CN108503512B - A kind of method of new catalyst synthesis antioxidant 330 - Google Patents
A kind of method of new catalyst synthesis antioxidant 330 Download PDFInfo
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- CN108503512B CN108503512B CN201810269195.8A CN201810269195A CN108503512B CN 108503512 B CN108503512 B CN 108503512B CN 201810269195 A CN201810269195 A CN 201810269195A CN 108503512 B CN108503512 B CN 108503512B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 180
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 230000015572 biosynthetic process Effects 0.000 title abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title abstract description 12
- 238000000034 method Methods 0.000 title description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000002808 molecular sieve Substances 0.000 claims abstract description 135
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 132
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 70
- 238000010189 synthetic method Methods 0.000 claims abstract description 64
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 claims abstract description 27
- SCXYLTWTWUGEAA-UHFFFAOYSA-N 2,6-ditert-butyl-4-(methoxymethyl)phenol Chemical compound COCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SCXYLTWTWUGEAA-UHFFFAOYSA-N 0.000 claims abstract description 25
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 23
- 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 abstract description 10
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims description 99
- 239000000203 mixture Substances 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 230000004913 activation Effects 0.000 claims description 40
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229960004756 ethanol Drugs 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 19
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 19
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 229910052724 xenon Inorganic materials 0.000 claims description 14
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- 229940043237 diethanolamine Drugs 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000004224 protection Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims 2
- 230000003213 activating effect Effects 0.000 claims 2
- RWPKQHSOHWJJBE-UHFFFAOYSA-N 4-(1-methoxypentyl)phenol Chemical compound COC(C1=CC=C(C=C1)O)CCCC RWPKQHSOHWJJBE-UHFFFAOYSA-N 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 abstract description 20
- 230000003078 antioxidant effect Effects 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 description 82
- 230000000052 comparative effect Effects 0.000 description 21
- 239000007788 liquid Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- -1 light Inorganic materials 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- PHQFMPNZCIHSPC-UHFFFAOYSA-N 1,3,5-tris(chloromethyl)-2,4,6-trimethylbenzene Chemical compound CC1=C(CCl)C(C)=C(CCl)C(C)=C1CCl PHQFMPNZCIHSPC-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical class CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AHXXIALEMINDAW-UHFFFAOYSA-N 4-(methoxymethyl)phenol Chemical compound COCC1=CC=C(O)C=C1 AHXXIALEMINDAW-UHFFFAOYSA-N 0.000 description 1
- BLPODHBKBPRTPG-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]phenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C=C(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C=2)=C1 BLPODHBKBPRTPG-UHFFFAOYSA-N 0.000 description 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKIIEJOIXGHUKX-UHFFFAOYSA-L Cadmium iodide Inorganic materials [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NWTLYIZAMXLXJI-UHFFFAOYSA-N [O-2].[O-2].[O-2].O.[Ti+4].[Mn+2] Chemical compound [O-2].[O-2].[O-2].O.[Ti+4].[Mn+2] NWTLYIZAMXLXJI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 235000019261 food antioxidant Nutrition 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- JWCKCCMWAGPCHA-UHFFFAOYSA-N methoxy(phenyl)methanol Chemical compound COC(O)C1=CC=CC=C1 JWCKCCMWAGPCHA-UHFFFAOYSA-N 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N o-hydroxybenzyl alcohol Natural products OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 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 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The object of the present invention is to provide a kind of synthetic methods of antioxidant 330, the present invention is prepared for the molecular sieve carried phosphoric acid of manganese dioxide-titanium dioxide-and the molecular sieve carried phosphoric acid catalyst of ferroso-ferric oxide-, in the presence of manganese dioxide-titanium dioxide-molecular sieve carried phosphoric acid catalyst, with 2, 6- di-tert-butyl p-cresol, methanol is to prepare Material synthesis 3, 5- di-t-butyl -4- hydroxyl benzyl methyl ether, methanol is to prepare Material synthesis 3, 5- di-t-butyl -4- hydroxyl benzyl methyl ether, then in the presence of Fe 3 O-molecular sieve carried phosphoric acid catalyst, by described 3, 5- di-t-butyl -4- hydroxyl benzyl methyl ether is reacted with mesitylene, it can be prepared by antioxidant 330, the yield for the antioxidant that the present invention synthesizes is high, and purity is high.
Description
Technical field
The invention belongs to high molecular material function additive fields, and in particular to a kind of synthetic method of antioxidant, more specifically
Ground is related to a kind of synthetic method of Hinered phenols antioxidant 330.
Background technique
Synthetic resin and its product be inevitably heated in its synthesis, processing and application process, oxygen, light, heavy metal
Particle and mechanical shearing are acted on and are degraded, and are caused product aging, discoloration and mechanical property to decrease up to and are lost use value completely,
The processing aids such as antioxidant must be thus added in the material.A small amount of antioxidant is added, the aging of high polymer can be risen and be prolonged
Slow effect, is widely used in the plastics and rubber such as ABS, PEA.Antioxidant is various in style.By state can be divided into solid antioxidant and
Liquid antioxidant；Plastic antioxidants, rubber antioxidant, petroleum antioxidant and food antioxidant can be divided by its purposes；By its function
It can be divided into primary antioxidant, auxiliary antioxidant, metallic ion passivation agent, resistant to thermal aging agent etc..If pressing classification of chemical structure, and can
It is divided into following a few classes: phenolic antioxidant, Phosphorus antioxidant, amine antioxidants, complex type antioxidant.Most of phenolic antioxidants are all
Structure with hindered phenol, hindered phenol antioxygen are the main bodys of antioxidant, although its protective capacities is less than amine antioxidants,
It has the characteristics that non-discolouring, non-staining not available for amine, thus is widely used in plastic products.
(3,5- di-tert-butyl-4-hydroxyl benzyl) benzene of 1,3,5- trimethyl -2,4,6- three (antioxidant 330) is that one kind is obstructed
Phenolic antioxidant, suitable for various polymer and the antioxidant stabilizer of organic material, with phosphite ester, thioesters, benzo furan
The auxiliary antioxidants such as ketone, carbon free radical trapers of muttering cooperation has good synergy, assigns the excellent processing of product and stablizes
Property and good lasting stability.With traditional antioxidant ratio, have the characteristics that efficiently, it is low toxicity, pollution-free, thus the product exists
Industrially by very big application prospect.
As existing preparation method, in the United States Patent (USP) US3026264A of early stage, describe using sulfuric acid as catalyst,
2,6- di-t-butyl -4- hydroxy-benzyl alcohol and mesitylene are the preparation method of raw material.Patent hereafter carries out the method
It improves, the patent report of United States Patent (USP) US4754007, US5292669 is a kind of equal as catalyst using sulfuric acid or methanesulfonic acid
Trimethylbenzene and 2, the method that 6- di-t-butyl -4- hydroxyl benzyl oxide prepares antioxidant 330, but the yield of this method is not still high,
Waste acid quantity is big, easily causes environmental pollution.
In existing preparation method, the preparation method of antioxidant 330 can be mainly divided into two kinds.One of which is 1,3,5-
Trihalomethyl -2,4,6- trimethylbenzene and 2,6 di t butyl phenol are to prepare raw material to prepare antioxidant 330.Chinese patent
CN101717326 disclose it is a kind of using solid super-strong acid be catalyst 1,3,5- trihalomethyl -2,4,6- trimethylbenzene and 2,
6- DI-tert-butylphenol compounds are the method for preparing raw material raw material to prepare antioxidant 330, and the method has operating process simple, reaction
Mild condition, the feature that product is easily isolated, catalyst is reusable and environmental pollution is small, Chinese patent
201210564493.2 disclose it is a kind of using silicon dioxide carried phosphotungstic acid as catalyst, with 1,3,5- trichloromethyl -2,4,
6- trimethylbenzene and DI-tert-butylphenol compounds are the synthetic method that raw material prepares antioxidant 330.Chinese patent 20151021181.8 is public
It has opened and has used a kind of trifluoro potassium sulfonate, -1,10 phenanthrolene of 3,4,7,8- tetramethyl and CdI2Mixture can be used as
Ternary complex catalyst, with 1,3,5- trichloromethyl -2,4,6- trimethylbenzene and DI-tert-butylphenol compounds are that raw material prepares antioxidant
330.However its method use prepare raw material 1,3,5- trihalomethyl -2,4,6- trimethylbenzene and 2,6 di t butyl phenol simultaneously
Without the source being suitably mass produced, and in reaction, active component is easy to be lost in the reaction, though this solid catalyst
So there is preferable initial catalytic activity, but catalyst life is shorter, is unfavorable for reusing.
Another method for preparing antioxidant 330 is to be with 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether and mesitylene
Raw material is prepared, using acid as catalyst preparation antioxidant 330.Chinese patent 201010516859.X passes through in surfactant
In the presence of organic solvent is evaporated off, to improve the reaction rate of 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether and mesitylene, improve and produce
Product form.Chinese patent 20111023.9048.4 disclose it is a kind of matched using amido organic sulfonic acid inner salt and sulfuric acid be made as
Catalyst, is catalyzed mesitylene and 3 in halohydrocarbon solution, and 5- di-t-butyl -4- hydroxyl benzyl methyl ether reaction prepares antioxidant 330
Method.With preparation method that 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether is raw material there are easily controllable, yield is high, and product is not
The advantages that recrystallizing is needed, but long there are the reaction time, the shortcomings that intermediate and acid need to be added dropwise simultaneously.The method produces antioxygen
The key of agent 330 is intermediate 3, the synthesis of 5- di-t-butyl -4- hydroxyl benzyl methyl ether, however, intermediate 3,5- di-t-butyl -4-
The price of hydroxyl benzyl methyl ether is higher, not yet domesticizes, the synthesis of current 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether reported in the literature
Method mainly with 2,6- DI-tert-butylphenol compounds, paraformaldehyde, methanol be Material synthesis (apply chemical industry, 2010,39 (7),
1021-1024；Plastic additive, 2006,6,29-33), the post-processing of reaction synthesis is complicated, it needs to use methanol repeated recrystallize,
Catalyst used in reaction is not easily recycled, and main active component is easy to run off.
As described above, there are many defects, what is needed although having existed the synthetic method of antioxidant 330 in more
It designs easily recycling, reusable, high catalytic efficiency catalyst and synthesizes antioxidant 330.
Summary of the invention
Present invention aim to address above-mentioned problem of the prior art.A kind of antioxidant 330 (1,3,5- trimethyl-is provided
2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene) synthetic method.The synthetic method is with 2,6- di-t-butyl
Paracresol, methanol are to prepare Material synthesis 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)) for the compound
(I) it is reacted with mesitylene, can be prepared by the antioxidant 330 (compound (II)).
On the one hand, the present invention provides the synthetic method of 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)), institutes
The synthetic method stated the following steps are included:
(1) after being uniformly mixed 2,6-di-tert-butyl p-cresol, methanol, catalyst A, mixture A is obtained；
(2) under xenon lamp irradiation, by mixture A under 50 DEG C -70 DEG C of reaction temperature, after stirring 2-3h, it is cooled to room
Temperature obtains mixture B；
(3) the mixture B that step (2) obtains is filtered while hot and recycles catalyst, obtain liquor C；
(4) step (4) being obtained into liquor C and is cooled to -5 DEG C -- 10 DEG C of crystallizations are washed after filtering obtained crystal with methanol
It washs 3 times, compound (I) is obtained after vacuum drying.
Wherein, catalyst A and 2 described in the step of above compound (I) synthetic method (1), 6- DI-tert-butylphenol compounds
With the weight fraction ratio of methanol are as follows: 1-3:10:50.
Preferably, the reaction temperature in the step of above compound (I) synthetic method (2) is 55 DEG C -65 DEG C.
Xenon lamp in above-mentioned steps (2) is all band light, optical energy density 300mw/cm2
Catalyst A described in the step of above compound (I) synthetic method (1) is MnO2-TiO2ZSM-5 molecular sieve is negative
Carry phosphoric acid catalyst, the preparation method of the catalyst A the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 3-5h, it is cooling after being activated 3 hours at 250 DEG C
ZSM-5 molecular sieve to room temperature, after being activated；
(S2) manganese nitrate is dissolved in deionized water and dehydrated alcohol, be slowly added into while stirring butyl titanate and
Diethanol amine, ultrasonic disperse 2-3h obtains colloidal sol after mixing evenly；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is mixed with the colloidal sol that step (S2) obtains, is stirred
After being uniformly dispersed, filter cake is obtained by filtration after standing 2h, is cleaned respectively with water and ethyl alcohol later, is dried in vacuo 4-6h at 60 DEG C,
3h is roasted at 450 DEG C in Muffle furnace, is cooled to room temperature to obtain manganese dioxide-titanium dioxide-ZSM-5 molecular sieve；
(S4) manganese dioxide-titanium dioxide-ZSM-5 molecular sieve obtained in step (S3) is immersed in phosphoric acid, room temperature
Lower dipping 8-12h, 100 DEG C of heat treatment 3-5h, activation 3h obtains ferroso-ferric oxide-ZSM-5 molecule after being cooled to room temperature at 250 DEG C
Sieve load phosphoric acid catalyst.
Manganese nitrate, deionized water in the preparation method step (S2) of the catalyst A, dehydrated alcohol, four fourth of metatitanic acid
The weight fraction ratio of ester and diethanol amine are as follows: 1-5:5:20:1-5:5.
The parts by weight of ZSM-5 molecular sieve and colloidal sol in the preparation method step (S3) of the catalyst A after activation
Than for 2-6:10.
Manganese dioxide-titanium dioxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst A preparation method step (S4)
Weight fraction ratio be 3-7:10.
Preferably, the manganese nitrate in the catalyst A preparation method step (2), deionized water, dehydrated alcohol, metatitanic acid
The weight fraction ratio of four butyl esters, diethanol amine are as follows: 1-3:5:20:3-5:5.
Preferably, the weight of the ZSM-5 molecular sieve in the preparation method step (3) of the catalyst A after activation and colloidal sol
Amount portion rate is 4-5:100.
Preferably, manganese dioxide-titanium dioxide-ZSM-5 molecular sieve in the catalyst B preparation method step (4)
Weight fraction ratio with phosphoric acid is 4-6:10.
On the other hand, the present invention provides the synthetic method of antioxidant 330 (compound (II)), the synthetic method packets
Include following steps:
(1) after catalyst B being added to mesitylene, mixture a is obtained after ultrasound is uniform；
(2) compound (I) is added in dichloromethane solvent, obtains mixture b after mixing evenly；
(3) mixture b is added dropwise to while stirring in mixture a, reacts 1-3h at 5-20 DEG C, is cooled to room temperature
Obtain mixture c；
(4) catalyst B is recycled after the mixture c filtering obtained step (3), obtains filtrate d；
(5) it is concentrated to dryness the filtrate d that step (4) obtains to obtain crude product, crude product is recrystallized through normal heptane, filters, is true
Up to above compound (II) after sky is dry.
Wherein, the step of above compound (II) preparation method (1), catalyst B, mesitylene, chemical combination described in (2)
Object (I), methylene chloride are respectively as follows: 1-4:10-50:10:60-100 by ratio of weight and the number of copies.
Preferably, the step of above compound (II) preparation method (1), catalyst B, mesitylene, change described in (2)
Close object (I), methylene chloride is respectively as follows: 2-4:20-40:10:70-90 by ratio of weight and the number of copies.
Catalyst B described in the step of above compound (II) preparation method (1) is ferroso-ferric oxide-ZSM-5 molecule
Sieve load phosphoric acid catalyst, it is similar to the preparation method of catalyst A, the preparation method of the catalyst B the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 3-5h, it is cooling after being activated 3 hours at 250 DEG C
ZSM-5 molecular sieve to room temperature, after being activated；
(S2) in deionized water by ferric nitrate dissolution, it is mixed after addition dehydrated alcohol mixing ultrasonic disperse is uniform
Liquid；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is immersed in mixing obtained in step (S2)
Liquid stands 2h, is cleaned respectively with water and ethyl alcohol later, be dried in vacuo 4-6h at 60 DEG C, roast 3- under 500 DEG C of nitrogen protections
4h is cooled to room temperature and obtains ferroso-ferric oxide-ZSM-5 molecular sieve；
(S4) ferroso-ferric oxide-ZSM-5 molecular sieve obtained in step (S3) is immersed in phosphoric acid, impregnates 8- at room temperature
Filter cake is dried in vacuo 4-6h after filtering by 12h at 6O DEG C, then calcination activation 2h obtains four after being cooled to room temperature at 250 DEG C
Fe 3 O-ZSM-5 molecular sieve loads phosphoric acid catalyst.
The parts by weight of ferric nitrate and deionized water and dehydrated alcohol in the catalyst B preparation method step (S2)
Than for 3-7:5:20.
The weight fraction ratio of ZSM-5 molecular sieve and mixed liquor is 2- in the preparation method step (S3) of the catalyst B
6:10.
The parts by weight of ferroso-ferric oxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst B preparation method step (S4)
Number is than being 1-5:10.
Preferably, the weight of the ferric nitrate in the catalyst B preparation method step (2) and deionized water and dehydrated alcohol
Amount portion rate is 4-6:5:20.
Preferably, in the preparation method step (3) of the catalyst B ZSM-5 molecular sieve and mixed liquor parts by weight
Than for 3-5:10.
Preferably, ferroso-ferric oxide-ZSM-5 molecular sieve in the catalyst B preparation method step (4) and phosphoric acid
Weight fraction ratio is 2-4:10.
Compared with prior art, the invention has the benefit that
(1) the application by by manganese dioxide and titanium dichloride load on ZSM-5 molecular sieve, and by the ZSM- after load
5 molecular sieves are handled with phosphoric acid, are prepared for manganese dioxide-titanium dioxide-ZSM-5 molecular sieve load phosphoric acid catalyst (catalysis
Agent A).
(2) prepare catalyst A can be used as a kind of solid acid photocatalyst, can be catalyzed 2,6-di-tert-butyl p-cresol and
Methanol-fueled CLC 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)).The solid catalyst of the synthetic reaction easily recycles, surely
Qualitative good, the reaction time is short, and still has good catalytic activity after reusing, and compound (I) yield obtained is high-purity
It spends.
(3) the application is by the way that ferroso-ferric oxide to be supported on ZSM-5 molecular sieve, and by the ZSM-5 molecular sieve after load
It is handled with phosphoric acid, is prepared for ferroso-ferric oxide-ZSM-5 molecular sieve load phosphoric acid catalyst (catalyst B).
(4) the catalyst B prepared can be used as a kind of solid acid catalyst, can be catalyzed 2,6-di-tert-butyl p-cresol and first
Alcohol synthesizes 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)).Compared with using concentrated sulfuric acid catalyst, the synthetic reaction
Solid catalyst can magnetic recycling, stability is good, and reaction condition is mild, and reuse after still have good catalysis work
Property, antioxidant 330 obtained yield with higher and purity.
Specific embodiment
The explanation of following embodiment is merely used to help understand method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.To disclosed implementation
The following the description of example, enables those skilled in the art to implement or use the present invention.Various modifications to these embodiments
It will be readily apparent to those skilled in the art, the general principles defined herein can not depart from this
In the case where the spirit or scope of invention, realize in other embodiments.Therefore, the present invention is not intended to be limited to illustrated herein
These embodiments in, but can be applied to meet broader model consistent with the principles and novel features disclosed in this article
It encloses.
Unless otherwise defined, all technical and scientific terms used herein have and the technical field of the invention
The normally understood identical meaning of those of ordinary skill.
1 one kind 3 of embodiment, the synthetic method of 5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)), including following step
It is rapid:
(1) after being uniformly mixed 2,6-di-tert-butyl p-cresol, methanol and catalyst A, mixture A is obtained；
(2) it under xenon lamp irradiation, by mixture A under 50 DEG C of reaction temperature, after stirring 2h, is cooled to room temperature and is mixed
Close object B；
(3) the mixture B that step (2) obtains is filtered while hot and recycles catalyst, obtain liquor C；
(4) step (4) is obtained into liquor C and is cooled to -5 DEG C of crystallizations, washed 3 times after obtained crystal is filtered with methanol,
Compound (I) is obtained after vacuum drying.
Wherein, catalyst A and 2 described in the step of above compound (I) synthetic method (1), 6- DI-tert-butylphenol compounds
With the weight fraction ratio of methanol are as follows: 1:10:50.
Xenon lamp is all band light, optical energy density 300mw/cm in above-mentioned steps (2)2。
Catalyst A described in the step of above compound (I) synthetic method (1) is MnO2-TiO2ZSM-5 molecular sieve is negative
Carry phosphoric acid catalyst, the preparation method of the catalyst A the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 3h, is cooled to after being activated 3 hours at 250 DEG C
Room temperature, the ZSM-5 molecular sieve after being activated；
(S2) manganese nitrate is dissolved in deionized water and ethyl alcohol, is slowly added into butyl titanate and diethyl while stirring
Hydramine, ultrasonic disperse 2h obtains colloidal sol after mixing evenly；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is mixed with the colloidal sol that step (S2) obtains, is stirred
After being uniformly dispersed, filter cake is obtained by filtration after standing 2h, is cleaned respectively with water and ethyl alcohol later, 4h, horse is dried in vacuo at 60 DEG C
3h not is roasted at 450 DEG C in furnace, is cooled to room temperature to obtain manganese dioxide-titanium dioxide-ZSM-5 molecular sieve；
(S4) manganese dioxide-titanium dioxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid,
Impregnate 8h at room temperature, 100 DEG C of heat treatment 3h, activation 3h obtains ferroso-ferric oxide-ZSM-5 molecule after being cooled to room temperature at 250 DEG C
Sieve load phosphoric acid catalyst.
Manganese nitrate, deionized water, dehydrated alcohol, butyl titanate in the catalyst A preparation method step (S2)
With the weight fraction ratio of diethanol amine are as follows: 1:5:20:1:5.
The weight fraction ratio of ZSM-5 molecular sieve and colloidal sol in the preparation method step (3) of the catalyst A after activation
For 2:10.
Manganese dioxide-titanium dioxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst A preparation method step (4)
Weight fraction ratio is 3:10.
2 one kind 3 of embodiment, the synthetic method of 5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)), including following step
It is rapid:
(1) after being uniformly mixed 2,6-di-tert-butyl p-cresol, methanol and catalyst A, mixture A is obtained；
(2) it under xenon lamp irradiation, by mixture A under 70 DEG C of reaction temperature, after stirring 3h, is cooled to room temperature and is mixed
Close object B；
(3) the mixture B that step (2) obtains is filtered while hot and recycles catalyst, obtain liquor C；
(4) step (4) is obtained into liquor C and is cooled to -10 DEG C of crystallizations, washed 3 times after obtained crystal is filtered with methanol,
Compound (I) is obtained after vacuum drying.
Wherein, catalyst A and 2 described in the step of above compound (I) synthetic method (1), 6- DI-tert-butylphenol compounds
With the weight fraction ratio of methanol are as follows: 3:10:50.
Xenon lamp is all band light, optical energy density 300mw/cm in above-mentioned steps (2)2。
Catalyst A described in the step of above compound (I) synthetic method (1) is MnO2-TiO2ZSM-5 molecular sieve is negative
Carry phosphoric acid catalyst, the preparation method of the catalyst A the following steps are included:
(S1) ZSM-5 molecular sieve ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 5h, activation 3 is small at 250 DEG C
When after be cooled to room temperature, the ZSM-5 molecular sieve after being activated；
(S2) manganese nitrate is dissolved in deionized water and ethyl alcohol, is slowly added into butyl titanate and diethyl while stirring
Hydramine, ultrasonic disperse 3h obtains colloidal sol after mixing evenly；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is mixed with the colloidal sol that step (S2) obtains, is stirred
After being uniformly dispersed, filter cake is obtained by filtration after standing 2h, is cleaned respectively with water and ethyl alcohol later, 6h, horse is dried in vacuo at 60 DEG C
3h not is roasted at 450 DEG C in furnace, is cooled to room temperature to obtain manganese dioxide-titanium dioxide-ZSM-5 molecular sieve；
(S4) manganese dioxide-titanium dioxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid,
Impregnate 12h at room temperature, 100 DEG C of heat treatment 5h, activation 3h obtains ferroso-ferric oxide-ZSM-5 molecule after being cooled to room temperature at 250 DEG C
Sieve load phosphoric acid catalyst.
Manganese nitrate, deionized water, dehydrated alcohol, butyl titanate in the catalyst A preparation method step (S2)
With the weight fraction ratio of diethanol amine are as follows: 5:5:20:5:5.
The parts by weight of ZSM-5 molecular sieve and colloidal sol in the preparation method step (S3) of the catalyst A after activation
Than for 6:10.
Manganese dioxide-titanium dioxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst A preparation method step (S4)
Weight fraction ratio be 7:10.
3 one kind 3 of embodiment, the synthetic method of 5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)), including following step
It is rapid:
(1) after being uniformly mixed 2,6-di-tert-butyl p-cresol, methanol and catalyst A, mixture A is obtained；
(2) it under xenon lamp irradiation, by mixture A under 55 DEG C of reaction temperature, after stirring 3h, is cooled to room temperature and is mixed
Close object B；
(3) the mixture B that step (2) obtains is filtered while hot and recycles catalyst, obtain liquor C；
(4) step (4) is obtained into liquor C and is cooled to -8 DEG C of crystallizations, washed 3 times after obtained crystal is filtered with methanol,
Compound (I) is obtained after vacuum drying.
Wherein, catalyst A and 2 described in the step of above compound (I) synthetic method (1), 6- DI-tert-butylphenol compounds
With the weight fraction ratio of methanol are as follows: 1.5:10:50.
Xenon lamp is all band light, optical energy density 300mw/cm in above-mentioned steps (2)2。
Catalyst A described in the step of above compound (I) synthetic method (1) is MnO2-TiO2ZSM-5 molecular sieve is negative
Carry phosphoric acid catalyst, the preparation method of the catalyst A the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 5h, is cooled to after being activated 3 hours at 250 DEG C
Room temperature, the ZSM-5 molecular sieve after being activated；
(S2) manganese nitrate is dissolved in deionized water and ethyl alcohol, is slowly added into butyl titanate and diethyl while stirring
Hydramine, ultrasonic disperse 3h obtains colloidal sol after mixing evenly；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is mixed with the colloidal sol that step (S2) obtains, is stirred
After being uniformly dispersed, filter cake is obtained by filtration after standing 2h, is cleaned respectively with water and ethyl alcohol later, 6h, horse is dried in vacuo at 60 DEG C
3h not is roasted at 450 DEG C in furnace, is cooled to room temperature to obtain manganese dioxide-titanium dioxide-ZSM-5 molecular sieve；
(S4) manganese dioxide-titanium dioxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid,
Impregnate 12h at room temperature, 100 DEG C of heat treatment 5h, activation 3h obtains ferroso-ferric oxide-ZSM-5 molecule after being cooled to room temperature at 250 DEG C
Sieve load phosphoric acid catalyst.
Manganese nitrate, deionized water, dehydrated alcohol, butyl titanate in the catalyst A preparation method step (S2)
With the weight fraction ratio of diethanol amine are as follows: 1:5:20:3:5.
The parts by weight of ZSM-5 molecular sieve and colloidal sol in the preparation method step (S3) of the catalyst A after activation
Than for 4:10.
Manganese dioxide-titanium dioxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst A preparation method step (S4)
Weight fraction ratio be 4:10.
4 one kind 3 of embodiment, the synthetic method of 5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)), including following step
It is rapid:
(1) after being uniformly mixed 2,6-di-tert-butyl p-cresol, methanol and catalyst A, mixture A is obtained；
(2) it under xenon lamp irradiation, by mixture A under 65 DEG C of reaction temperature, after stirring 3h, is cooled to room temperature and is mixed
Close object B；
(3) the mixture B that step (2) obtains is filtered while hot and recycles catalyst, obtain liquor C；
(4) step (4) is obtained into liquor C and is cooled to -10 DEG C of crystallizations, washed 3 times after obtained crystal is filtered with methanol,
Compound (I) is obtained after vacuum drying.
Wherein, catalyst A and 2 described in the step of above compound (I) synthetic method (1), 6- DI-tert-butylphenol compounds
With the weight fraction ratio of methanol are as follows: 3:10:50.
Xenon lamp is all band light, optical energy density 300mw/cm in above-mentioned steps (2)2。
Preferably, the reaction temperature in the step of above compound (I) synthetic method (2) is 60 DEG C.
Catalyst A described in the step of above compound (I) synthetic method (1) is MnO2-TiO2ZSM-5 molecular sieve is negative
Carry phosphoric acid catalyst, the preparation method of the catalyst A the following steps are included:
(S1) ZSM-5 molecular sieve ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 5h, activation 3 is small at 250 DEG C
When after be cooled to room temperature, the ZSM-5 molecular sieve after being activated；
(S2) manganese nitrate is dissolved in deionized water and ethyl alcohol, is slowly added into butyl titanate and diethyl while stirring
Hydramine, ultrasonic disperse 3h obtains colloidal sol after mixing evenly；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is mixed with the colloidal sol that step (S2) obtains, is stirred
After being uniformly dispersed, filter cake is obtained by filtration after standing 2h, is cleaned respectively with water and ethyl alcohol later, 6h, horse is dried in vacuo at 60 DEG C
3h not is roasted at 450 DEG C in furnace, is cooled to room temperature to obtain manganese dioxide-titanium dioxide-ZSM-5 molecular sieve；
(S4) manganese dioxide-titanium dioxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid,
Impregnate 12h at room temperature, 100 DEG C of heat treatment 5h, activation 3h obtains ferroso-ferric oxide-ZSM-5 molecule after being cooled to room temperature at 250 DEG C
Sieve load phosphoric acid catalyst.
Manganese nitrate, deionized water, dehydrated alcohol, butyl titanate in the catalyst A preparation method step (S2)
With the weight fraction ratio of diethanol amine are as follows: 3:5:20:5:5.
The parts by weight of ZSM-5 molecular sieve and colloidal sol in the preparation method step (S3) of the catalyst A after activation
Than for 5:10.
Manganese dioxide-titanium dioxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst A preparation method step (S4)
Weight fraction ratio be 6:10.
5 one kind 3 of embodiment, the synthetic method of 5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)), including following step
It is rapid:
(1) after being uniformly mixed 2,6-di-tert-butyl p-cresol, methanol and catalyst A, mixture A is obtained；
(2) it under xenon lamp irradiation, by mixture A under 60 DEG C of reaction temperature, after stirring 3h, is cooled to room temperature and is mixed
Close object B；
(3) the mixture B that step (2) obtains is filtered while hot and recycles catalyst, obtain liquor C；
(4) step (4) is obtained into liquor C and is cooled to -8 DEG C of crystallizations, washed 3 times after obtained crystal is filtered with methanol,
Compound (I) is obtained after vacuum drying.
Wherein, catalyst A and 2 described in the step of above compound (I) synthetic method (1), 6- DI-tert-butylphenol compounds
With the weight fraction ratio of methanol are as follows: 2:10:50.
Xenon lamp is all band light, optical energy density 300mw/cm in above-mentioned steps (2)2。
Catalyst A described in the step of above compound (I) synthetic method (1) is MnO2-TiO2ZSM-5 molecular sieve is negative
Carry phosphoric acid catalyst, the preparation method of the catalyst A the following steps are included:
(S1) ZSM-5 molecular sieve ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 5h, activation 3 is small at 250 DEG C
When after be cooled to room temperature, the ZSM-5 molecular sieve after being activated；
(S2) manganese nitrate is dissolved in deionized water and ethyl alcohol, is slowly added into butyl titanate and diethyl while stirring
Hydramine, ultrasonic disperse 3h obtains colloidal sol after mixing evenly；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is mixed with the colloidal sol that step (S2) obtains, is stirred
After being uniformly dispersed, filter cake is obtained by filtration after standing 2h, is cleaned respectively with water and ethyl alcohol later, 6h, horse is dried in vacuo at 60 DEG C
3h not is roasted at 450 DEG C in furnace, is cooled to room temperature to obtain manganese dioxide-titanium dioxide-ZSM-5 molecular sieve；
(S4) manganese dioxide-titanium dioxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid,
Impregnate 12h at room temperature, 100 DEG C of heat treatment 5h, activation 3h obtains ferroso-ferric oxide-ZSM-5 molecule after being cooled to room temperature at 250 DEG C
Sieve load phosphoric acid catalyst.
Manganese nitrate, deionized water, dehydrated alcohol, butyl titanate in the catalyst A preparation method step (S2)
With the weight fraction ratio of diethanol amine are as follows: 2:5:20:4:5.
The parts by weight of ZSM-5 molecular sieve and colloidal sol in the preparation method step (S3) of the catalyst A after activation
Than for 4.5:10.
Manganese dioxide-titanium dioxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst A preparation method step (S4)
Weight fraction ratio be 5:10.
Embodiment 6-10 is using 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)) prepared by embodiment 5 as raw material
Synthesize antioxidant 330.
A kind of synthetic method of the antioxidant 330 of embodiment 6 (compound (II)), the preparation method includes following step
It is rapid:
(1) after catalyst B being added to mesitylene, mixture a is obtained after mixing evenly；
(2) compound (I) is added in dichloromethane solvent, obtains mixture b after mixing evenly；
(3) mixture b is added dropwise to while stirring in mixture a, reacts 1h at 5 DEG C, be cooled to room temperature to obtain
Mixture c；
(4) catalyst B is recycled after the mixture c filtering obtained step (3), obtains filtrate d；
(5) it is concentrated to dryness the filtrate d that step (4) obtains to obtain crude product, crude product is recrystallized through normal heptane, recrystallization
Method is that normal heptane dissolution is added into crude product, after being heated to 85 DEG C of reflux 2h, is cooled to room temperature to obtain crystal, by crystal mistake
Up to above compound (II) after filter, vacuum drying.
Wherein, the step of above compound (II) preparation method (1), catalyst B, mesitylene, chemical combination described in (2)
Object (I), methylene chloride are respectively as follows: 1:10:10:60 by ratio of weight and the number of copies.
Preferably, the step of above compound (II) preparation method (1), catalyst B, mesitylene, change described in (2)
Close object (I), methylene chloride is respectively as follows: 2:20:10:70 by ratio of weight and the number of copies.
Catalyst B described in the step of above compound (II) preparation method (1) is ferroso-ferric oxide-ZSM-5 molecule
Sieve load phosphoric acid catalyst, it is similar to the preparation method of catalyst A, the preparation method of the catalyst B the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 3h, is cooled to after being activated 3 hours at 250 DEG C
Room temperature, the ZSM-5 molecular sieve after being activated；
(S2) in deionized water by ferric nitrate dissolution, it is mixed after addition dehydrated alcohol mixing ultrasonic disperse is uniform
Liquid；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is immersed in mixing obtained in step (S2)
Liquid stands 2h, is cleaned respectively with water and ethyl alcohol later, be dried in vacuo 4h at 60 DEG C, roast 3h under 500 DEG C of nitrogen protections,
It is cooled to room temperature and obtains ferroso-ferric oxide-ZSM-5 molecular sieve；
(S4) ferroso-ferric oxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid, is soaked at room temperature
Filter cake is dried in vacuo 4h after filtering by stain 8h at 6O DEG C, then calcination activation 2h obtains four oxygen at 250 DEG C after being cooled to room temperature
Change three-iron-ZSM-5 molecular sieve and loads phosphoric acid catalyst.
The parts by weight of ferric nitrate and deionized water and dehydrated alcohol in the catalyst B preparation method step (S2)
Than for 3:5:20.
The weight fraction ratio of ZSM-5 molecular sieve and mixed liquor is 2 in the preparation method step (S3) of the catalyst B:
10。
The parts by weight of ferroso-ferric oxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst B preparation method step (S4)
Number is than being 1:10.
A kind of synthetic method of the antioxidant 330 of embodiment 7 (compound (II)), the synthetic method includes following step
It is rapid:
(1) after catalyst B being added to mesitylene, mixture a is obtained after mixing evenly；
(2) compound (I) is added in dichloromethane solvent, obtains mixture b after mixing evenly；
(3) mixture b is added dropwise to while stirring in mixture a, reacts 3h at 20 DEG C, be cooled to room temperature to obtain
Mixture c；
(4) catalyst B is recycled after the mixture c filtering obtained step (3), obtains filtrate d；
(5) it is concentrated to dryness the filtrate d that step (4) obtains to obtain crude product, crude product is recrystallized through normal heptane, recrystallization
Method is that normal heptane dissolution is added into crude product, after being heated to 85 DEG C of reflux 2h, is cooled to room temperature to obtain crystal, by crystal mistake
Up to above compound (II) after filter, vacuum drying.
Wherein, the step of above compound (II) preparation method (1), catalyst B, mesitylene, chemical combination described in (2)
Object (I), methylene chloride are respectively as follows: 4:10:10:100 by ratio of weight and the number of copies.
Catalyst B described in the step of above compound (II) preparation method (1) is ferroso-ferric oxide-ZSM-5 molecule
Sieve load phosphoric acid catalyst, it is similar to the preparation method of catalyst A, the preparation method of the catalyst B the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 5h, is cooled to after being activated 3 hours at 250 DEG C
Room temperature, the ZSM-5 molecular sieve after being activated；
(S2) in deionized water by ferric nitrate dissolution, it is mixed after addition dehydrated alcohol mixing ultrasonic disperse is uniform
Liquid；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is immersed in mixing obtained in step (S2)
Liquid stands 2h, is cleaned respectively with water and ethyl alcohol later, be dried in vacuo 6h at 60 DEG C, roast 4h under 500 DEG C of nitrogen protections,
It is cooled to room temperature and obtains ferroso-ferric oxide-ZSM-5 molecular sieve；
(S4) ferroso-ferric oxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid, is soaked at room temperature
Filter cake is dried in vacuo 6h after filtering by stain 12h at 6O DEG C, then calcination activation 2h obtains four after being cooled to room temperature at 250 DEG C
Fe 3 O-ZSM-5 molecular sieve loads phosphoric acid catalyst.
The parts by weight of ferric nitrate and deionized water and dehydrated alcohol in the catalyst B preparation method step (S2)
Than for 7:5:20.
The weight fraction ratio of ZSM-5 molecular sieve and mixed liquor is 6 in the preparation method step (S3) of the catalyst B:
10。
The parts by weight of ferroso-ferric oxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst B preparation method step (S4)
Number is than being 5:10.
A kind of synthetic method of the antioxidant 330 of embodiment 8 (compound (II)), the synthetic method includes following step
It is rapid:
(1) after catalyst B being added to mesitylene, mixture a is obtained after mixing evenly；
(2) compound (I) is added in dichloromethane solvent, obtains mixture b after mixing evenly；
(3) mixture b is added dropwise to while stirring in mixture a, reacts 1.5h at 8 DEG C, is cooled to room temperature
To mixture c；
(4) catalyst B is recycled after the mixture c filtering obtained step (3), obtains filtrate d；
(5) it is concentrated to dryness the filtrate d that step (4) obtains to obtain crude product, crude product is recrystallized through normal heptane, recrystallization
Method is that normal heptane dissolution is added into crude product, after being heated to 85 DEG C of reflux 2h, is cooled to room temperature to obtain crystal, by crystal mistake
Up to above compound (II) after filter, vacuum drying.
Wherein, the step of above compound (II) preparation method (1), catalyst B, mesitylene, chemical combination described in (2)
Object (I), methylene chloride are respectively as follows: 2:20:10:70 by ratio of weight and the number of copies.
Catalyst B described in the step of above compound (II) preparation method (1) is ferroso-ferric oxide-ZSM-5 molecule
Sieve load phosphoric acid catalyst, it is similar to the preparation method of catalyst A, the preparation method of the catalyst B the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 5h, is cooled to after being activated 3 hours at 250 DEG C
Room temperature, the ZSM-5 molecular sieve after being activated；
(S2) in deionized water by ferric nitrate dissolution, it is mixed after addition dehydrated alcohol mixing ultrasonic disperse is uniform
Liquid；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is immersed in mixing obtained in step (S2)
Liquid stands 2h, is cleaned respectively with water and ethyl alcohol later, be dried in vacuo 6h at 60 DEG C, roast 4h under 500 DEG C of nitrogen protections,
It is cooled to room temperature and obtains ferroso-ferric oxide-ZSM-5 molecular sieve；
(S4) ferroso-ferric oxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid, is soaked at room temperature
Filter cake is dried in vacuo 6h after filtering by stain 12h at 6O DEG C, then calcination activation 2h obtains four after being cooled to room temperature at 250 DEG C
Fe 3 O-ZSM-5 molecular sieve loads phosphoric acid catalyst.
The parts by weight of ferric nitrate and deionized water and dehydrated alcohol in the catalyst B preparation method step (S2)
Than for 4:5:20.
The weight fraction ratio of ZSM-5 molecular sieve and mixed liquor is 3 in the preparation method step (S3) of the catalyst B:
10。
The parts by weight of ferroso-ferric oxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst B preparation method step (S4)
Number is than being 2:10.
A kind of synthetic method of the antioxidant 330 of embodiment 9 (compound (II)), the synthetic method includes following step
It is rapid:
(1) after catalyst B being added to mesitylene, mixture a is obtained after mixing evenly；
(2) compound (I) is added in dichloromethane solvent, obtains mixture b after mixing evenly；
(3) mixture b is added dropwise to while stirring in mixture a, reacts 2.5h at 8 DEG C, is cooled to room temperature
To mixture c；
(4) catalyst B is recycled after the mixture c filtering obtained step (3), obtains filtrate d；
(5) it is concentrated to dryness the filtrate d that step (4) obtains to obtain crude product, crude product is recrystallized through normal heptane, recrystallization
Method is that normal heptane dissolution is added into crude product, after being heated to 85 DEG C of reflux 2h, is cooled to room temperature to obtain crystal, by crystal mistake
Up to above compound (II) after filter, vacuum drying.
Wherein, the step of above compound (II) preparation method (1), catalyst B, mesitylene, chemical combination described in (2)
Object (I), methylene chloride are respectively as follows: 4:20:10:90 by ratio of weight and the number of copies.
Catalyst B described in the step of above compound (II) preparation method (1) is ferroso-ferric oxide-ZSM-5 molecule
Sieve load phosphoric acid catalyst, it is similar to the preparation method of catalyst A, the preparation method of the catalyst B the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 5h, is cooled to after being activated 3 hours at 250 DEG C
Room temperature, the ZSM-5 molecular sieve after being activated；
(S2) in deionized water by ferric nitrate dissolution, it is mixed after addition dehydrated alcohol mixing ultrasonic disperse is uniform
Liquid；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is immersed in mixing obtained in step (S2)
Liquid stands 2h, is cleaned respectively with water and ethyl alcohol later, be dried in vacuo 6h at 60 DEG C, roast 4h under 500 DEG C of nitrogen protections,
It is cooled to room temperature and obtains ferroso-ferric oxide-ZSM-5 molecular sieve；
(S4) ferroso-ferric oxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid, is soaked at room temperature
Filter cake is dried in vacuo 6h after filtering by stain 12h at 6O DEG C, then calcination activation 2h obtains four after being cooled to room temperature at 250 DEG C
Fe 3 O-ZSM-5 molecular sieve loads phosphoric acid catalyst.
The parts by weight of ferric nitrate and deionized water and dehydrated alcohol in the catalyst B preparation method step (S2)
Than for 6:5:20.
The weight fraction ratio of ZSM-5 molecular sieve and mixed liquor is 5 in the preparation method step (S3) of the catalyst B:
10。
The parts by weight of ferroso-ferric oxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst B preparation method step (S4)
Number is than being 4:10.
A kind of synthetic method of the antioxidant 330 of embodiment 10 (compound (II)), the synthetic method includes following step
It is rapid:
(1) after catalyst B being added to mesitylene, mixture a is obtained after mixing evenly；
(2) compound (I) is added in dichloromethane solvent, obtains mixture b after mixing evenly；
(3) mixture b is added dropwise to while stirring in mixture a, reacts 2h at 10 DEG C, be cooled to room temperature to obtain
Mixture c；
(4) catalyst B is recycled after the mixture c filtering obtained step (3), obtains filtrate d；
(5) it is concentrated to dryness the filtrate d that step (4) obtains to obtain crude product, crude product is recrystallized through normal heptane, recrystallization
Method is that normal heptane dissolution is added into crude product, after being heated to 85 DEG C of reflux 2h, is cooled to room temperature to obtain crystal, by crystal mistake
Up to above compound (II) after filter, vacuum drying.
Wherein, the step of above compound (II) preparation method (1), catalyst B, mesitylene, chemical combination described in (2)
Object (I), methylene chloride are respectively as follows: 3:30:10:80 by ratio of weight and the number of copies.
Catalyst B described in the step of above compound (II) preparation method (1) is ferroso-ferric oxide-ZSM-5 molecule
Sieve load phosphoric acid catalyst, it is similar to the preparation method of catalyst A, the preparation method of the catalyst B the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 5h, is cooled to after being activated 3 hours at 250 DEG C
Room temperature, the ZSM-5 molecular sieve after being activated；
(S2) in deionized water by ferric nitrate dissolution, it is mixed after addition dehydrated alcohol mixing ultrasonic disperse is uniform
Liquid；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is immersed in mixing obtained in step (S2)
Liquid stands 2h, is cleaned respectively with water and ethyl alcohol later, be dried in vacuo 6h at 60 DEG C, roast 4h under 500 DEG C of nitrogen protections,
It is cooled to room temperature and obtains ferroso-ferric oxide-ZSM-5 molecular sieve；
(S4) ferroso-ferric oxide-ZSM-5 molecular sieve obtained in above-mentioned steps (S3) is immersed in phosphoric acid, is soaked at room temperature
Filter cake is dried in vacuo 6h after filtering by stain 12h at 6O DEG C, then calcination activation 2h obtains four after being cooled to room temperature at 250 DEG C
Fe 3 O-ZSM-5 molecular sieve loads phosphoric acid catalyst.
The parts by weight of ferric nitrate and deionized water and dehydrated alcohol in the catalyst B preparation method step (S2)
Than for 5:5:20.
The weight fraction ratio of ZSM-5 molecular sieve and mixed liquor is 4 in the preparation method step (S3) of the catalyst B:
10。
The parts by weight of ferroso-ferric oxide-ZSM-5 molecular sieve and phosphoric acid in the catalyst B preparation method step (S4)
Number is than being 3:10.
A kind of synthetic method of the 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)) of comparative example 1
Preparation method is substantially with embodiment 5, with embodiment 1 the difference is that irradiating in step (1) without xenon lamp.
A kind of synthetic method of the 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)) of comparative example 2
Preparation method is substantially with embodiment 1, with embodiment 1 the difference is that the tertiary fourth of the catalyst A and 2 of step (1), 6- bis-
The weight fraction ratio of base phenol and methanol is 5:10:50.
A kind of synthetic method of the 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether intermediate (compound (I)) of comparative example 3
Preparation method is substantially with embodiment 5, with embodiment 1 the difference is that being added without manganese nitrate in step (S2).
A kind of synthetic method of the 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether intermediate (compound (I)) of comparative example 4
Preparation method is substantially with embodiment 5, with embodiment 1 the difference is that being added without four fourth of metatitanic acid in step (S2)
Ester.
A kind of synthetic method of the 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether intermediate (compound (I)) of comparative example 5
Preparation method is substantially with embodiment 5, with embodiment 1 the difference is that manganese nitrate, deionization in step (S2)
The ratio of water, dehydrated alcohol, butyl titanate and diethanol amine are as follows: 8:5:20:1:5.
A kind of synthetic method of the 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether intermediate (compound (I)) of comparative example 6
Preparation method is substantially with embodiment 1, with embodiment 1 the difference is that ZSM-5 molecule in step (S3) after activation
The weight fraction ratio of sieve and colloidal sol is 10:100.
A kind of synthetic method of the 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether intermediate (compound (I)) of comparative example 7
Preparation method is substantially with embodiment 1, with embodiment 1 the difference is that middle manganese dioxide-titanium dioxide of step (S4)
The weight fraction ratio of titanium-ZSM-5 molecular sieve and phosphoric acid is 8:10.
A kind of synthetic method of the antioxidant 330 of comparative example 8 (compound (II))
Preparation method substantially with embodiment 10, with embodiment 10 the difference is that catalyst B described in step (1), (2),
Mesitylene, compound (I), methylene chloride are 6:50:10:40 by ratio of weight and the number of copies.
A kind of synthetic method of the antioxidant 330 of comparative example 9 (compound (II))
Preparation method is substantially with embodiment 10, with embodiment 10 the difference is that reaction temperature is 25 DEG C in step (3).
A kind of synthetic method of the antioxidant 330 of comparative example 10 (compound (II))
Preparation method is substantially with embodiment 10, with embodiment 10 the difference is that the reaction temperature in step (3) is 0 DEG C.
A kind of synthetic method of the antioxidant 330 of comparative example 11 (compound (II))
Preparation method is substantially with embodiment 10, with embodiment 10 the difference is that ferric nitrate and deionized water in step (S2)
Weight fraction ratio with dehydrated alcohol is 1:5:20.
A kind of synthetic method of the antioxidant 330 of comparative example 12 (compound (II))
Preparation method is substantially with embodiment 10, with embodiment 10 the difference is that being added without ferric nitrate in step (S2).
A kind of synthetic method of the antioxidant 330 of comparative example 13 (compound (II))
Preparation method is substantially with embodiment 10, with embodiment 10 the difference is that ferroso-ferric oxide-ZSM-5 in step (S4)
The weight fraction ratio of molecular sieve and phosphoric acid is 7:10.
A kind of 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether (compound (I)) for calculating embodiment 1-5 and comparative example 1-7 produces
Rate detects purity, the result is as follows:
By above-mentioned experimental result it is found that a kind of synthesis side of 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether provided by the invention
The yield of method, 3, the 5- di-t-butyl -4- hydroxyl benzyl methyl ether of preparation is high, purity is high, wherein implementing 3, the 5- di-t-butyl-in 5
The yield of 4- hydroxyl benzyl methyl ether is 92.2%, purity 99.2%.
Antioxidant 330 (compound (II)) yield that embodiment 6-10 and comparative example 8-13 is provided is calculated, purity, knot are detected
Fruit is as follows:
| Yield (%) | Purity (%) | |
| Embodiment 6 | 89.2 | 99.3 |
| Embodiment 7 | 88.5 | 99.4 |
| Embodiment 8 | 89.1 | 99.4 |
| Embodiment 9 | 88.4 | 99.2 |
| Embodiment 10 | 91.2 | 99.6 |
| Comparative example 8 | 81.6 | 92.3 |
| Comparative example 9 | 79.2 | 93.2 |
| Comparative example 10 | 72.3 | 90.0 |
| Comparative example 11 | 74.3 | 86.5 |
| Comparative example 12 | 76.3 | 82.1 |
| Comparative example 13 | 69.3 | 84.1 |
By above-mentioned experimental result it is found that the synthetic method of antioxidant 330 provided by the invention (compound (II)), preparation
The yield of antioxidant 330 is high, purity is high, wherein the yield for implementing the antioxidant 330 in 10 is 91.2%, purity 99.6%.
By the catalyst A after being reacted in the embodiment of the present invention 5 after recycling washing and drying, according to the embodiment of the present invention 5
In method be recycled twice after, the yield of 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether obtained is 86.6%, and purity is
96.1%.
By the catalyst B after being reacted in the embodiment of the present invention 10 after recycling washing and drying, according to the embodiment of the present invention
After method in 10 is recycled twice, the yield of antioxidant 330 obtained is 82.3%, purity 95.3%.
The synthetic method of 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether provided by the invention, the present invention have adjusted catalysis meticulously
Manganese nitrate in agent preparation, butyl titanate, ZSM-5 molecular sieve and phosphoric acid ratio be prepared for manganese dioxide-titanium dioxide-ZSM-
5 molecular sieve carried phosphoric acid catalysts, reaction temperature is lower, and catalyst easily recycles separation, still has after recycling good
Catalytic activity, the present invention have adjusted catalyst and 2 in reaction process meticulously, the ratio of 6- DI-tert-butylphenol compounds and methanol, not only
The yield of 3, the 5- di-t-butyl -4- hydroxyl benzyl methyl ether of synthesis is high, and purity is also high.
The synthetic method of antioxidant 330 provided by the invention, it is negative that the present invention is prepared for ferroso-ferric oxide-ZSM-5 molecular sieve
Phosphoric acid catalyst is carried, not only makes catalyst that there is Magneto separate, still there is good catalytic activity, no after recycling
The yield of the antioxidant 330 only synthesized is high, and purity is also high.
Only as described above, is only a preferred embodiment of the present invention, when the model that cannot limit implementation of the invention with this
It encloses, i.e., generally according to simple equivalent changes and modifications made by content documented by the claims in the present invention and description of the invention,
All it is still covered by the claims of the invention.It is searched in addition, abstract part and title are intended merely to auxiliary patent document
It seeks and being used, the interest field being not intended to limit the invention.
Claims (8)
1. a kind of synthetic method of antioxidant 330, it is characterised in that: the following steps are included:
(1) after catalyst B being added to mesitylene, mixture a is obtained after ultrasound is uniform；
(2) 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether is added in dichloromethane solvent, obtains mixture b after mixing evenly；
(3) mixture b is added dropwise to while stirring in mixture a, reacts 1-3h at 5-20 DEG C, be cooled to room temperature to obtain
Mixture c；
(4) catalyst B is recycled after the mixture c filtering obtained step (3), obtains filtrate d；
(5) it is concentrated to dryness the filtrate d that step (4) obtains to obtain crude product, crude product is done through normal heptane recrystallization, filtering, vacuum
Up to above-mentioned antioxidant 330 after dry；
The catalyst B is that ferroso-ferric oxide-ZSM-5 molecular sieve loads phosphoric acid catalyst；
The preparation method of the catalyst B the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 3-5h, is cooled to room after activating 3 hours at 250 DEG C
Temperature, the ZSM-5 molecular sieve after being activated；
(S2) in deionized water by ferric nitrate dissolution, mixed liquor is obtained after addition dehydrated alcohol mixing ultrasonic disperse is uniform；
(S3) ZSM-5 molecular sieve after activation that step (S1) obtains is immersed in mixed liquor obtained in step (S2), it is quiet
2h is set, is cleaned respectively with water and ethyl alcohol later, is dried in vacuo 4-6h at 60 DEG C, 3-4h is roasted under 500 DEG C of nitrogen protections, it is cold
But ferroso-ferric oxide-ZSM-5 molecular sieve is obtained to room temperature；
(S4) ferroso-ferric oxide-ZSM-5 molecular sieve obtained in step (S3) is immersed in phosphoric acid, impregnates 8-12h at room temperature,
Filter cake is dried in vacuo 4-6h at 6O DEG C after filtering, then calcination activation 2h obtains four oxidations at 250 DEG C after being cooled to room temperature
Three-iron-ZSM-5 molecular sieve loads phosphoric acid catalyst.
2. synthetic method according to claim 1, it is characterised in that: the catalyst B, mesitylene, 3,5-, bis- uncle
Butyl -4- hydroxyl benzyl methyl ether, methylene chloride are respectively as follows: 1-4:10-50:10:60-100 by ratio of weight and the number of copies.
3. synthetic method according to claim 1, it is characterised in that: ferric nitrate and deionized water and nothing in step (S2)
The weight fraction ratio of water-ethanol is 3-7:5:20.
4. synthetic method according to claim 1, it is characterised in that: ZSM-5 molecular sieve and mixed liquor in step (S3)
Weight fraction ratio is 2-6:10.
5. synthetic method according to claim 1, it is characterised in that: the ferroso-ferric oxide-ZSM-5 molecule in step (S4)
The weight fraction ratio of sieve and phosphoric acid is 1-5:10.
6. synthetic method according to claim 1, it is characterised in that: 3, the 5- di-t-butyl -4- hydroxyl benzyl methyl ether
Synthetic method are as follows:
(1) after being uniformly mixed 2,6-di-tert-butyl p-cresol, methanol, catalyst A, mixture A is obtained；
(2) it under xenon lamp irradiation, by mixture A under 50 DEG C -70 DEG C of reaction temperature, after stirring 2-3h, is cooled to room temperature
To mixture B；
(3) the mixture B that step (2) obtains is filtered while hot and recycles catalyst, obtain liquor C；
(4) step (4) being obtained into liquor C and is cooled to -5 DEG C -- 10 DEG C of crystallizations wash 3 with methanol after filtering obtained crystal
It is secondary, 3,5- di-t-butyl -4- hydroxyl benzyl methyl ether is obtained after vacuum drying；
The catalyst A is manganese dioxide-titanium dioxide-ZSM-5 molecular sieve catalyst；
The preparation method of the catalyst A the following steps are included:
(S1) ZSM-5 molecular sieve is crushed, in an oven 100 DEG C of heat treatment 3-5h, is cooled to room after activating 3 hours at 250 DEG C
Temperature, the ZSM-5 molecular sieve after being activated；
(S2) manganese nitrate is dissolved in deionized water and ethyl alcohol, is slowly added into butyl titanate and diethanol while stirring
Amine, ultrasonic disperse 2-3h obtains colloidal sol after mixing evenly；
(S3) molecular sieve after activation that step (S1) obtains is mixed with the colloidal sol that step (S2) obtains, is dispersed with stirring uniformly
Afterwards, filter cake is obtained by filtration after standing 2h, is cleaned respectively with water and ethyl alcohol later, is dried in vacuo 4-6h at 60 DEG C, in Muffle furnace
3h is roasted at 450 DEG C, is cooled to room temperature to obtain manganese dioxide-titanium dioxide-molecular sieve；
(S4) manganese dioxide-titanium dioxide-ZSM-5 molecular sieve obtained in step (S3) is immersed in phosphoric acid, is soaked at room temperature
Stain 8-12h, 100 DEG C of heat treatment 3-5h, it is negative to obtain ferroso-ferric oxide-ZSM-5 molecular sieve after being cooled to room temperature by activation 3h at 250 DEG C
Carry phosphoric acid catalyst.
7. synthetic method according to claim 6, it is characterised in that: bis- uncle of catalyst A and 2 described in step (1), 6-
The weight fraction ratio of butylphenol and methanol are as follows: 1-3:10:50.
8. synthetic method according to claim 6, it is characterised in that:
The weight fraction ratio of manganese nitrate, deionized water, dehydrated alcohol, diethanol amine in step (S2) are as follows: 1-5:5:20:1-5:
5；
The weight fraction ratio of molecular sieve and colloidal sol in step (S3) after activation is 2-6:10；
The weight fraction ratio of manganese dioxide-titanium dioxide-ZSM-5 molecular sieve and phosphoric acid in step (S4) is 3-7:10.
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| PT67131A (en) * | 1976-10-12 | 1977-11-01 | Nii R I Latexnykh Izdely | Method for the production of 2,4,6-tri-(3,5-ditertiary butyl-4-hydroxybenzyl)mesitylene |
| US4754077A (en) * | 1982-12-16 | 1988-06-28 | Ethyl Corporation | Antioxidant synthesis |
| US7378069B2 (en) * | 2004-07-27 | 2008-05-27 | Los Alamos National Security, Llc | Catalyst and method for reduction of nitrogen oxides |
| CN102452903A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene |
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