CN113214187A - Method for preparing sulfenamide rubber vulcanization accelerator by heterogeneous catalysis and molecular oxygen oxidation - Google Patents

Method for preparing sulfenamide rubber vulcanization accelerator by heterogeneous catalysis and molecular oxygen oxidation Download PDF

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CN113214187A
CN113214187A CN202010255718.0A CN202010255718A CN113214187A CN 113214187 A CN113214187 A CN 113214187A CN 202010255718 A CN202010255718 A CN 202010255718A CN 113214187 A CN113214187 A CN 113214187A
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vulcanization accelerator
preparing
rubber vulcanization
molecular oxygen
sulfenamide
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CN113214187B (en
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郭亚菲
董乐
段永华
齐凯言
马军营
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Henan University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/76—Sulfur atoms attached to a second hetero atom
    • C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract

The invention relates to a method for preparing a sulfenamide rubber vulcanization accelerator by heterogeneous catalysis molecular oxygen oxidation, which belongs to the field of chemical industry and comprises the step of taking a heterogeneous metal cobalt-based nano material as a catalyst, and reacting a sulfhydryl compound and amines in an organic phase for 0.5-16 hours under the conditions of 1-7 atmospheric pressures and the temperature of 40-100 ℃ in an oxygen or air environment to prepare the sulfenamide rubber vulcanization accelerator. The catalyst has the characteristics of high catalytic activity, high reaction efficiency, low price, easy obtaining and repeated use; the method has the advantages of simple synthesis steps of sulfenamide, high conversion rate and few byproducts, and is more suitable for industrial production.

Description

Method for preparing sulfenamide rubber vulcanization accelerator by heterogeneous catalysis and molecular oxygen oxidation
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for preparing a sulfenamide rubber vulcanization accelerator by heterogeneous catalysis and molecular oxygen oxidation.
Background
The sulfenamide rubber accelerator synthesized by taking 2-mercaptobenzothiazole as a matrix is a vulcanization accelerator widely applied at present, and the two most common rubber vulcanization accelerators used at home and abroad are N-tert-butyl-2-benzothiazole sulfenamide (TBBS) and N-cyclohexyl-2-benzothiazole sulfenamide (CBS). TBBS has become the leading accelerant variety in foreign markets. The synthetic method of the sulfenamide rubber accelerator comprises a sodium hypochlorite oxidation method, a catalytic oxidation method, a hydrogen peroxide oxidation method, an electrolytic oxidation method, a chlorine oxidation method and the like.
The sodium hypochlorite oxidation method is a method which is adopted in the current domestic and overseas production, tert-butylamine and 2-mercaptobenzothiazole (M) are used as raw materials, and sodium hypochlorite is dripped for oxidation reaction. Has the advantages of simplicity, easy control, low cost, high conversion rate and yield of raw materials and the like. However, the method is difficult to recover tert-butylamine, generates a large amount of inorganic salt wastewater, is not favorable for environment and is inconsistent with the national green chemistry idea and the production requirements of energy conservation and emission reduction.
The hydrogen peroxide oxidation method is to use hydrogen peroxide to replace sodium hypochlorite for oxidation, and 2-mercaptobenzothiazole and tert-butylamine are used for generating TBBS. The method avoids the generation of a large amount of chlorine-containing wastewater in the production process, does not need sewage treatment, reduces the production cost, but has high reaction temperature, causes the volatilization waste of the tert-butylamine, is unfavorable for the environment, and simultaneously brings a series of production safety problems due to the gradual accumulation of the hydrogen peroxide in a system.
The sulfenamide rubber accelerator prepared by catalytic oxidation of 2-mercaptobenzothiazole by molecular oxygen (oxygen or air) has fewer related reports, is a green and environment-friendly process route due to the advantages of low cost, green process, no pollution and the like, has huge development potential, and is more and more emphasized. Chinese patent CN 106866577B reports a cobalt phthalocyanine catalyst, but the method is a homogeneous catalyst, and a heterogeneous catalyst is convenient to recycle and is more suitable for industrial production. Therefore, the development of a high-activity heterogeneous catalyst is an urgent need for the development of a green process of a sulfenamide promoter.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a method for preparing a sulfenamide rubber vulcanization accelerator by heterogeneous catalytic molecular oxygen oxidation. The method is environment-friendly, the adopted heterogeneous catalyst can be recycled for multiple times, and the reaction efficiency is high.
In order to achieve the purpose, the invention adopts the specific scheme that:
a method for preparing a sulfenamide rubber vulcanization accelerator by heterogeneous catalysis and molecular oxygen oxidation comprises the steps of taking a heterogeneous metal cobalt-based nano material as a catalyst, taking oxygen or air as an oxidant, enabling 2-mercaptobenzothiazole and an amine compound to generate oxidation cross coupling reaction in an organic solvent, enabling the reaction temperature to be 40-100 ℃ and the reaction time to be 0.5-16h, cooling and filtering after the reaction is finished, separating a mother liquor from the catalyst after filtering, extracting the mother liquor, and passing through a silica gel column to obtain a pure product, namely the sulfenamide rubber vulcanization accelerator.
The metal element type contained in the catalyst is single metal Co or Co-containing polymetallic, and the Co-containing polymetallic also contains at least one of Ag, Au, Ce, Cs, Cu, Fe, Ni, Pd, Zn and Mn besides Co.
As a further optimization of the above scheme, the organic solvent is selected from dimethyl sulfoxide, tert-butanol or dimethylformamide.
As a further optimization of the above scheme, the amine compound is used in an amount of 1-4 equivalents based on 2-mercaptobenzothiazole. The amine compound is tert-butylamine or cyclohexylamine.
As a further optimization of the above scheme, the partial pressure of oxygen in the oxidant is 1-7 atm.
As a further optimization of the scheme, organic base or inorganic base is added in the reaction process, and the dosage of the organic base or the inorganic base is less than or equal to 1.0 equivalent of that of the 2-mercaptobenzothiazole; still further, the inorganic base is potassium carbonate.
Has the advantages that:
1. the invention adopts the heterogeneous metal nano catalyst, and after the product is separated after the oxidation reaction is finished, the catalyst can be repeatedly used, so that the cost can be obviously reduced, the pollution is small, and the method is suitable for industrial production.
2. According to the preparation method, the oxidation cross-coupling reaction is carried out in an organic phase; the catalyst has high catalytic activity, high reaction efficiency and simple recovery operation, and can be repeatedly used; the synthesis process is simple, the product selectivity is high, and the byproducts are few; less waste, environment-friendly and has stronger industrial application prospect.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the rubber vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide (TBBS) prepared by the method of the invention.
Detailed Description
A method for preparing a sulfenamide rubber accelerator by catalyzing molecular oxygen oxidation in an organic solvent comprises the step of enabling 2-mercaptobenzothiazole and an amine compound to perform oxidation cross-coupling reaction for 0.5-16 hours in an organic phase under the conditions of pressure of 1-5 atmospheric pressures and temperature of 40-100 ℃ by taking a heterogeneous metal cobalt-based nano material as a catalyst in an oxygen or air environment to generate the sulfenamide compound.
The organic solvent is dimethyl sulfoxide, tert-butyl alcohol, dimethylformamide and the like, but is not limited to the above.
The amine compound is tert-butylamine or cyclohexylamine, and the using amount of the amine compound is 1-4 equivalents of 2-mercaptobenzothiazole. If tert-butylamine is used, the product is N-tert-butyl-2-benzothiazolesulfenamide (TBBS); if cyclohexylamine is used, the product is N-cyclohexyl-2-benzothiazolesulfenamide (CBS).
In the invention, the addition of alkali in the reaction process is promoted, the types of the alkali comprise organic alkali and inorganic alkali, and the addition amount is 0-1.0 equivalent of that of the 2-mercaptobenzothiazole.
After the synthesis reaction is finished, the post-treatment process is simple, and the product can be separated and purified by the following method: after the oxidation reaction is finished, cooling, separating the mother liquor from the catalyst after filtration, extracting, and passing through a silica gel column to obtain a pure product, as shown in figure 1.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1:
1 mmol of 2-mercaptobenzothiazole and 4mmol of tert-butylamine, 0.2 mmol of potassium carbonate, 0.05 g of a metallic Co-Cu nanocatalyst, and 10 ml of tert-butanol were charged in a 38 ml reaction tube with a branch tube, and 0.1 MPa of O was charged2Magnetically stir at 70 ℃ for 15 hours. After the reaction was stopped, the solid catalyst was removed by filtration, extracted, dried, passed through a silica gel column, and dried to give the product in 95% yield and 89% isolated yield by gas chromatography. The catalyst obtained after filtration can be reused for many times after being washed and dried.
Example 2:
2 mmol of 2-mercaptobenzothiazole and 4.5 mmol of tert-butylamine, 0.1 mmol of potassium carbonate, 0.05 g of metallic Co nano-catalyst, and 10 ml of dimethylformamide are added into a 38 ml reaction tube with a branch tube, and 0.1 MPa of O is filled in2Magnetically stirred at 100 ℃ for 0.5 hour. After the reaction was stopped, the product was obtained by extraction, drying, passing through a silica gel column and drying, and the yield was 93% and the isolated yield was 87% as determined by gas chromatography. The catalyst obtained after filtration can be reused for many times after being washed and dried.
Example 3:
1 mmol of 2-mercaptobenzothiazole and 2 mmol of tert-butylamine, 0.1 mmol of sodium methoxide, 0.05 g of metallic Co-Mn nano catalyst and 10 ml of dimethyl sulfoxide solvent are added into a 38 ml reaction tube with a branch tube, simultaneously, the reaction tube is vacuumized, charged with 0.1 MPa of oxygen and magnetically stirred for 16 hours at the temperature of 40 ℃. After the reaction is stopped, the solid catalyst is removed by filtration, extracted, dried, passed through a silica gel column, and dried to obtain the product, the yield is 96% by gas chromatography detection, and the isolation yield is 90%. The catalyst obtained after filtration can be reused for many times after being washed and dried.
Example 4:
1 mmol of 2-mercaptobenzothiazole and 4mmol of cyclohexylamine, 0.05 g of metal Co-Zn nano catalyst and 10 ml of dimethyl sulfoxide solvent are added into a reaction test tube, air is filled simultaneously, and the mixture is magnetically stirred for 16 hours at the temperature of 80 ℃. After the reaction was stopped, the solid catalyst was removed by filtration, extracted, dried, passed through a silica gel column, and dried to give the product in a yield of 90% as determined by gas chromatography and an isolated yield of 83%. The catalyst obtained after filtration can be reused for many times after being washed and dried.
Comparative example: 1 mmol of 2-mercaptobenzothiazole and 4mmol of tert-butylamine, 0.5 mmol of potassium carbonate, 0.05 g of metallic Co nano-catalyst and 10 ml of water are added into a 38 ml reaction test tube with a branch pipe, and 0.1 MPa of O is filled into the reaction tube2Magnetically stirred at 70 ℃ for 10 hours. After the reaction was stopped, the solid catalyst was removed by filtration, extracted, dried, passed through a silica gel column, and dried to give the product in a yield of 25% by gas chromatography and an isolated yield of 18%.
It should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.

Claims (8)

1. A method for preparing sulfenamide rubber vulcanization accelerator by heterogeneous catalysis molecular oxygen oxidation is characterized in that: taking a heterogeneous metal cobalt-based nano material as a catalyst, taking oxygen or air as an oxidant, carrying out oxidation cross-coupling reaction on 2-mercaptobenzothiazole and an amine compound in an organic solvent, wherein the reaction temperature is 40-100 ℃, the reaction time is 0.5-16h, cooling and filtering after the reaction is finished, separating a filtered mother solution from the catalyst, extracting the mother solution, and passing through a silica gel column to obtain a pure product, namely the sulfenamide rubber vulcanization accelerator.
2. The method for preparing the sulfenamide rubber vulcanization accelerator by heterogeneous catalysis of molecular oxygen oxidation according to claim 1, wherein: the metal element type contained in the catalyst is single metal Co or Co-containing polymetallic, and the Co-containing polymetallic also contains at least one of Ag, Au, Ce, Cs, Cu, Fe, Ni, Pd and Zn besides Co.
3. The method for preparing the sulfenamide rubber vulcanization accelerator by heterogeneous catalysis of molecular oxygen oxidation according to claim 1, wherein: the organic solvent is selected from dimethyl sulfoxide, tert-butyl alcohol or dimethylformamide.
4. The method for preparing the sulfenamide rubber vulcanization accelerator by heterogeneous catalysis of molecular oxygen oxidation according to claim 1, wherein: the dosage of the amine compound is 1-4 equivalents of 2-mercaptobenzothiazole.
5. The method for preparing the sulfenamide rubber vulcanization accelerator by heterogeneous catalysis of molecular oxygen oxidation according to claim 1, wherein: the amine compound is tert-butylamine or cyclohexylamine.
6. The method for preparing the sulfenamide rubber vulcanization accelerator by heterogeneous catalysis of molecular oxygen oxidation according to claim 1, wherein: the oxygen partial pressure of the oxidant is 1-7 atm.
7. The method for preparing the sulfenamide rubber vulcanization accelerator by heterogeneous catalysis of molecular oxygen oxidation according to claim 1, wherein: adding organic base or inorganic base in the reaction process, wherein the dosage of the organic base or the inorganic base is less than or equal to 1.0 equivalent of that of the 2-mercaptobenzothiazole.
8. The method for preparing the sulfenamide rubber vulcanization accelerator by heterogeneous catalysis of molecular oxygen oxidation according to claim 7, wherein: the inorganic base is potassium carbonate; the organic base is sodium methoxide.
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Cited By (1)

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CN114768882A (en) * 2022-06-20 2022-07-22 科迈(天津)建设工程股份有限公司 Heterogeneous catalyst for producing vulcanization accelerator TBBS by oxygen method and preparation method and application thereof
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