Method for preparing p-phenylenediamine anti-aging agent without hydrogenation
Through the hydrogen-borrowing and hydrogen-returning process without hydrogenation and the use of metal-supported catalysts, the p-phenylenediamine anti-aging agent was successfully prepared, solving the dangerous problems of traditional hydrogenation processes and achieving green and environmentally friendly and efficient production.
Patent Information
- Application Number
- CN202411775322.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-05
- Publication Date
- 2025-03-14
AI Technical Summary
The nitrogen alkylation method of traditional p-phenylenediamine anti-aging agents requires a hydrogenation process, which is characterized by high temperature, high pressure, hydrogen and other characteristics of high risk and high risk, making accidents prone to accidents.
The hydrogen-boring and hydrogen-returning process is adopted without hydrogenation, and a metal-supported catalyst is used to react in a nitrogen atmosphere to prepare a p-phenylenediamine anti-aging agent.
It avoids dangerous hydrogenation processes, has the advantages of green and environmental protection, no waste emissions, and improves production safety and efficiency.
Smart Images
Figure CN119613268A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of preparation of p-phenylenediamine antioxidants, and specifically relates to a method for preparing p-phenylenediamine antioxidants without hydrogenation. Background Art
[0002] P-phenylenediamine antioxidants have a wide range of applications and have protective effects on heat, oxygen, ozone, mechanical fatigue, and harmful metals. They are one of the most important antioxidant types in rubber anti-aging systems. Their general structural formula is shown in Formula I. The main varieties include N-(1,3-dimethylbutyl)-N'-phenyl p-phenylenediamine (antioxidant 6PPD), N-phenyl-N'-isopropyl p-phenylenediamine (antioxidant 4010NA), etc.
[0003]
[0004] The traditional methods of nitrogen alkylation are all reductive amination processes, which require the participation of hydrogenation process. The reaction equation is as follows
[0005]
[0006] The hydrogenation process has the special characteristics of high temperature, high pressure, presence of hydrogen, and high material danger. These factors determine that hydrogenation is a dangerous and high-risk process. Therefore, the probability of major accidents is high. Once an accident occurs, it will cause huge economic losses and casualties. Summary of the invention
[0007] In view of the problems existing in the prior art, the present invention provides a method for preparing a p-phenylenediamine antioxidant without hydrogenation.
[0008] The specific technical solutions are as follows:
[0009] A method for preparing a p-phenylenediamine antioxidant without hydrogenation, characterized in that it comprises the following steps: subjecting compound A and compound B to a hydrogenation reduction process under a nitrogen atmosphere and a metal-supported catalyst to obtain a compound as shown in formula I, wherein the reaction process is as follows:
[0010]
[0011] In the formula, each substituent R1 is independently selected from H, C1-C18 chain hydrocarbon group or C3-C18 alicyclic hydrocarbon group, a is an integer of 1-5; R2, R3, R4, R5 are each independently selected from H, C1-C18 chain hydrocarbon group or C3-C18 alicyclic hydrocarbon group; R6, R7 are each independently selected from C1-C18 chain hydrocarbon group or C3-C18 alicyclic hydrocarbon group, or R6 and R7 form a C3-C18 aliphatic ring.
[0012] Preferably, a is 1, the substituents R1, R2, R3, R4, R5 are each independently selected from H or alkyl, R6, R7 are each independently selected from alkyl, cyclopropane, or R6 and R7 form cyclopentane.
[0013] Furthermore, the metal in the metal-supported catalyst is selected from one or more of Ni, Cu, Fe, Zr, Co, Sn, Cr, Ga, Ge, Pd, Pt, In, Mn, Zn, Ag, La, and Ce, and the carrier in the metal-supported catalyst is selected from one or more of carbon, alumina, silica gel, and molecular sieve.
[0014] Furthermore, the molar ratio of compound A to compound B is 1:6-1:14, preferably 1:8-1:14.
[0015] Furthermore, the reaction temperature is 150-280° C., preferably 200-250° C., the reaction time is 3-12 h, and the nitrogen pressure is 0.5-4 MPa, preferably 1-2 MPa.
[0016] Furthermore, the preparation method of the metal supported catalyst comprises the following steps:
[0017] Step 1, adding an active component precursor to a deionized water solution to a fixed volume to prepare an active component solution;
[0018] Step 2, loading the active component precursor onto the catalyst carrier, impregnating, drying, calcining and reducing to obtain a loaded catalyst, wherein the active component solution is a metal acid solution.
[0019] Furthermore, the active component precursor is loaded on the catalyst carrier by vacuum impregnation, the impregnation temperature is 40-80° C., and the number of impregnations is at least one.
[0020] Furthermore, the drying temperature is 50-100°C, the drying time is 1-48 hours, the calcination temperature is 400-600°C, the calcination time is 1-10 hours, and the reduction is H2 reduction treatment, the reduction temperature is 200°C-300°C, and the reduction time is 1-6 hours.
[0021] Furthermore, based on the total mass of the supported catalyst, the amount of the active component precursor added in terms of metal element is 1-30% (wt).
[0022] The beneficial effects of the present invention are:
[0023] The present invention utilizes the active dehydrogenation and hydrogenation characteristics of the active components of the supported catalyst, and adopts a synthesis method without providing an additional external hydrogen source through a hydrogen-borrowing and hydrogen-reducing reaction process. The synthesis method avoids dangerous hydrogenation processes and has the advantages of being green, environmentally friendly, and free of three wastes. DETAILED DESCRIPTION
[0024] Herein, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all substitutes, improvements and equivalents of the methods and materials described in the present invention can be included in the scope limited by the claims.
[0025] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.
[0026] In this article, chain hydrocarbon refers to a straight chain or branched saturated hydrocarbon or unsaturated hydrocarbon, usually containing Examples of chain hydrocarbon groups include, but are not limited to, methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, vinyl, ethynyl, propenyl, allyl, hexenyl, 1,3-dimethylbutyl, 1,4-dimethylpentyl, tert-octyl, and the like.
[0027] Herein, alicyclic hydrocarbon groups refer to groups in which carbon atoms are linked in a ring, usually containing Examples of alicyclic hydrocarbon groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, norbornenyl, BCP, BCB, BCH, cyclopentadienyl, ethynylcyclohexyl, and adamantyl.
[0028] As used herein, an alkyl group refers to a linear or branched monovalent saturated hydrocarbon group, usually containing Examples of alkyl groups include, but are not limited to, methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, vinyl, and ethynyl.
[0029] Herein, cycloalkyl refers to carbon atoms, preferably containing Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, BCP, cyclopentadienyl, ethynylcyclohexenyl, and adamantyl.
[0030] The present invention finds that polyalkyl p-phenylenediamine compounds having a structure shown in Formula I (referred to as compounds of Formula I) can be used as rubber antioxidants:
[0031]
[0032] In Formula I, each R1 is independently selected from H, C1-C18 chain hydrocarbon group or C3-C18 alicyclic hydrocarbon group, and a is an integer of 1-5;
[0033] R2, R3, R4, and R5 are each independently selected from a C1-C18 chain hydrocarbon group or a C3-C18 alicyclic hydrocarbon group;
[0034] R6 and R7 are each independently selected from a C1-C18 chain hydrocarbon group or a C3-C18 alicyclic hydrocarbon group, or R6 and R7 form a C3-C18 aliphatic ring.
[0035] In some preferred embodiments, each R1 is independently selected from H or C1-C18 alkyl, and in some embodiments, a is 1 or 2. When a is 1, R1 is preferably located at the ortho or para position of the -NH- group, and when a is 2, preferably, two R1s are located at the ortho and meta positions of the -NH- group, respectively.
[0036] In some preferred embodiments, R2, R3, R4, R5 are each independently selected from H or C1-C18 alkyl, and preferably, R2, R3, R4, R5 have In some embodiments, R2, R3, R4, and R5 are each independently selected from C1-C4 alkyl. When three of R2, R3, R4, and R5 are H, preferably, R2 is not H. When two of R2, R3, R4, and R5 are H, preferably, R2 and R4 are not H.
[0037] In some preferred embodiments, R6 and R7 are each independently selected from C1-C18 alkyl or C3-C18 cycloalkyl, or R6 and R7 form a C3-C18 aliphatic ring. Preferably, the aliphatic ring formed by R6 and R7 is a saturated aliphatic ring. In some embodiments, the compound of formula I is selected from:
[0038]
[0039] The compound represented by formula II is obtained by the corresponding compound represented by A and B through a hydrogen reduction reaction process under the action of N2 and a supported catalyst to obtain the corresponding compound represented by formula I;
[0040]
[0041] The catalyst is a metal-supported catalyst; the metal in the metal-supported catalyst is preferably selected from one or more of nickel, cobalt, copper, tin, platinum, palladium, lanthanum, ruthenium and rhodium, and the carrier in the metal-supported catalyst is preferably selected from one or more of carbon, alumina, silica gel and molecular sieve.
[0042] Example 1: Preparation of 5%wt Pt / Al2O3 catalyst
[0043] (1) Weigh 1.32 g of chloroplatinic acid hexahydrate and mix with deionized water to prepare a chloroplatinic acid aqueous solution.
[0044] (2) Weigh 10 g of Al2O3 carrier (purchased from MacLean Reagent Platform), place the Al2O3 carrier in a glass dish, slowly add hexahydrate chloroplatinic acid aqueous solution with a pipette, and then vacuum immerse at 60°C for 2 hours.
[0045] (3) After standing, dry in an oven at 80°C for 4 hours.
[0046] (4) After drying, calcination was carried out in a muffle furnace at 520°C for 4 h.
[0047] (5) After calcination, the catalyst was reduced in a tubular furnace at 250° C. for 3 h under hydrogen to obtain a 5% wt Pt / Al 2 O 3 catalyst, which was used in subsequent examples.
[0048] Example 2: Preparation of 5%wt-5%wt Pt-Sn / Al2O3 catalyst
[0049] (1) Weigh 1.32 g of chloroplatinic acid hexahydrate and mix it with deionized water to prepare a chloroplatinic acid aqueous solution. Weigh 1.09 g of tin tetrachloride and mix it with deionized water to prepare a tin tetrachloride aqueous solution.
[0050] (2) Weigh 10 g of Al2O3 carrier (purchased from MacLean Reagent Platform), place the Al2O3 carrier in a glass dish, slowly add hexahydrate chloroplatinic acid aqueous solution and tin tetrachloride aqueous solution with a pipette, and then vacuum immerse at 55°C for 3 hours.
[0051] (3) After standing, dry in an oven at 80°C for 4 hours.
[0052] (4) After drying, calcination was carried out in a muffle furnace at 520°C for 4 h.
[0053] (5) After calcination, the catalyst was reduced in a tubular furnace at 250°C for 3 h under hydrogen to obtain a 5%wt-5%wtPt-Sn / Al2O3 catalyst, which was used in subsequent examples.
[0054] Example 3: Preparation of 5%wt-5%wt Ni-Sn / Al2O3 catalyst
[0055] (1) Weigh 2.04 g of nickel chloride hexahydrate and mix it with deionized water to prepare a chloroplatinic acid aqueous solution, and weigh 1.09 g of tin tetrachloride and mix it with deionized water to prepare a tin tetrachloride aqueous solution.
[0056] (2) Weigh 10 g of Al2O3 carrier (purchased from MacLean Reagent Platform), place the Al2O3 carrier in a glass dish, slowly add nickel chloride hexahydrate aqueous solution and tin tetrachloride aqueous solution with a pipette, and then vacuum immerse at 55°C for 3 hours.
[0057] (3) After standing, dry in an oven at 70°C for 4 hours.
[0058] (4) After drying, calcination was carried out in a muffle furnace at 450°C for 5 h.
[0059] (5) After calcination, the catalyst was reduced in a tubular furnace at 300°C for 3 h with hydrogen to obtain a 5%wt-5%wt Ni-Sn / Al2O3 catalyst, which was used in subsequent examples.
[0060] Example 4: Preparation of 5%wt-5%wt Fe-Mn / Al2O3 catalyst
[0061] (1) Weigh 2.41 g of ferric chloride hexahydrate and mix it with deionized water to prepare a ferric chloride aqueous solution; weigh 2.188 g of manganese acetate tetrahydrate and mix it with deionized water to prepare a manganese acetate iron aqueous solution.
[0062] (2) Weigh 10 g of Al2O3 carrier (purchased from McLean Reagent Platform), place the Al2O3 carrier in a glass dish, slowly add hexahydrate ferric chloride aqueous solution and tetrahydrate manganese acetate aqueous solution with a pipette, and then vacuum immerse at 50°C for 3 hours.
[0063] (3) After standing, dry in an oven at 80°C for 4 hours.
[0064] (4) After drying, calcination was carried out in a muffle furnace at 480°C for 4 h.
[0065] (5) After calcination, the catalyst was reduced in a tubular furnace at 350° C. for 5 h under hydrogen to obtain a 5% wt-5% wt Fe—Mn / Al 2 O 3 catalyst, which was used in subsequent examples.
[0066] Example 5: Preparation of 5%wt Co / Al2O3 catalyst
[0067] (1) Weigh 2.46 g of cobalt nitrate hexahydrate and mix with deionized water to prepare a cobalt nitrate aqueous solution.
[0068] (2) Weigh 10 g of Al2O3 carrier (purchased from MacLean Reagent Platform), place the Al2O3 carrier in a glass dish, slowly add cobalt nitrate hexahydrate aqueous solution with a pipette, and then vacuum impregnate at 55°C for 3 hours.
[0069] (3) After standing, dry in an oven at 80°C for 4 hours.
[0070] (4) After drying, calcination was carried out in a muffle furnace at 500°C for 4 h.
[0071] (5) After calcination, the catalyst was reduced with hydrogen at 320° C. for 3 h in a tube furnace to obtain a 5% wt Co / Al 2 O 3 catalyst, which was used in subsequent examples.
[0072] Example 6: Preparation of 5%wt Ru / Al2O3 catalyst
[0073] (1) Weigh 1.02 g of water and ruthenium trichloride and deionized water to prepare a ruthenium trichloride aqueous solution.
[0074] (2) Weigh 10 g of Al2O3 carrier (purchased from McLean Reagent Platform), place the Al2O3 carrier in a glass dish, slowly add ruthenium trichloride aqueous solution with a pipette, and then vacuum immerse at 50°C for 3 hours.
[0075] (3) After standing, dry in an oven at 70°C for 4 hours.
[0076] (4) After drying, calcination was carried out in a muffle furnace at 450°C for 4 h.
[0077] (5) After calcination, the catalyst was reduced in a tubular furnace at 350° C. for 4 h under hydrogen to obtain a 5% wt Ru / Al 2 O 3 catalyst, which was used in subsequent examples.
[0078] Example 7: Compound 2,6-dimethyl-N 4 -(4-methylpentan-2-yl)-N 1 Synthesis of phenylbenzene-1,4-diamine
[0079] (1) 10.0 g (0.047 mol) of 2,6-dimethyl-N1-phenylbenzene-1,4-diamine, 60.0 g (0.58 mol) of 4-methyl-2-pentanol, and 0.5 g of 5% Pt / Al2O3 were added to a reaction kettle. The reaction kettle was sealed, and N2 was introduced through the gas phase valve for replacement three times. Then N2 was introduced again. The N2 pressure was 1.5 MPa, and the reaction was carried out at 250°C for 3 h.
[0080] (2) After the reaction, the temperature in the reactor was lowered to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and maintained for 5 min, 20°C / min to 280°C and maintained for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 92.33%.
[0081] Example 8: Compound N 1 -(4-methylpentan-2-yl)-N 4 Synthesis of -(p-Tolyl)benzene-1,4-diamine
[0082] (1) Add 10.0 g (0.05 mol) N 1 -(p-Tolyl)benzene-1,4-diamine, 60.0g (0.58mol) 4-methyl-2-pentanol, 0.5g 5% Pt / Al2O3, closed the reaction kettle, introduced N2 from the gas phase valve for replacement three times, and then introduced N2, the N2 pressure was 1.0Mpa, and reacted at 250°C for 6h.
[0083] (2) After the reaction, the temperature in the reactor dropped to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and held for 5 min, 20°C / min to 280°C and held for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 90.56%.
[0084] Example 9: Compound 2-methyl-N 1 -(4-methylpentan-2-yl)-N 4 Synthesis of -(o-Tolyl)benzene-1,4-diamine
[0085]
[0086] (1) Add 10.0 g (0.047 mol) of 3-methyl-N 1 -(o-Tolyl)benzene-1,4-diamine, 60.0g (0.58mol) 4-methyl-2-pentanol, 0.5g 5% Pt / Al2O3, closed the reaction kettle, introduced N2 from the gas phase valve for replacement three times, and then introduced N2, the N2 pressure was 1.5Mpa, and reacted at 220°C for 4h.
[0087] (2) After the reaction, the temperature in the reactor was lowered to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and held for 5 min, 20°C / min to 280°C and held for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 93.31%.
[0088] Example 10: Compound N 1 -isopropyl-N 4 Synthesis of phenylbenzene-1,4-diamine
[0089]
[0090] (1) 10.0 g (0.05 mol) of 2,6-dimethyl-N1-phenylbenzene-1,4-diamine, 40.0 g (0.67 mol) of propan-2-ol, and 0.5 g of 5% Pt-Sn / Al2O3 were added to a reaction kettle. The reaction kettle was sealed, and N2 was introduced through the gas phase valve for replacement three times. Then N2 was introduced again. The N2 pressure was 1.5 MPa, and the reaction was carried out at 200°C for 3 hours.
[0091] (2) After the reaction, the temperature in the reactor dropped to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and held for 5 min, 20°C / min to 280°C and held for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 94.23%.
[0092] Example 11: Compound N 1 -cyclohexyl-N 4 Synthesis of phenylbenzene-1,4-diamine
[0093]
[0094] (1) 10.0 g (0.05 mol) of 2,6-dimethyl-N1-phenylbenzene-1,4-diamine, 60.0 g (0.60 mol) of cyclohexanol, and 0.5 g of 5% Pt-Sn / Al2O3 were added to a reaction kettle. The reaction kettle was sealed, and N2 was introduced through the gas phase valve for replacement three times. Then N2 was introduced again. The N2 pressure was 1.5 MPa, and the reaction was carried out at 250°C for 3 h.
[0095] (2) After the reaction, the temperature in the reactor was lowered to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and held for 5 min, 20°C / min to 280°C and held for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 92.56%.
[0096] Example 12: Compound N 1 -(Dicyclopropylmethyl)-N 4Synthesis of phenylbenzene-1,4-diamine
[0097] (1) 10.0 g (0.05 mol) of 2,6-dimethyl-N1-phenylbenzene-1,4-diamine, 60.0 g (0.53 mol) of dicyclopropylmethanol, and 0.5 g of 5% Pt-Sn / Al2O3 were added to a reaction kettle. The reaction kettle was sealed, and N2 was introduced through the gas phase valve for replacement three times. Then N2 was introduced again. The N2 pressure was 1.5 MPa, and the reaction was carried out at 200°C for 4 hours.
[0098] (2) After the reaction, the temperature in the reactor was lowered to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and maintained for 5 min, 20°C / min to 280°C and maintained for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 89.82%.
[0099] Example 13: 5%wt-5%wt Ni-Cu / Al2O3 Synthesis of Compound N 1 -(4-methylpentan-2-yl)-N 4 -(p-Tolyl)benzene-1,4-diamine
[0100]
[0101] (1) Add 10.0 g (0.05 mol) N 1 -(p-Tolyl)benzene-1,4-diamine, 60.0g (0.58mol) 4-methyl-2-pentanol, 0.5g 5% Ni-Cu / Al2O3, closed the reaction kettle, introduced N2 from the gas phase valve for replacement three times, and then introduced N2, the N2 pressure was 1.0Mpa, and reacted at 250°C for 6h.
[0102] (2) After the reaction, the temperature in the reactor dropped to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and maintained for 5 min, 20°C / min to 280°C and maintained for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 89.63%.
[0103] Example 14: 5%wt-5%wt Ni-Sn / Al2O3 Synthetic Compound N 1 -(4-methylpentan-2-yl)-N 4 -(p-Tolyl)benzene-1,4-diamine
[0104]
[0105] (1) Add 10.0 g (0.05 mol) N 1 -(p-Tolyl)benzene-1,4-diamine, 60.0g (0.58mol) 4-methyl-2-pentanol, 0.5g 5% Ni-Sn / Al2O3, closed the reaction kettle, introduced N2 from the gas phase valve for replacement three times, and then introduced N2, the N2 pressure was 1.0Mpa, and reacted at 250°C for 6h.
[0106] (2) After the reaction, the temperature in the reactor dropped to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and maintained for 5 min, 20°C / min to 280°C and maintained for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 91.56%.
[0107] Example 15: 5%wtRu / Al2O3 Synthesis of Compound N 1 -(4-methylpentan-2-yl)-N 4 -(p-Tolyl)benzene-1,4-diamine
[0108]
[0109] (1) Add 10.0 g (0.05 mol) N 1 -(p-Tolyl)benzene-1,4-diamine, 60.0g (0.58mol) 4-methyl-2-pentanol, 0.5g 5% Ru / Al2O3, closed the reaction kettle, introduced N2 from the gas phase valve for replacement three times, and then introduced N2, the N2 pressure was 1.0Mpa, and reacted at 250°C for 6h.
[0110] (2) After the reaction, the temperature in the reactor dropped to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and maintained for 5 min, 20°C / min to 280°C and maintained for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 90.22%.
[0111] Example 16: 5%wt Co / Al2O3 Synthesis of Compound N 1 -(4-methylpentan-2-yl)-N 4 -(p-Tolyl)benzene-1,4-diamine
[0112]
[0113] (1) Add 10.0 g (0.05 mol) N 1 -(p-Tolyl)benzene-1,4-diamine, 60.0g (0.58mol) 4-methyl-2-pentanol, 0.5g 5% Co / Al2O3, closed the reaction kettle, introduced N2 from the gas phase valve for replacement three times, and then introduced N2, the N2 pressure was 1.0Mpa, and reacted at 250°C for 6h.
[0114] (2) After the reaction, the temperature in the reactor was lowered to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and maintained for 5 min, 20°C / min to 280°C and maintained for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 88.93%.
[0115] Example 17: 5%wt-5%wt Fe-Mn / Al2O3 Synthesis of Compound N 1 -(4-methylpentan-2-yl)-N 4 -(p-Tolyl)benzene-1,4-diamine
[0116]
[0117] (1) Add 10.0 g (0.05 mol) N 1-(p-Tolyl)benzene-1,4-diamine, 60.0g (0.58mol) 4-methyl-2-pentanol, 0.5g 5% Fe-Mn / Al2O3, closed the reaction kettle, introduced N2 from the gas phase valve for replacement three times, and then introduced N2, the N2 pressure was 1.0Mpa, and reacted at 250°C for 6h.
[0118] (2) After the reaction, the temperature in the reactor dropped to room temperature, the product liquid was taken out from the liquid valve, the excess N2 was discharged from the gas valve, and the product was detected by FULI9790 gas chromatograph using a DB-1 non-polar low-bleed chromatographic column with a column temperature of 50°C. The heating conditions were: 50°C for 5 min, 20°C / min to 180°C and held for 5 min, 20°C / min to 280°C and held for 10 min, the vaporization chamber temperature was 250°C, the detector temperature was 250°C, the retention time was 31.5 min, and the gas phase result was a selectivity of 92.21%.
Claims
1. A method for preparing a p-phenylenediamine antioxidant without hydrogenation, characterized in that: The method comprises the following steps: subjecting compound A and compound B to a hydrogen reduction process under a nitrogen atmosphere and a metal-supported catalyst to obtain a compound as shown in formula I. The reaction process is as follows: In the formula, each substituent R1 is independently selected from H, C1-C18 chain hydrocarbon group or C3-C18 alicyclic hydrocarbon group, a is an integer of 1-5; R2, R3, R4, R5 are each independently selected from H, C1-C18 chain hydrocarbon group or C3-C18 alicyclic hydrocarbon group; R6, R7 are each independently selected from C1-C18 chain hydrocarbon group or C3-C18 alicyclic hydrocarbon group, or R6 and R7 form a C3-C18 aliphatic ring.
2. The method for preparing a p-phenylenediamine antioxidant without hydrogenation as claimed in claim 1, characterized in that: a is 1, the substituents R1, R2, R3, R4, and R5 are each independently selected from H or an alkyl group, and R6 and R7 are each independently selected from an alkyl group, a cyclopropane group, or R6 and R7 form a cyclopentane group.
3. A method for preparing a p-phenylenediamine antioxidant without hydrogenation as claimed in claim 1 or 2, characterized in that: The metal in the metal-supported catalyst is selected from one or more of Ni, Cu, Fe, Zr, Co, Sn, Cr, Ga, Ge, Pd, Pt, In, Mn, Zn, Ag, La, and Ce, and the carrier in the metal-supported catalyst is selected from one or more of carbon, alumina, silica gel, and molecular sieve.
4. A method for preparing a p-phenylenediamine antioxidant without hydrogenation as claimed in claim 1 or 2, characterized in that: The molar ratio of compound A to compound B is 1:6-1:14, preferably 1:8-1:
14.
5. A method for preparing a p-phenylenediamine antioxidant without hydrogenation as claimed in claim 1 or 2, characterized in that: The reaction temperature is 150-280°C, preferably 200-250°C, the reaction time is 3-12h, and the nitrogen pressure is 0.5-4MPa, preferably 1-2MPa.
6. The method for preparing a p-phenylenediamine antioxidant without hydrogenation as claimed in claim 3, characterized in that: The preparation method of the metal supported catalyst comprises the following steps: Step 1, adding an active component precursor to a deionized water solution to a fixed volume to prepare an active component solution; Step 2, loading the active component precursor onto the catalyst carrier, impregnating, drying, calcining and reducing to obtain a loaded catalyst, wherein the active component solution is a metal acid solution.
7. The method for preparing a p-phenylenediamine antioxidant without hydrogenation as claimed in claim 6, characterized in that: The active component precursor is loaded on the catalyst carrier by vacuum impregnation, the impregnation temperature is 40-80° C., and the number of impregnations is at least one.
8. The method for preparing a p-phenylenediamine antioxidant without hydrogenation as claimed in claim 6, characterized in that: The drying temperature is 50-100°C, the drying time is 1-48 hours, the roasting temperature is 400-600°C, the roasting time is 1-10 hours, and the reduction is H2 reduction treatment, the reduction temperature is 200°C-300°C, and the reduction time is 1-6 hours.
9. The method for preparing a p-phenylenediamine antioxidant without hydrogenation as claimed in claim 6, characterized in that: Based on the total mass of the supported catalyst, the amount of the active component precursor added in terms of metal element is 1-30%wt.