CN112759523B - Styryl diphenylamine antioxidant and preparation method thereof - Google Patents
Styryl diphenylamine antioxidant and preparation method thereof Download PDFInfo
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- CN112759523B CN112759523B CN202110188687.6A CN202110188687A CN112759523B CN 112759523 B CN112759523 B CN 112759523B CN 202110188687 A CN202110188687 A CN 202110188687A CN 112759523 B CN112759523 B CN 112759523B
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 27
- -1 Styryl diphenylamine Chemical compound 0.000 title claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 109
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 63
- 239000002608 ionic liquid Substances 0.000 claims abstract description 41
- 239000004927 clay Substances 0.000 claims abstract description 39
- 150000003608 titanium Chemical class 0.000 claims abstract description 34
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 15
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 8
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 5
- 238000005804 alkylation reaction Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 238000005303 weighing Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method for producing styryl diphenylamine antioxidant, which takes diphenylamine and alpha-methylstyrene as raw materials and SO 4 2‑ Taking a compound of the modified titanium pillared argil and the titanium-based ionic liquid as a catalyst, and carrying out alkylation reaction and recrystallization to obtain an antioxidant; the catalyst is prepared by preparing titanium pillared argil and SO 4 2‑ Preparation of modified titanium pillared argil, preparation of ionic liquid precursor MIMPS, and preparation of Ti-based ionic liquid and SO 4 2‑ Obtained by in-situ compounding of modified titanium pillared clay, and SO in catalyst 4 2‑ The mass fraction of the modified titanium pillared argil is 50-70wt%, and the titanium-based ionic liquid is Ti 0.25 [MIMPS] 2 PMo 12 O 40 、Ti 0.50 [MIMPS]PMo 12 O 40 、Ti 0.25 [MIMPS]HPMo 12 O 40 To (3) is provided. The invention can solve the problem of the traditional AlCl 3 The base catalyst has the defects of easy loss of acid to cause inactivation in the using process, has the advantages of no corrosion to a reaction device and high catalytic efficiency, and can effectively avoid the traditional AlCl 3 The base catalyst has the disadvantage of producing a large amount of sewage in the separation process.
Description
Technical Field
The invention belongs to the technical field of chemical additives, relates to a production technology of diphenylamine-based antioxidant, and particularly relates to a preparation method of styryl diphenylamine antioxidant.
Background
Antioxidants are a class of substances that block, inhibit or retard the oxidation or autoxidation process of polymers. The antioxidant can obviously improve the oxidation stability of oil products and prolong the service life of polymers, and is widely applied to the fields of oil products, rubber, plastics and the like. The amine antioxidant is the earliest antioxidant, has excellent high-temperature oxidation resistance and good compatibility with oil products, and is widely used in the fields of oil products, rubber and the like. As an additive of lubricating oil, the amine antioxidant and the antiwear agent are compounded to generate a synergistic effect, so that the oxidation resistance of the lubricating oil can be improved, and the mechanical friction loss of an engine can be reduced; as an anti-aging agent for rubber, the amine antioxidant can prevent rubber from aging caused by external factors such as heat, oxygen and the like, and prolong the service life of the rubber.
The diphenylamine antioxidant is easily influenced by operating conditions and reaction environment in the production process, and presents a dark reddish brown color mainly due to oxidation in the process of synthesizing diphenylamine and residual discoloration in products. The diphenylamine residual in the product not only reduces the antioxidant performance of the antioxidant, but also can deepen the color of the product gradually in the storage process due to the overhigh residual quantity, thereby influencing the use of the product in industries such as synthetic rubber and the like.
In the preparation process of the diphenylamine antioxidant, a catalyst is the core of the synthesis reaction technology. Anhydrous AlCl 3 And AlCl 3 The complex catalyst is an important catalyst in the reaction process, but the AlCl is prepared 3 The raw materials of the base catalyst are toxic, and the prepared catalyst is easy to absorb moisture and hydrolyze, and the storage condition is harsh, so that inconvenience is brought to actual production. In addition, the catalyst has the defects that the using amount is large, hydrogen chloride gas introduced in the reaction process is easy to corrode equipment, and a large amount of chlorine-containing sewage is generated in the product aftertreatment. Activated clay is a catalyst for producing diphenylamine-based antioxidants, which is commonly used by manufacturers such as Ciba. The activated clay is a catalyst prepared by using clay as a raw material, treating the clay by using sulfuric acid or hydrochloric acid, and then washing and drying the clay. With AlCl 3 Compared with the base catalyst, the activated clay is easier to filter and separate on one hand, and on the other hand, the product obtained under the catalysis of the activated clay is lighter in color. However, the activated clay catalyst has the problems of large catalyst consumption, long reaction time, additional equipment required for secondary alkylation and non-ideal product distribution, and the existence of the defects seriously limits the industrialization process of products.
CN1995904A discloses a method for synthesizing dialkyl diphenylamine, which comprises adopting beta zeolite and gamma-Al 2 O 3 The catalyst has reaction temperature of 175-185 deg.c and reaction pressure of 0.8-1.0 MPa, and is used in fixed bed for continuous production, the catalyst has use period over 300 hr and the content of 4, 4-di-tert-octyl diphenylamine in the product is less than 20%.
CN101745423A discloses a catalyst and a method for alkylating diphenylamine, wherein the catalyst is prepared by contacting activated clay with an aqueous solution of acid with a concentration of less than 20wt%, dehydrating and drying. The acid is selected from water-soluble inorganic acid and/or p-toluenesulfonic acid. The catalyst is used for diphenylamine alkylation reaction, but has poor activity, high diphenylamine residual quantity in reaction products and short repeated service life.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method for producing styryl diphenylamine antioxidant, which takes diphenylamine and alpha-methylstyrene as raw materials and SO 4 2- The compound of the modified titanium pillared argil and the titanium-based ionic liquid is used as a catalyst to carry out alkylation reaction to prepare a mixture with 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine as a main component, and then the mixture is recrystallized to prepare the antioxidant.
The invention aims to prepare a high-content styrenated diphenylamine product, wherein the relative molar content of 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine in the product is more than or equal to 80 percent. In order to achieve the purpose, the invention is implemented by the following technical scheme:
in one aspect, the invention discloses a catalyst for producing styryl diphenylamine antioxidant, which is prepared from SO 4 2- Modified titanium pillared argil and titanium-based ionic liquid in-situ composite catalyst, wherein SO in catalyst 4 2- The mass fraction of the modified titanium pillared argil is 50-70wt%, and the titanium-based ionic liquid is Ti 0.25 [MIMPS] 2 PMo 12 O 40 、Ti 0.50 [MIMPS]PMo 12 O 40 、Ti 0.25 [MIMPS] HPMo 12 O 40 To (3) is provided.
On the other hand, the invention also discloses a preparation method of the catalyst for producing the styryl diphenylamine antioxidant, which is realized by the following steps:
(1) Preparation of titanium pillared argil
Slowly dropwise adding butyl titanate into 1.0mol/L nitric acid solution to ensure that the molar concentration of Ti is 1.0mol/L, treating for 30min under vigorous stirring, standing and aging for 12h to form titanium sol serving as a cross-linking agent; dispersing carclazyte into deionized water, violently stirring for 2 hours to form a mixture A, slowly adding titanium sol into the mixture A, continuously stirring for 12 hours to obtain a mixture B, carrying out centrifugal separation on the mixture B, sequentially drying for 12 hours at 105 ℃, and roasting for 5 hours at 500 ℃ to obtain titanium pillared carclazyte;
（2）SO 4 2- preparation of modified titanium pillared argil
Sequentially adding titanium pillared argil and ammonium sulfate into deionized water, slowly evaporating the obtained mixture to dryness in a 70 ℃ water bath, roasting the evaporated material at 500 ℃ for 5 hours to obtain SO 4 2- SO with a content of 10 to 15 wt% 4 2- Modifying titanium pillared clay;
(3) Preparation of ionic liquid precursor MIMPS
Dissolving 1, 3-propane sultone into p-xylene to obtain a mixed solution A, transferring the mixed solution A into a reaction kettle, introducing nitrogen into the reaction kettle for 1h to remove residual oxygen, raising the temperature of the reaction kettle to 80 ℃, dropwise adding N-methylimidazole under the stirring condition of 500r/min, continuously stirring for reaction for 3h to obtain a milky reaction liquid, carrying out reduced pressure suction filtration on the milky reaction liquid, washing the obtained white precipitate with ethyl acetate for three times, and carrying out vacuum drying at 80 ℃ for 12h to obtain white powder solid, namely an ionic liquid precursor, which is marked as MIMPS;
(4) Ti-based ionic liquid and SO 4 2- In-situ compounding of modified titanium pillared clay
SO is added 4 2- Modified titanium pillared argil, phosphomolybdic acid and TiOSO 4 Adding MIMPS into deionized water to obtain
Stirring the mixture C at room temperature for 12h, and then sequentially centrifuging, washing and vacuum drying to obtain SO 4 2- The composite catalyst of modified titanium pillared argil and Ti-based solid ionic liquid.
In a preferred embodiment, in the step (1), the mass-to-volume ratio of the clay to the deionized water in the mixture A is 1g/mL, and the molar mass ratio of the Ti to the clay in the mixture B is 15mmol/g.
As a preferred embodiment, in the step (2), the mass-to-volume ratio of the titanium pillared argil to the deionized water is 1g/mL, and SO is contained in ammonium sulfate 4 2- The mass ratio of the titanium-pillared argil to the titanium-pillared argil is (10 to 15) to (85 to 90).
As a preferred embodiment, in the step (3), the mass concentration of the substance of N-methylimidazole to 1, 3-propane sultone in p-xylene is 1.
As a preferred embodiment, in step (4), phosphomolybdic acid, tiOSO 4 The titanium-based ionic liquid prepared by MIMPS in the reaction process is Ti 0.25 [MIMPS] 2 PMo 12 O 40 、Ti 0.50 [MIMPS]PMo 12 O 40 、Ti 0.25 [MIMPS]HPMo 12 O 40 One of (1); further, the ratio of the amounts of MIMPS to the amount of substance of phosphomolybdic acid is (1 to 2): 1, 4 the amount ratio of the catalyst to the phosphotungstic acid is (0.25 to 0.50): 1, and SO is contained in the composite catalyst 4 2- The mass fraction of the modified titanium pillared argil is 50-70wt%.
In addition, the invention also discloses a method for producing styryl diphenylamine by using the catalyst, which comprises the steps of adding the composite catalyst, diphenylamine and polymerization inhibitor into a reaction kettle, introducing nitrogen into the system for 1h before reaction to expel residual oxygen, stirring under the protection of nitrogen, heating to 120-150 ℃, dropwise adding alpha-methyl styrene into the reaction system, continuing to react for 2-3 h, carrying out thermal filtration on the reacted mixed solution to separate the catalyst, cooling the filtrate, and then sequentially crystallizing, filtering, washing and drying to obtain the antioxidant rich in 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine.
As a preferred embodiment, the molar ratio of diphenylamine to alpha-methylstyrene is (0.5 to 0.7) 1.0; the mass ratio of the composite catalyst to the diphenylamine is (0.05-0.10) to 1.0; the mass ratio of the polymerization inhibitor to the diphenylamine is (0.002 to 0.005) to 1.0; the polymerization inhibitor is one of 2, 6-di-tert-butyl-4-methylphenol or 2, 4-dimethyl-6-tert-butylphenol.
Compared with the prior art, the invention has the following advantages:
1) The titanium-based solid ionic liquid uses heteropoly acid radicals with multi-charge characteristics as anions and simultaneously uses organic cations, metal cations and protons as counter ions to construct a heteropoly acid functional ionic liquid organic-inorganic hybrid material with B-L dual acidity, so that the overall acid strength of the catalyst can reach the level of super acid, and higher catalytic activity is expressed in the reaction process.
2) SO 4 2- Compared with the conventional clay, the specific surface area of the modified titanium pillared clay is obviously increased; and SO 4 2- And TiO 2 The superacid formed between can be intercalated in highly dispersed form into the interlayer domains of the clay. Thus, SO 4 2- The modified titanium pillared argil has good catalytic activity and reaction stability.
3) Titanium-based solid ionic liquid and SO 4 2- The modified titanium pillared clay can generate a synergistic effect, and SO on the surface of the modified titanium pillared clay 4 2- Can interact with Ti species on the titanium-based solid ionic liquid to generate super acidic catalytic active sites; at the same time, the titanium column supports SiO on the carclazyte 2 Can be reacted with PO on solid ionic liquid 4 3- Can generate another solid phosphoric acid catalytic active site, titanium-based solid ionic liquid and SO by interaction between the two 4 2- The catalytic system composed of the modified titanium pillared argil and the synergistic effect between the two catalytic systems can make up for the reduction of the reaction activity of the whole catalyst caused by the loss or inactivation of one type of active sites in the reaction process.
4) The prepared composite catalyst can solve the problem of the traditional AlCl 3 The catalyst has the advantages of no corrosion to a reaction device and high catalytic efficiency, and can effectively avoid the defect of inactivation caused by easy loss of acid in the using process of the base catalyst, and the prepared catalyst has the advantages of no corrosion to the reaction device and high catalytic efficiency 3 The base catalyst is produced in a separate processThe shortage of large amount of sewage.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments described below are by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
A preparation method of an antioxidant catalyst for producing styryl diphenylamine is realized by the following specific steps:
(1) Preparation of titanium pillared argil
Slowly dropwise adding butyl titanate into 1.0mol/L nitric acid solution to ensure that the molar concentration of Ti is 1.0mol/L, treating for 30min under the stirring condition of 1000r/min, standing and aging for 12h to form titanium sol serving as a cross-linking agent; weighing clay, dispersing the clay into deionized water, vigorously stirring for 2 hours to form a mixture A, slowly adding titanium sol into the mixture A, continuously stirring for 12 hours to obtain a mixture B, carrying out centrifugal separation on the obtained mixture, drying for 12 hours at 105 ℃, and roasting for 5 hours at 500 ℃ to obtain titanium pillared clay; wherein the mass volume ratio of the argil to the deionized water in the mixture A is 1g/mL, and the molar mass ratio of the Ti to the argil in the mixture B is 15mmol/g;
（2）SO 4 2- preparation of modified titanium pillared argil
Dispersing titanium pillared argil into deionized water, adding ammonium sulfate, slowly evaporating the obtained mixture to dryness under the condition of 70 ℃ water bath, and roasting the evaporated material at 500 ℃ for 5 hours to obtain SO 4 2- In an amount of 10 wt.% of SO 4 2- Modified titanium pillared argil; wherein the mass volume ratio of the titanium pillared argil to the deionized water is 1g/mL, and SO in ammonium sulfate 4 2- The mass ratio of the titanium pillared argil to the titanium pillared argil is 10;
(3) Preparation of ionic liquid precursor MIMPS
Weighing 1, 3-propane sultone, dissolving into p-xylene to obtain a mixed solution A, transferring the solution A into a reaction kettle, introducing nitrogen into the reaction kettle for 1h to remove residual oxygen, raising the temperature of the reaction kettle to 80 ℃, dropwise adding N-methylimidazole under the stirring condition of 500r/min, continuously stirring for reaction for 3h to obtain a milky reaction liquid, carrying out reduced pressure suction filtration on the reaction liquid, washing the obtained white precipitate with ethyl acetate for three times, and carrying out vacuum drying at 80 ℃ for 12h to obtain a white powder solid, namely MIMPS; wherein the mass concentration of the substances of the N-methylimidazole and the 1, 3-propane sultone in the paraxylene is 0.15mol/L, and the mass ratio of the substances of the N-methylimidazole to the 1, 3-propane sultone is 1;
(4) Ti-based ionic liquid and SO 4 2- In-situ compounding of modified titanium pillared clay
SO is added 4 2- Modified titanium pillared argil, phosphomolybdic acid and TiOSO 4 Adding MIMPS into deionized water to obtain
Stirring the mixture C at room temperature for reaction for 12 hours, and then sequentially carrying out centrifugation, washing and vacuum drying to obtain SO 4 2- A composite catalyst of modified titanium pillared argil and Ti-based solid ionic liquid; wherein phosphomolybdic acid, tiOSO 4 The titanium-based solid ionic liquid prepared by MIMPS in the reaction process is Ti 0.25 [MIMPS] 2 PMo 12 O 40 . Wherein the mass ratio of MIMPS to phosphomolybdic acid is 2 4 The ratio of the amount of the substance to the amount of the phosphotungstic acid is 0.25 4 2- The mass fraction of the modified titanium pillared argil is 50wt%.
Adding the prepared composite catalyst, diphenylamine and polymerization inhibitor 2, 6-di-tert-butyl-4-methylphenol into a reaction kettle according to a ratio, introducing nitrogen into a system before reaction for 1h to remove residual oxygen, stirring under the protection of nitrogen, heating to 120 ℃, dropwise adding alpha-methylstyrene into the reaction system, continuing to react for 3h, thermally filtering the mixed solution after reaction to separate the catalyst, and sequentially crystallizing, filtering, washing and drying the filtrate after the filtrate is cooled to obtain a mixture rich in 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine. In the reaction process, the molar ratio of diphenylamine to alpha-methylstyrene is 0.5; the mass ratio of the catalyst to the diphenylamine is 0.05; the mass ratio of the polymerization inhibitor 2, 6-di-tert-butyl-4-methylphenol to the diphenylamine is 0.002. The yield of the styrenated diphenylamine mixed product is 96.5 percent by using diphenylamine raw materials as a measuring standard and performing liquid chromatography analysis, wherein the content of 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine is 82.4 percent, and the content of unreacted diphenylamine is 0.15 percent
Example 2
A preparation method of an antioxidant catalyst for producing styryl diphenylamine is realized by the following specific steps:
(1) Preparation of titanium pillared argil
Slowly dripping butyl titanate into 1.0mol/L nitric acid solution to ensure that the molar concentration of Ti is 1.0mol/L, treating for 30min under vigorous stirring, standing and aging for 12h to form titanium sol serving as a cross-linking agent. Weighing carclazyte, dispersing the carclazyte in deionized water, vigorously stirring for 2 hours to form a mixture A, slowly adding titanium sol into the mixture A, continuously stirring for 12 hours to form a mixture B, carrying out centrifugal separation on the obtained mixture, drying for 12 hours at 105 ℃, and roasting for 5 hours at 500 ℃ to obtain the titanium pillared carclazyte. Wherein the mass volume ratio of the argil to the deionized water in the mixture A is 1g/mL; the molar mass ratio of Ti to argil in the mixture B is 15mmol/g;
（2）SO 4 2- preparation of modified titanium pillared argil
Dispersing titanium pillared argil into deionized water, adding ammonium sulfate, slowly evaporating the obtained mixture to dryness in a 70 ℃ water bath, roasting the evaporated material at 500 ℃ for 5 hours to obtain SO 4 2- With an SO content of 15 wt.% 4 2- Modified titanium pillared argil; wherein the mass volume ratio of the titanium pillared argil to the deionized water is 1g/mL, and SO in ammonium sulfate 4 2- The mass ratio of the titanium-pillared clay to the titanium-pillared clay is 15;
(3) Preparation of ionic liquid precursor MIMPS
Weighing 1, 3-propane sultone to dissolve into p-xylene to obtain a mixed solution A, transferring the solution A into a reaction kettle, introducing nitrogen into the reaction kettle for 1h to remove residual oxygen, raising the temperature of the reaction kettle to 80 ℃, dropwise adding N-methylimidazole into the reaction kettle under the stirring condition of 500r/min, continuously stirring for reaction for 3h to obtain milky reaction liquid, carrying out reduced pressure suction filtration on the reaction liquid, washing the obtained white precipitate with ethyl acetate for three times, and carrying out vacuum drying at 80 ℃ for 12h to obtain white powder solid, namely MIMPS; wherein the mass concentration of the substances of the N-methylimidazole and the 1, 3-propane sultone in the paraxylene is 0.15mol/L, and the mass ratio of the substances of the N-methylimidazole to the 1, 3-propane sultone is 1;
(4) Ti-based ionic liquid and SO 4 2- In-situ compounding of modified titanium pillared clay
Adding SO 4 2- Modified titanium pillared argil, phosphomolybdic acid and TiOSO 4 Adding MIMPS into deionized water to obtain
Stirring the mixture C at room temperature for 12h, and then sequentially centrifuging, washing and vacuum drying to obtain SO 4 2- A composite catalyst of modified titanium pillared argil and Ti-based solid ionic liquid; wherein phosphomolybdic acid, tiOSO 4 The titanium-based solid ionic liquid prepared by MIMPS in the reaction process is Ti 0.50 [MIMPS]PMo 12 O 40 . Wherein the mass ratio of MIMPS to phosphomolybdic acid is 1, tiOSO 4 The mass ratio of the catalyst to phosphotungstic acid is 0.5 4 2- The mass fraction of the modified titanium pillared argil is 70wt%.
Adding a catalyst, diphenylamine and a polymerization inhibitor 2, 4-dimethyl-6-tert-butylphenol into a reaction kettle according to a ratio, introducing nitrogen into the system before reaction for 1h to remove residual oxygen, stirring under the protection of nitrogen, heating to 150 ℃, dropwise adding alpha-methylstyrene into the reaction system, continuing to react for 2h, thermally filtering the mixed solution after reaction to separate the catalyst, and after cooling the filtrate, sequentially crystallizing, filtering, washing and drying to obtain a mixture rich in 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine. In the reaction process, the molar ratio of diphenylamine to alpha-methylstyrene is 0.7; the mass ratio of the catalyst to the diphenylamine is 0.10; the mass ratio of the polymerization inhibitor to the diphenylamine is 0.005 and the yield of the styrenated diphenylamine mixed product is 97.3 percent by liquid chromatography analysis by taking the diphenylamine raw material as a measurement standard, wherein the content of the 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine is 84.6 percent, and the content of unreacted diphenylamine is 0.12 percent
Example 3
A preparation method of an antioxidant catalyst for producing styryl diphenylamine is realized by the following specific steps:
(1) Preparation of titanium pillared argil
Slowly dropwise adding butyl titanate into 1.0mol/L nitric acid solution to ensure that the molar concentration of Ti is 1.0mol/L, treating for 30min under vigorous stirring, standing and aging for 12h to form titanium sol serving as a crosslinking agent. Weighing clay, dispersing into deionized water, vigorously stirring for 2h to form a mixture A, slowly adding titanium sol into the mixture A, continuously stirring for 12h to form a mixture B, carrying out centrifugal separation on the obtained mixture, drying at 105 ℃ for 12, and roasting at 500 ℃ for 5h to obtain titanium pillared clay; wherein the mass volume ratio of the argil to the deionized water in the mixture A is 1g/mL; the molar mass ratio of Ti to argil in the mixture B is 15mmol/g;
（2）SO 4 2- preparation of modified titanium pillared argil
Dispersing titanium pillared argil into deionized water, adding ammonium sulfate, slowly evaporating the obtained mixture to dryness under the condition of 70 ℃ water bath, and roasting the evaporated material at 500 ℃ for 5 hours to obtain SO 4 2- With an SO content of 12 wt.% 4 2- Modifying titanium pillared clay; wherein the mass volume ratio of the titanium pillared argil to the deionized water is 1g/mL, and SO is contained in ammonium sulfate 4 2- The mass ratio of the titanium pillared argil to the titanium pillared argil is 12;
(3) Preparation of ionic liquid precursor MIMPS
Weighing 1, 3-propane sultone, dissolving into p-xylene to obtain a mixed solution A, transferring the solution A into a reaction kettle, introducing nitrogen into the reaction kettle for 1h to remove residual oxygen, raising the temperature of the reaction kettle to 80 ℃, dropwise adding N-methylimidazole under the stirring condition of 500r/min, continuously stirring for reaction for 3h to obtain a milky reaction liquid, carrying out reduced pressure suction filtration on the reaction liquid, washing the obtained white precipitate with ethyl acetate for three times, and carrying out vacuum drying at 80 ℃ for 12h to obtain a white powder solid, namely MIMPS; wherein the mass concentration of the substances of N-methylimidazole and 1, 3-propane sultone in p-xylene is 1;
(4) Ti-based ionic liquid and SO 4 2- In-situ compounding of modified titanium pillared clay
Adding SO 4 2- Modified titanium pillared argil, phosphomolybdic acid and TiOSO 4 Adding MIMPS into deionized water to obtain
Stirring the mixture C at room temperature for 12h, and then sequentially centrifuging, washing and vacuum drying to obtain SO 4 2- A composite catalyst of modified titanium pillared argil and Ti-based solid ionic liquid; wherein phosphomolybdic acid, tiOSO 4 The titanium-based solid ionic liquid prepared by MIMPS in the reaction process is Ti 0.25 [MIMPS]HPMo 12 O 40 . Wherein the mass ratio of MIMPS to phosphomolybdic acid is 1, tiOSO 4 The ratio of the amount of the phosphotungstic acid to the amount of the phosphotungstic acid is 0.25 4 2- The mass fraction of the modified titanium pillared argil is 58wt%.
Adding the prepared catalyst, diphenylamine and polymerization inhibitor 2, 6-di-tert-butyl-4-methylphenol into a reaction kettle according to a ratio, introducing nitrogen into the system before reaction for 1h to remove residual oxygen, stirring under the protection of nitrogen, heating to 135 ℃, dropwise adding alpha-methylstyrene into the reaction system, continuing to react for 2.5h, carrying out thermal filtration on the reacted mixed solution to separate the catalyst, and after cooling the filtrate, sequentially crystallizing, filtering, washing and drying to obtain a mixture rich in 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine. In the reaction process, the molar ratio of diphenylamine to alpha-methylstyrene is 0.60; the mass ratio of the catalyst to the diphenylamine is 0.078; the mass ratio of the polymerization inhibitor to the diphenylamine is 0.0032 and is 1.0, the yield of the styrenated diphenylamine mixed product is 92.3 percent by liquid chromatography analysis by taking the diphenylamine raw material as a metering standard, wherein the content of the 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine is 83.6 percent, and the content of the unreacted diphenylamine is 0.14 percent
Comparative example 1
(1) Preparation of titanium pillared argil
Slowly dropwise adding butyl titanate into 1.0mol/L nitric acid solution to ensure that the molar concentration of Ti is 1.0mol/L, treating for 30min under vigorous stirring, standing and aging for 12h to form titanium sol serving as a crosslinking agent. Weighing clay, dispersing into deionized water, vigorously stirring for 2h to form a mixture A, slowly adding titanium sol into the mixture A, continuously stirring for 12h to form a mixture B, carrying out centrifugal separation on the obtained mixture, drying at 105 ℃ for 12, and roasting at 500 ℃ for 5h to obtain titanium pillared clay; wherein the mass volume ratio of the argil to the deionized water in the mixture A is 1g/mL; the molar mass ratio of Ti to the argil in the mixture B is 15mmol/g;
（2）SO 4 2- preparation of modified titanium pillared argil
Dispersing titanium pillared argil into deionized water, adding ammonium sulfate, slowly evaporating the obtained mixture to dryness in a 70 ℃ water bath, roasting the evaporated material at 500 ℃ for 5 hours to obtain SO 4 2- SO content of 15 wt.% 4 2- Modifying titanium pillared clay; wherein the mass volume ratio of the titanium pillared argil to the deionized water is 1g/mL, and SO is contained in ammonium sulfate 4 2- The mass ratio of the titanium-pillared clay to the titanium-pillared clay is 15;
the prepared SO 4 2- Adding modified titanium pillared clay, diphenylamine and polymerization inhibitor 2, 6-di-tert-butyl-4-methylphenol into a reaction kettle in proportion, introducing nitrogen into the system for 1h before reaction to remove residual oxygen, stirring under the protection of nitrogen, heating to 120 ℃, dropwise adding alpha-methylstyrene into the reaction system, continuing to react for 3h, carrying out thermal filtration on the reacted mixed solution to separate the catalyst, and after cooling the filtrate, sequentially crystallizing, filtering, washing and drying to obtain a mixture containing 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine. In the reaction process, the molar ratio of diphenylamine to alpha-methylstyrene is 0.5; the mass ratio of the catalyst to the diphenylamine is 0.05; polymerization inhibitor 2, 6-di-tert-butylThe mass ratio of the butyl-4-methylphenol to the diphenylamine is 0.002. The yield of the styrenated diphenylamine mixed product is 72.6 percent by using diphenylamine raw materials as a measuring standard and performing liquid chromatography analysis, wherein the content of 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine is 67.2 percent, and the content of unreacted diphenylamine is 0.94 percent.
Comparative example 2
(1) Preparation of ionic liquid precursor MIMPS
Weighing 1, 3-propane sultone, dissolving into p-xylene to obtain a mixed solution A, transferring the solution A into a reaction kettle, introducing nitrogen into the reaction kettle for 1h to remove residual oxygen, raising the temperature of the reaction kettle to 80 ℃, dropwise adding N-methylimidazole under the stirring condition, continuously stirring for reacting for 3h to obtain a milky reaction liquid, carrying out reduced pressure suction filtration on the reaction liquid, washing the obtained white precipitate with ethyl acetate for three times, and carrying out vacuum drying at 80 ℃ for 12h to obtain a white powder solid, namely MIMPS; wherein the mass concentration of the substances of N-methylimidazole and 1, 3-propane sultone in p-xylene is 1;
(2) Preparation of Ti-based ionic liquid
Phosphomolybdic acid, tiOSO 4 Adding MIMPS into deionized water to obtain a mixture, and stirring at room temperature
Reacting for 12 hours, and then sequentially carrying out centrifugation, washing and vacuum drying to obtain the Ti-based solid ionic liquid catalyst Ti 0.25 [MIMPS] 2 PMo 12 O 40 . Wherein the mass ratio of MIMPS to phosphomolybdic acid is 2 4 The mass ratio to phosphotungstic acid is 0.25;
adding the prepared Ti-based solid ionic liquid, diphenylamine and polymerization inhibitor 2, 6-di-tert-butyl-4-methylphenol into a reaction kettle according to a ratio, introducing nitrogen into the system for 1h before reaction to remove residual oxygen, stirring under the protection of nitrogen, heating to 120 ℃, dropwise adding alpha-methylstyrene into the reaction system, continuing to react for 3h, carrying out thermal filtration on the mixed solution after reaction to separate the catalyst, and after cooling the filtrate, sequentially crystallizing, filtering, washing and drying to obtain a mixture containing 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine. In the reaction process, the molar ratio of diphenylamine to alpha-methylstyrene is 0.5; the mass ratio of the catalyst to the diphenylamine is 0.05; the mass ratio of the polymerization inhibitor 2, 6-di-tert-butyl-4-methylphenol to the diphenylamine is 0.002. The yield of the styrenated diphenylamine mixed product is 80.2 percent by liquid chromatography analysis by taking the diphenylamine raw material as a measuring standard, wherein the content of 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine is 72.3 percent, and the content of unreacted diphenylamine is 0.72 percent.
Example 6
The catalyst prepared in example 1 was subjected to the following cycle test:
TABLE 1 results of cycle testing of catalysts
| 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine content | Diphenylamine content | |
| Cycle 1 | 82.1% | 0.16% |
| 2 nd cycle | 81.7% | 0.17% |
| Cycle 3 | 81.2% | 0.19% |
| Cycle 4 | 80.9% | 0.16% |
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A preparation method of a catalyst for producing styryl diphenylamine antioxidant is characterized by comprising the following steps: is prepared from SO 4 2- Modified titanium pillared argil and titanium-based ionic liquid in-situ composite catalyst, wherein SO in catalyst 4 2- The mass fraction of the modified titanium pillared argil is 50-70wt%, and the titanium-based ionic liquid is Ti 0.25 [MIMPS] 2 PMo 12 O 40 、Ti 0.50 [MIMPS]PMo 12 O 40 、Ti 0.25 [MIMPS] HPMo 12 O 40 One of (a) and (b);
the preparation method of the catalyst for producing the styryl diphenylamine antioxidant is realized by the following steps:
(1) Preparation of titanium pillared argil
Slowly dropwise adding butyl titanate into 1.0mol/L nitric acid solution to ensure that the molar concentration of Ti is 1.0mol/L, treating for 30min under vigorous stirring, standing and aging for 12h to form titanium sol; dispersing carclazyte into deionized water, violently stirring for 2 hours to form a mixture A, slowly adding titanium sol into the mixture A, continuously stirring for 12 hours to obtain a mixture B, carrying out centrifugal separation on the mixture B, sequentially drying for 12 hours at 105 ℃, and roasting for 5 hours at 500 ℃ to obtain titanium pillared carclazyte;
（2）SO 4 2- preparation of modified titanium pillared argil
Sequentially adding titanium pillared argil and ammonium sulfate into deionized water, slowly evaporating the obtained mixture to dryness in a 70 ℃ water bath, roasting the evaporated material at 500 ℃ for 5 hours to obtain SO 4 2- SO with a content of 10 to 15 wt% 4 2- Modified titanium pillared argil;
(3) Preparation of ionic liquid precursor MIMPS
Dissolving 1, 3-propane sultone into p-xylene to obtain a mixed solution A, transferring the mixed solution A into a reaction kettle, introducing nitrogen into the reaction kettle for 1h to remove residual oxygen, raising the temperature of the reaction kettle to 80 ℃, dropwise adding N-methylimidazole under the stirring condition of 500r/min, continuously stirring for reaction for 3h to obtain a milky reaction liquid, carrying out reduced pressure suction filtration on the milky reaction liquid, washing the obtained white precipitate with ethyl acetate for three times, and carrying out vacuum drying at 80 ℃ for 12h to obtain a white powder solid, namely an ionic liquid precursor, which is marked as MIMPS;
(4) Ti-based ionic liquid and SO 4 2- In-situ compounding of modified titanium pillared clay
SO is added 4 2- Modified titanium pillared argil, phosphomolybdic acid and TiOSO 4 Adding MIMPS into deionized water to obtain
Stirring the mixture C at room temperature for reaction for 12h, and then sequentially carrying out centrifugation, washing and vacuum drying to obtain SO 4 2- The composite catalyst of modified titanium pillared argil and Ti-based solid ionic liquid.
2. The process for preparing a catalyst for the production of styrenated diphenylamine antioxidants of claim 1, wherein: in the step (1), the mass-to-volume ratio of the clay to the deionized water in the mixture A is 1g/mL, and the molar mass ratio of the Ti to the clay in the mixture B is 15mmol/g.
3. The process as claimed in claim 1 for producing styreneThe preparation method of the catalyst of the diphenylamine antioxidant is characterized by comprising the following steps: in the step (2), the mass-to-volume ratio of the titanium pillared argil to the deionized water is 1g/mL, and SO in ammonium sulfate 4 2- The mass ratio of the titanium pillared argil to the titanium pillared argil is 10 to 15.
4. The method of preparing a catalyst for the production of styrylated diphenylamine antioxidants as claimed in claim 1, characterized in that: in the step (3), the mass concentration of the substance of the 1, 3-propane sultone in p-xylene is 0.15mol/L, wherein the mass ratio of the substance of the N-methylimidazole to the substance of the 1, 3-propane sultone is 1.
5. The process for preparing a catalyst for the production of styrenated diphenylamine antioxidants of claim 1, wherein: in the step (4), phosphomolybdic acid, tiOSO 4 The titanium-based ionic liquid prepared by MIMPS in the reaction process is Ti 0.25 [MIMPS] 2 PMo 12 O 40 、Ti 0.50 [MIMPS]PMo 12 O 40 、Ti 0.25 [MIMPS]HPMo 12 O 40 To (3) is provided.
6. The process for preparing a catalyst for the production of styrenated diphenylamine antioxidants of claim 1, wherein: in the step (4), the mass ratio of MIMPS to phosphomolybdic acid is 1 to 2 4 The amount ratio of the compound to the phosphotungstic acid is 0.25 to 0.50, and SO in the composite catalyst is as follows 4 2- The mass fraction of the modified titanium pillared argil is 50-70wt%.
7. A process for producing styrenated diphenylamine using the catalyst of claim 1, characterized in that: adding the composite catalyst, diphenylamine and polymerization inhibitor into a reaction kettle, introducing nitrogen into a system before reaction for 1h to remove residual oxygen, stirring under the protection of nitrogen, heating to 120-150 ℃, dropwise adding alpha-methylstyrene into the reaction system, continuing to react for 2-3 h, carrying out thermal filtration on a reacted mixed solution to separate the catalyst, cooling a filtrate, and then sequentially crystallizing, filtering, washing and drying to obtain the antioxidant rich in 4, 4-bis (alpha, alpha-dimethylbenzyl) diphenylamine.
8. The process for producing styrenated diphenylamine of claim 7, characterized in that: the molar ratio of diphenylamine to alpha-methylstyrene is 0.5 to 0.7; the mass ratio of the composite catalyst to the diphenylamine is 0.05-0.10; the mass ratio of the polymerization inhibitor to the diphenylamine is 0.002 to 0.005; the polymerization inhibitor is one of 2, 6-di-tert-butyl-4-methylphenol or 2, 4-dimethyl-6-tert-butylphenol.
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