting three kettles in series, namely a first-level kettle 5L, a second-level kettle 5L and a third-level kettle 10L. The total dead volume was 6.4L, the residence time was 5 h. Aniline and bis-quaternary ammonium base (for convenience, ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) is replaced by bis-quaternary ammonium base) are salified and then added into a 65 ℃ jacket water bath heat preservation elevated tank, the mixture is fed from a first-stage kettle, and the mixture of nitrobenzene and aniline is respectively fed from the first-stage kettle and a second-stage kettle by a peristaltic pump, wherein the proportion of the mixture is respectively 50%. And a set of negative pressure distillation device is respectively assembled on the second-level kettle and the third-level kettle and connected to the same negative pressure system, and the third-level kettles respectively overflow and discharge. The molar ratio of the reactants aniline, diquaternary ammonium base and nitrobenzene is 6: 1.2: 1, wherein 5 parts of aniline and 1 part of diquaternary ammonium base form salt, and 1 part of aniline and 1 part of nitrobenzene are mixed and fed.
Detailed description of the experimental procedures:
33.4kg of aqueous solution containing 32.35% of diquaternary ammonium base and 46.7kg of 99.5% aniline are put into a 100L reaction kettle, the absolute pressure is adjusted to 40mmHg, the reaction kettle is heated in a water bath, dehydration and salification are carried out simultaneously, 11.9kg of water is removed by metering, and the reaction is stopped. Respectively synthesizing partial clinker in a third-stage kettle, keeping the temperature of the kettle at 70-75 ℃, starting a nitrobenzene/aniline peristaltic pump in the second-stage kettle and the third-stage kettle, simultaneously opening an aniline biquaternary ammonium salt head tank valve, respectively feeding 70.3kg of aniline biquaternary ammonium salt, 21.6kg of aniline and nitrobenzene mixture and 81.84kg of shrinkage compound for 68 hours, wherein the aniline biquaternary ammonium salt is 1L/h, and the aniline and nitrobenzene mixture in the second-stage kettle and the third-stage kettle are respectively 130mL/h and 150 mL/h.
81.84kg of the above-mentioned condensed liquid was charged into a single-stage hydrogenation autoclave, to which 26.8kg of water and 100g of 0.8% Pd/C catalyst were added, and the reaction mixture was heated with N2And H2Respectively replacing for 4 times, introducing hydrogen, controlling the pressure of the reaction kettle to be 2.0MPa and the temperature to be 85 ℃, and finishing the reaction when the reaction does not absorb hydrogen; after the temperature is reduced to room temperature, the reaction solution is subjected to nitrogen pressure filtration, and the catalyst is recovered and reused; after standing and layering the filtrate, washing the oil layer with 10kg of deionized water for 2 times respectively until the oil layer is neutral to obtain 66.8kg of a first-stage hydrogenation oil layer, and recovering 51.2kg of a water layer.
And putting 66.8kg of the first-stage hydrogenation oil layer into a second-stage hydrogenation high-pressure kettle, simultaneously adding 60g of a skeletal nickel catalyst, sealing the kettle, replacing, controlling the pressure of the reaction kettle to be 0.8MPa and the temperature to be 90 ℃, and finishing the reaction when the reaction is carried out until hydrogen is not absorbed. Thereby obtaining 66.9kg of a second-stage hydrogenation oil layer.
66.9kg of second-stage hydrogenation liquid is put into a 100L stainless kettle, the kettle is vacuumized to 5mmHg, the temperature is slowly increased, aniline and water in the hydrogenation liquid are removed, and when the temperature of the kettle bottom is 210 ℃ and almost no solvent is discharged, the temperature is slightly reduced. 44.8kg aniline and 1.4kg water are obtained. The aniline content by liquid spectrum analysis is 99.3%. And (3) putting the crude product after the aniline removal into a 10L stainless steel kettle, performing simple distillation in batches, gradually raising the temperature, controlling the discharging speed by heating, switching the fractions in the process, collecting the front fraction and the main fraction, cooling after the reaction is finished, and breaking the empty part to obtain 0.87kg of kettle residue. Front cut fraction 1.24kg, content by liquid chromatography: BA 79.05%, 4-ADPA 17.72%, PHZ 3.0%; main fraction 17.39kg, content by liquid chromatography: 99.54 percent of 4-ADPA and 0.28 percent of PHZ. The yield of the main fraction was 94.08%, and the total yield was 95.27%.
Application of comparative example 2 Change of BiQuaternary ammonium base to MonoQuaternary ammonium base
Continuous condensation reaction of nitrobenzene and aniline catalyzed by tetramethyl ammonium hydroxide
The experimental device is formed by connecting three kettles in series, namely a first-level kettle 5L, a second-level kettle 5L and a third-level kettle 10L. The total dead volume was 6.4L, the residence time was 5 h. The aniline and tetramethyl ammonium hydroxide are salified and then added into a 65 ℃ jacket water bath heat preservation elevated tank, the materials are fed from a first-stage kettle, and the mixed solution of nitrobenzene and aniline is respectively fed from the first-stage kettle and a second-stage kettle by a peristaltic pump, wherein the proportion of the mixed solution is respectively 50%. And a set of negative pressure distillation device is respectively assembled on the second-level kettle and the third-level kettle and connected to the same negative pressure system, and the third-level kettles respectively overflow and discharge. The molar ratio of the reactants aniline, tetramethyl ammonium hydroxide and nitrobenzene is 6: 1.2: 1, wherein 5mol of aniline and tetramethyl ammonium hydroxide form salt, and 1mol of aniline and nitrobenzene are mixed and fed.
Detailed description of the experimental procedures:
32.9kg of a 33.2% tetramethylammonium hydroxide aqueous solution and 46.7kg of 99.5% aniline were put into a 100L reaction vessel, the absolute pressure was adjusted to 40mmHg, the reaction vessel was heated in a water bath to dehydrate and form a salt, 10.1kg of water was removed by metering, and the reaction was stopped. Respectively synthesizing partial clinker in a third-stage kettle, keeping the temperature of the kettle at 70-75 ℃, starting a nitrobenzene/aniline peristaltic pump in the second-stage kettle and the third-stage kettle, simultaneously opening an aniline biquaternary ammonium salt head tank valve, respectively feeding aniline biquaternary ammonium salt into the second-stage kettle and the third-stage kettle for 68 hours by using the aniline biquaternary ammonium salt at 1L/h and the aniline and nitrobenzene mixture at 130mL/h and 146mL/h, adding 69.5kg of aniline biquaternary ammonium salt, 21.6kg of aniline and nitrobenzene mixture and shrinking the mixture by 80.3 kg.
80.3kg of the above condensation liquid was charged into a first-stage hydrogenation autoclave, to which 26.8kg of water and 100g of 0.8% Pd/C catalyst were added, and N was added2And H2Respectively replacing for 4 times, introducing hydrogen, controlling the pressure of the reaction kettle to be 2.0MPa and the temperature to be 85 ℃, and finishing the reaction when the reaction does not absorb hydrogen; after the temperature is reduced to room temperature, the reaction solution is subjected to nitrogen pressure filtration, and the catalyst is recovered and reused; standing the filtrate for layering, washing the oil layer with 10kg deionized water for 2 times respectively until the oil layer is neutral to obtain65.2kg of the first-stage hydrogenated oil layer and 51.8kg of the recovered water layer.
And (3) putting 65.2kg of the first-stage hydrogenation oil layer into a second-stage hydrogenation high-pressure kettle, simultaneously adding 60g of a skeletal nickel catalyst, sealing the kettle, replacing, controlling the pressure of the reaction kettle to be 0.8MPa and the temperature to be 90 ℃, and finishing the reaction when the reaction is carried out until hydrogen is not absorbed. 65.2kg of second-stage hydrogenation oil layer is obtained.
65.2kg of the second-stage hydrogenation liquid is put into a 100L stainless kettle, the kettle is vacuumized to 5mmHg, the temperature is slowly increased, aniline and water in the hydrogenation liquid are removed, and when the temperature of the kettle bottom is 210 ℃ and almost no solvent is discharged, the temperature is slightly reduced. 44.4kg aniline and 1.3kg water are obtained. The aniline content by liquid spectrum analysis is 99.2%. And (3) putting the crude product after the aniline removal into a 10L stainless steel kettle, performing simple distillation in batches, gradually raising the temperature, controlling the discharging speed by heating, switching the fractions in the process, collecting the front fraction and the main fraction, cooling after the reaction is finished, and emptying to obtain 1.1kg of kettle residue. 1.8kg of front cut fraction, liquid chromatography content: 79.5% of BA, 27.0% of 4-ADPA and 2.9% of PHZ; 16.3kg of main fraction, liquid chromatography content: 4-ADPA 99.46%, PHZ 0.38%. The yield of the main fraction was 88.11%, and the total yield was 90.75%.
The results of comparing the catalytic performance of the mono-and bis-quaternary ammonium bases under the same use conditions in the above application examples and comparative application examples are shown in Table 3.
TABLE 3 Overall comparison of catalytic batch and continuous Performance of Mono-and BiQuaternary ammonium bases
Figure G2009102502035D0000291
Application example 3
Investigation of the Effect of Water on the conversion of the condensation reaction
(1) Ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) is used as catalyst
167g of 35% ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) aqueous solution and 279g of aniline are put into a 500mL four-necked flask, and 44g of aniline is dehydrated at a negative pressure of 35mmHg and a temperature of 45-60 ℃ to form salt. After salifying, the negative pressure is adjusted to 60mmHg, 61.5g of nitrobenzene is slowly dripped for about 2 hours at the temperature of 72 ℃ for condensation and dehydration, the temperature is kept for 1 hour after the dripping of the nitrobenzene, and 50g of water is distilled out after the temperature is kept. After the reaction, the nitrobenzene conversion rate was 99.8% and the system water content was 8.5%.
(2) Tetramethyl ammonium hydroxide is selected as catalyst
169g of 35% tetramethylammonium hydroxide aqueous solution and 279g of aniline are put into a 500mL four-necked flask, and 44g of aniline is dehydrated by heating to 45-60 ℃ under negative pressure of 35mmHg to form a salt. After the salification, the negative pressure is adjusted to 60mmHg, 61.5g of nitrobenzene is slowly dripped for about 2 hours at the temperature of 72 ℃ for condensation and dehydration, the temperature is kept for 1 hour after the dripping of the nitrobenzene, and 73.7g of water is distilled after the temperature is kept. After the reaction, the conversion rate of nitrobenzene is 99.5 percent, and the water content of the system is 3.2 percent.
(3) Tetramethyl ammonium hydroxide and ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) are mixed and used according to equal molar ratio
169g of an aqueous solution containing 29.6g of tetramethylammonium hydroxide and 29.0g of ethyl-alpha, beta-bis (trimethylammonium hydroxide), 279g of aniline, and 44g of dehydrated salt are put into a 500mL four-necked flask under a negative pressure of 35mmHg and heated to 45-60 ℃. After the salification, the negative pressure is adjusted to 60mmHg, 61.5g of nitrobenzene is slowly dripped for about 2 hours at the temperature of 72 ℃ for condensation and dehydration, the temperature is kept for 1 hour after the dripping of the nitrobenzene, and 71.7g of water is distilled after the temperature is kept. After the reaction, the conversion rate of nitrobenzene is 99.5 percent, and the water content of the system is 1.7 percent.
The effect of water on the condensation conversion in the above 3 base systems is shown in Table 4.
TABLE 4 Effect of Water on condensation conversion in different base systems
Alkali system Water content/% of the reaction-terminated System Conversion rate/%
Ethyl-alpha, beta-bis (trimethylammonium hydroxide) 8.5 99.8
Tetramethyl ammonium hydroxide 1.5 99.5
Ethyl-alpha, beta-bis (trimethyl ammonium hydroxide) and tetramethyl ammonium hydroxide in equal molar ratio 3.2 99.5
As can be seen from Table 4, as the ratio of the bis-quaternary ammonium hydroxide catalyst was increased, the water content of the reaction system at the end of the reaction was increased. The use of the diquaternary ammonium hydroxide catalyst of the present invention allows the range of allowable water content in the reaction mixture at the end of the reaction to be wide, and satisfactory yield can be obtained even when the system contains a relatively high amount of water. Because the water content is less in the later stage of the reaction, the dehydration efficiency is lower, and the difficulty of the reaction is reduced by the method. If only tetramethyl ammonium hydroxide is used as a catalyst, the system needs to be dehydrated to below 2 percent, and the nitrobenzene conversion rate is 99 percent, which brings difficulty to the control of the reaction and increases energy consumption.

Claims (15)

1. A bis-quaternary ammonium base compound having the structure shown in formula I:
Figure F2009102502035C0000011
wherein,
R1and R2Independently of one another, a hydrocarbon radical from C1 to C18;
R3、R4、R5and R6Independently of one another, a linear or branched hydrocarbon radical having from C1 to C6;
R7is C2-C6 alkylene or alkoxy substituted C2-C6 alkylene, the alkoxy is methoxy, ethoxy, propoxy, isopropoxy, - (OCH)2CH2)nOH or- (OCH (CH)3)CH2)nOH, wherein n is 1-6.
2. The bis-quaternary ammonium base compound according to claim 1, wherein R is1And R2Independently of one another, a hydrocarbon radical from C1 to C12;
R3、R4、R5and R6Independently of one another, a linear or branched hydrocarbon radical having from C1 to C3;
R7is C2-C4 alkylene or alkoxy substituted C2-C4 alkylene, the alkoxy is methoxy, ethoxy, propoxy, isopropoxy, - (OCH)2CH2)nOH or- (OCH (CH)3)CH2)nOH, wherein n is 1-2.
3. The bis-quaternary ammonium base compound according to claim 2, wherein R is1And R2Independently of one another, methyl, ethyl, n-propyl, isopropyl, allyl or butyl; r3、R4、R5And R6Independently of one another, methyl, ethyl or propyl; r7Is ethylene, propylene, butylene, 2-methoxypropylene, 2-ethoxypropylene or 2-hydroxyethoxypropylene.
4. A method of synthesizing the bis-quaternary ammonium base compound of claim 1, comprising the steps of:
the bis-quaternary ammonium salt of formula II
Figure F2009102502035C0000012
The quaternary ammonium salt and hydroxide or oxide of alkali metal or alkaline earth metal are subjected to ion exchange in the presence of a solvent to prepare the quaternary ammonium salt, the molar ratio of the quaternary ammonium salt to the hydroxide or oxide of alkali metal or alkaline earth metal is 1: 1.0-1: 4.0, the solvent is C1-C4 straight chain and/or branched chain alcohol, the using amount of the solvent is 1-15 times of the weight of the quaternary ammonium salt, the reaction temperature is 20-150 ℃, the reaction time is 1-10 hours, and the reaction is carried out under normal pressure;
wherein,
R1and R2Independently of one another, a hydrocarbon radical from C1 to C18;
R3、R4、R5and R6Independently of one another, a linear or branched hydrocarbon radical having from C1 to C6;
R7is C2-C6 alkylene or alkoxy substituted C2-C6 alkylene, the alkoxy is methoxy, ethoxy, propoxy, isopropoxy, - (OCH)2CH2)nOH or- (OCH (CH)3)CH2)nOH, wherein n is 1-6;
X-is a halide, sulfate, bisulfate, carbonate, bicarbonate, oxalate, phosphate, carboxylate, alkyl-substituted sulfate, carbonate or oxalate.
5. The method of synthesizing bis-quaternary ammonium base compounds according to claim 4,
the R is1And R2Independently of one another, a hydrocarbon radical from C1 to C12;
R3、R4、R5and R6Independently of one another, a linear or branched hydrocarbon radical having from C1 to C3;
R7is C2-C4 alkylene or alkoxy substituted C2-C4 alkylene, the alkoxy is methoxy, ethoxy, propoxy, isopropoxy, - (OCH)2CH2)nOH or- (OCH (CH)3)CH2)nOH, wherein n is 1-2;
the halide is chloride, bromide or iodide; the carboxylate is formate, acetate, propionate; the alkyl-substituted sulfate, carbonate or oxalate is methyl sulfate, ethyl sulfate, methyl carbonate, ethyl carbonate, methyl oxalate or ethyl oxalate.
6. The method of synthesizing bis-quaternary ammonium base compounds according to claim 5, wherein R is1And R2Independently of one another, methyl, ethyl, n-propyl, isopropyl, allyl or butyl; r3、R4、R5And R6Independently of one another, methyl, ethyl or propyl; r7Is ethylene, propylene, butylene, 2-methoxypropylene, 2-ethoxypropylene or 2-hydroxyethoxypropylene; x-Is chloride, bromide, sulfate, carbonate or oxalate.
7. The method of synthesizing bis-quaternary ammonium base compounds according to claim 4, wherein the hydroxide or oxide of an alkali metal or alkaline earth metal is sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium oxide, potassium oxide, calcium oxide, or barium oxide; the solvent is one or more of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
8. The method for synthesizing a diquaternary ammonium base compound according to claim 4, wherein the molar ratio of the diquaternary ammonium salt to the hydroxide or oxide of the alkali metal or the alkaline earth metal is 1: 1.8-1: 2.5, the amount of the solvent is 3-10 times of the weight of the diquaternary ammonium salt, the reaction temperature is 30-100 ℃, and the reaction time is 1.5-6 hours.
9. The method of synthesizing a diquaternary ammonium salt compound according to claim 4, wherein the synthesis of the diquaternary ammonium salt compound comprises the steps of:
(1) firstly, dihalohydrocarbon reacts with dialkyl amine in the presence of solvent to generate N, N, N ', N' -tetraalkyl alkylene diamine; the molar ratio of the dihalogenated hydrocarbon to the dialkylamine is 1: 1.0-1: 4.0, the reaction temperature is 10-200 ℃, the reaction time is 2-20 h, and the reaction pressure is 0-2 MPa;
(2) adding halogenated hydrocarbon into the N, N, N ', N' -tetraalkyl alkylene diamine obtained by the reaction, and carrying out addition reaction in the presence of a solvent to obtain biquaternary ammonium salt; the molar ratio of the N, N, N ', N' -tetraalkylalkylene diamine to the halogenated hydrocarbon is 1: 1.0-1: 4.0, the reaction temperature is 30-200 ℃, the reaction time is 3-20 h, and the reaction pressure is 0-1.5 MPa;
wherein,
the dihalo-hydrocarbon is 1, 2-dichloroethane, 1, 2-dibromoethane, 1-chloro-2-bromoethane, 1, 3-dichloropropane, 1, 3-dichloro-2-propanol, 1, 3-dichloro-2-methoxypropane, 1, 4-dibromobutane, 1, 4-dichlorobutane, 1, 4-dichloro-2-butene or 1, 4-dibromo-2-butene;
the dialkylamine is dimethylamine, diethylamine, dipropylamine or dibutylamine;
the halogenated hydrocarbon is methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, allyl chloride, allyl bromide, chlorobutane, butyl bromide, 1-chloro-2-butene, 1-bromo-2-butene or dodecyl bromide;
the solvent is one or more of water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
10. The method for synthesizing bis-quaternary ammonium base compounds according to claim 9, wherein the molar ratio of the dihalo-hydrocarbon to the dialkylamine in step (1) is 1: 1.8 to 1: 2.5, the reaction temperature is 30 to 120 ℃, the reaction time is 2 to 12 hours, and the reaction pressure is 0 to 1.0 MPa; in the step (2), the molar ratio of the N, N, N ', N' -tetraalkylalkylene diamine to the halogenated hydrocarbon is 1: 1.8-1: 2.5, the reaction temperature is 40-150 ℃, the reaction time is 4-12 h, and the reaction pressure is 0-1.0 MPa.
11. The method of synthesizing a diquaternary ammonium salt compound according to claim 4, wherein the synthesis of the diquaternary ammonium salt compound comprises the steps of:
dihalogenated hydrocarbon and trialkylamine are used as raw materials and react in the presence of a solvent to prepare biquaternary ammonium salt; the molar ratio of the dihalogenated hydrocarbon to the trialkylamine is 1: 1.0-1: 4.0, the reaction temperature is 10-180 ℃, the reaction time is 1-20 h, and the reaction pressure is 0-3 MPa;
wherein,
the dihalo-hydrocarbon is 1, 2-dichloroethane, 1, 2-dibromoethane, 1-chloro-2-bromoethane, 1, 3-dichloropropane, 1, 3-dichloro-2-propanol, 1, 3-dichloro-2-methoxypropane, 1, 4-dibromobutane, 1, 4-dichlorobutane, 1, 4-dichloro-2-butene or 1, 4-dibromo-2-butene;
the trialkylamine is trimethylamine, dodecyldimethylamine, hexadecyldimethylamine, triethylamine, dodecyldiethylamine, hexadecyldiethylamine, tripropylamine, dodecyldipropylamine, hexadecyldipropylamine or tributylamine;
the reaction solvent is one or more of water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
12. The method for synthesizing bis-quaternary ammonium base compounds according to claim 11, wherein the molar ratio of the dihalogenated hydrocarbon to the trialkylamine is 1: 1.8 to 1: 2.5, the reaction temperature is 30 to 120 ℃, the reaction time is 3 to 12 hours, and the reaction pressure is 0 to 1.5 MPa.
13. The method of synthesizing a diquaternary ammonium salt compound according to claim 4, wherein the synthesis of the diquaternary ammonium salt compound comprises the steps of:
reacting N, N, N ', N' -tetraalkyl alkylene diamine and dibasic acid dimethyl or ethyl ester in a solvent to prepare biquaternary ammonium salt; the molar ratio of the tetraalkylalkylene diamine to the dibasic acid dimethyl or ethyl ester is 1: 1.0-1: 4.0, the reaction temperature is 10-200 ℃, the reaction time is 2-20 h, and the reaction pressure is 0-3 MPa;
wherein,
the dibasic acid dimethyl or ethyl ester is dimethyl sulfate, diethyl sulfate, dimethyl carbonate, diethyl carbonate, dimethyl oxalate, diethyl oxalate, dimethyl phosphate or diethyl phosphate;
the reaction solvent is one or more of water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
14. The method for synthesizing bis-quaternary ammonium base compounds according to claim 13, wherein the molar ratio of the tetraalkylalkylenediamine to the diacid dimethyl or ethyl ester is 1: 1.8 to 1: 2.5; the reaction temperature is 50-150 ℃; the reaction time is 3-12 h; the reaction pressure is 0.1-2.0 MPa.
15. The use of a bis-quaternary ammonium base compound according to any one of claims 1 to 3 as a condensation catalyst for the condensation of nitrobenzene and aniline followed by hydrogenation to synthesize 4-aminodiphenylamine.
CN200910250203A 2009-12-08 2009-12-08 Double quaternary ammonium base compound and preparation method as well as application thereof Pending CN101717339A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN200910250203A CN101717339A (en) 2009-12-08 2009-12-08 Double quaternary ammonium base compound and preparation method as well as application thereof
PCT/CN2009/076245 WO2011069309A1 (en) 2009-12-08 2009-12-30 Di-quaternary ammonium base compound and its preparation method and use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910250203A CN101717339A (en) 2009-12-08 2009-12-08 Double quaternary ammonium base compound and preparation method as well as application thereof

Publications (1)

Publication Number Publication Date
CN101717339A true CN101717339A (en) 2010-06-02

Family

ID=42431984

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910250203A Pending CN101717339A (en) 2009-12-08 2009-12-08 Double quaternary ammonium base compound and preparation method as well as application thereof

Country Status (2)

Country Link
CN (1) CN101717339A (en)
WO (1) WO2011069309A1 (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101830811A (en) * 2010-02-23 2010-09-15 江苏扬农化工集团有限公司 Preparation method of 4-aminodiphenylamine
CN101870659A (en) * 2010-07-20 2010-10-27 江苏扬农化工集团有限公司 Preparation method for tetra-alkyl ammonium hydroxide and application
CN102309985A (en) * 2011-10-12 2012-01-11 大连理工大学 Highly active catalyst used for hydrosilation reaction of aldehyde and trimethylsilyl cyanide
US20120157713A1 (en) * 2010-12-21 2012-06-21 Korea Kumho Petrochemical Co., Ltd. Method for preparation of 4,4'-dinitrodiphenylamine and 4,4'-bis(alkylamino)diphenylamine with the base catalyst complex
CN102533238A (en) * 2012-01-06 2012-07-04 西南石油大学 Block polyether quaternary ammonium salt surfactant and preparation method thereof
US8759587B2 (en) 2010-12-21 2014-06-24 Korea Kumho Petrochemical Co., Ltd. Method for preparation of 4,4′-dinitrodiphenylamine and 4,4′-bis(alkylamino)diphenylamine by using 4-nitroaniline
CN103936634A (en) * 2014-05-14 2014-07-23 中国石油化工股份有限公司 Synthesis method and application of Gemini surfactant
CN105017032A (en) * 2015-03-27 2015-11-04 河南维诺生物科技有限公司 Organic diammonium compound, as well as synthetic method and use thereof
CN105647500A (en) * 2016-02-24 2016-06-08 李�诚 Molecular deposition film oil displacement agent as well as preparation method and application thereof
CN107118107A (en) * 2017-06-23 2017-09-01 中国科学院武汉物理与数学研究所 1,3 Hexaethyl hydroxide propane diamine and preparation method and application
CN107235846A (en) * 2017-06-23 2017-10-10 中国科学院武汉物理与数学研究所 Isosorbide-5-Nitrae Hexaethyl hydroxide butanediamine and preparation method and application
CN107243294A (en) * 2017-07-14 2017-10-13 泉州坤莎新材料科技有限公司 A kind of Bis-quaternary Ammonium Salt Surfactant and its synthetic method
CN107434769A (en) * 2016-05-26 2017-12-05 中国石油化工股份有限公司 A kind of 4-aminodiphenylamine produces desalination method
CN108499508A (en) * 2018-06-04 2018-09-07 绍兴东湖高科股份有限公司 A kind of multipoles reactors and the method for preparing cycocel using the device
CN108558675A (en) * 2018-04-25 2018-09-21 南通理工学院 Synthesis method of 4-aminodiphenylamine
CN109529921A (en) * 2018-11-15 2019-03-29 太原理工大学 Hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve, Ni type method for preparing catalyst
CN109535015A (en) * 2018-11-11 2019-03-29 广州市金浪星非织造布有限公司 A kind of four ethoxy dibromo propane-diammonium of double octadecyls and preparation method thereof
CN111500269A (en) * 2020-06-08 2020-08-07 保定市三拓化工产品有限公司 Drilling fluid filtrate reducer
CN111808598A (en) * 2020-08-26 2020-10-23 肯特催化材料股份有限公司 Clay anti-swelling agent
CN112341338A (en) * 2019-08-07 2021-02-09 中石化南京化工研究院有限公司 Catalytic hydrogenation method of 4-nitrodiphenylamine and 4-nitrosodiphenylamine
CN112439454A (en) * 2019-09-05 2021-03-05 中石化南京化工研究院有限公司 RT base condensation catalyst and preparation method thereof
CN112441928A (en) * 2019-09-05 2021-03-05 中石化南京化工研究院有限公司 Preparation method of RT base condensation liquid
CN113233986A (en) * 2021-05-31 2021-08-10 中石化南京化工研究院有限公司 Method for removing salt from condensation liquid in water phase in RT base production
CN114308122A (en) * 2022-01-12 2022-04-12 万华化学集团股份有限公司 Quaternary ammonia base phase transfer catalyst, preparation method and application thereof in preparation of 1, 3-di (2-hydroxy isopropyl) benzene
CN116410348A (en) * 2023-04-03 2023-07-11 华侨大学 Preparation method of chitosan quaternary ammonium salt

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5117063A (en) * 1991-06-21 1992-05-26 Monsanto Company Method of preparing 4-aminodiphenylamine
CA2454603A1 (en) * 2001-07-23 2003-02-06 Flexsys America L.P. Process for preparing 4-aminodiphenylamine
CN1228310C (en) * 2003-07-04 2005-11-23 兰溪市钱塘合成新材料有限公司 Method for preparing tetraalkylammonium hydroxide

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101830811B (en) * 2010-02-23 2013-04-03 江苏扬农化工集团有限公司 Preparation method of 4-aminodiphenylamine
CN101830811A (en) * 2010-02-23 2010-09-15 江苏扬农化工集团有限公司 Preparation method of 4-aminodiphenylamine
CN101870659A (en) * 2010-07-20 2010-10-27 江苏扬农化工集团有限公司 Preparation method for tetra-alkyl ammonium hydroxide and application
US8835687B2 (en) * 2010-12-21 2014-09-16 Korea Kumho Petrochemical Co., Ltd. Method for preparation of 4,4′-dinitrodiphenylamine and 4,4′-bis(alkylamino)diphenylamine with the base catalyst complex
US20120157713A1 (en) * 2010-12-21 2012-06-21 Korea Kumho Petrochemical Co., Ltd. Method for preparation of 4,4'-dinitrodiphenylamine and 4,4'-bis(alkylamino)diphenylamine with the base catalyst complex
US8759587B2 (en) 2010-12-21 2014-06-24 Korea Kumho Petrochemical Co., Ltd. Method for preparation of 4,4′-dinitrodiphenylamine and 4,4′-bis(alkylamino)diphenylamine by using 4-nitroaniline
CN102309985A (en) * 2011-10-12 2012-01-11 大连理工大学 Highly active catalyst used for hydrosilation reaction of aldehyde and trimethylsilyl cyanide
CN102533238A (en) * 2012-01-06 2012-07-04 西南石油大学 Block polyether quaternary ammonium salt surfactant and preparation method thereof
CN103936634B (en) * 2014-05-14 2016-05-25 中国石油化工股份有限公司 A kind of synthetic method of Gemini surface active agent
CN103936634A (en) * 2014-05-14 2014-07-23 中国石油化工股份有限公司 Synthesis method and application of Gemini surfactant
CN105017032A (en) * 2015-03-27 2015-11-04 河南维诺生物科技有限公司 Organic diammonium compound, as well as synthetic method and use thereof
CN105647500A (en) * 2016-02-24 2016-06-08 李�诚 Molecular deposition film oil displacement agent as well as preparation method and application thereof
CN107434769B (en) * 2016-05-26 2019-09-17 中国石油化工股份有限公司 A kind of 4-aminodiphenylamine production desalination method
CN107434769A (en) * 2016-05-26 2017-12-05 中国石油化工股份有限公司 A kind of 4-aminodiphenylamine produces desalination method
CN107118107A (en) * 2017-06-23 2017-09-01 中国科学院武汉物理与数学研究所 1,3 Hexaethyl hydroxide propane diamine and preparation method and application
CN107235846A (en) * 2017-06-23 2017-10-10 中国科学院武汉物理与数学研究所 Isosorbide-5-Nitrae Hexaethyl hydroxide butanediamine and preparation method and application
CN107243294A (en) * 2017-07-14 2017-10-13 泉州坤莎新材料科技有限公司 A kind of Bis-quaternary Ammonium Salt Surfactant and its synthetic method
CN108558675A (en) * 2018-04-25 2018-09-21 南通理工学院 Synthesis method of 4-aminodiphenylamine
CN108499508A (en) * 2018-06-04 2018-09-07 绍兴东湖高科股份有限公司 A kind of multipoles reactors and the method for preparing cycocel using the device
CN109535015A (en) * 2018-11-11 2019-03-29 广州市金浪星非织造布有限公司 A kind of four ethoxy dibromo propane-diammonium of double octadecyls and preparation method thereof
CN109529921A (en) * 2018-11-15 2019-03-29 太原理工大学 Hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve, Ni type method for preparing catalyst
CN109529921B (en) * 2018-11-15 2021-12-07 太原理工大学 Preparation method of hierarchical pore Beta molecular sieve and Ni type catalyst for hydrogen production by ethanol steam reforming
CN112341338B (en) * 2019-08-07 2023-09-08 中石化南京化工研究院有限公司 Catalytic hydrogenation method for 4-nitrodiphenylamine and 4-nitrosodiphenylamine
CN112341338A (en) * 2019-08-07 2021-02-09 中石化南京化工研究院有限公司 Catalytic hydrogenation method of 4-nitrodiphenylamine and 4-nitrosodiphenylamine
CN112439454A (en) * 2019-09-05 2021-03-05 中石化南京化工研究院有限公司 RT base condensation catalyst and preparation method thereof
CN112441928A (en) * 2019-09-05 2021-03-05 中石化南京化工研究院有限公司 Preparation method of RT base condensation liquid
CN112439454B (en) * 2019-09-05 2023-04-07 中国石油化工股份有限公司 RT base condensation catalyst and preparation method thereof
CN112441928B (en) * 2019-09-05 2023-06-20 中国石油化工股份有限公司 Preparation method of RT pessary condensation liquid
CN111500269A (en) * 2020-06-08 2020-08-07 保定市三拓化工产品有限公司 Drilling fluid filtrate reducer
CN111500269B (en) * 2020-06-08 2022-06-28 保定市三拓化工产品有限公司 Filtrate reducer for drilling fluid
CN111808598B (en) * 2020-08-26 2022-05-20 肯特催化材料股份有限公司 Clay anti-swelling agent
CN111808598A (en) * 2020-08-26 2020-10-23 肯特催化材料股份有限公司 Clay anti-swelling agent
CN113233986A (en) * 2021-05-31 2021-08-10 中石化南京化工研究院有限公司 Method for removing salt from condensation liquid in water phase in RT base production
CN114308122A (en) * 2022-01-12 2022-04-12 万华化学集团股份有限公司 Quaternary ammonia base phase transfer catalyst, preparation method and application thereof in preparation of 1, 3-di (2-hydroxy isopropyl) benzene
CN114308122B (en) * 2022-01-12 2023-12-29 万华化学集团股份有限公司 Quaternary ammonia base phase transfer catalyst, preparation method and application thereof in preparation of 1, 3-di (2-hydroxyisopropyl) benzene
CN116410348A (en) * 2023-04-03 2023-07-11 华侨大学 Preparation method of chitosan quaternary ammonium salt

Also Published As

Publication number Publication date
WO2011069309A1 (en) 2011-06-16

Similar Documents

Publication Publication Date Title
CN101717339A (en) Double quaternary ammonium base compound and preparation method as well as application thereof
CN102795970B (en) Clean, environmentally-friendly and economical bisphenol fluorene synthesizing method
CN107778183B (en) Preparation method of 2,4, 6-trifluorobenzylamine
CN111662185A (en) Synthesis method of N-methyl o-fluoroaniline
WO2011145867A2 (en) Method for preparing alkyl lactate, and method for preparing lactamide by using same
CN106748763B (en) The method of two kettles joint phase-transfer Wittig reaction methyl benzoate
CN117658831A (en) Preparation method of m-hydroxylamine intermediate 2-amino-1- (3- (benzyloxy) phenyl) propanol
CN101830811A (en) Preparation method of 4-aminodiphenylamine
CN106748630A (en) A kind of synthetic method of antalgesic intermediate Bromomethylcyclobutane
CN110776475A (en) A kind of synthetic method of oxadiazon
CN109956884A (en) A kind of preparation method of benzyloxyamine hydrochloride
CN117820135A (en) Method for continuously preparing tert-butylaminoethoxyethanol
CN112409149B (en) Preparation method of benzophenone ultraviolet absorbent
CN104276928A (en) Preparation method of 4,6-bi[1-(4-hydroxypheny)-1-methyl ethyl]-1,3-hydroquinone
CN116284031A (en) A kind of preparation method of R-glabridin
CN104262189A (en) Method for liquid-phase preparation of high-purity N, N-diethylformamide
CN114716331A (en) Preparation method of dopamine hydrochloride
CN111072500A (en) Preparation method of ambroxol hydrochloride
CN106957235B (en) A kind of preparation method of tamoxifen
CN107118104B (en) A kind of preparation method of three long aliphatic hydrocarbon chain ammonium carbonate salts of methyl
CN115286519B (en) Preparation method of 4,4' -bis (3-aminophenoxy) biphenyl
CN114478315B (en) Method for catalytic reduction of irosartan biphenyl waste residues by using halogen-modified Pd/C catalyst
CN115448858B (en) Efficient synthesis process of 2-chloroethyl sodium sulfonate
CN108929273A (en) A kind of preparation method of imidazole ethyl vanillic acid ether sodium salt
CN110590576A (en) Preparation method of 4-polyfluoro methoxy o-phenylenediamine

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20100602