CN107522623A - 一种二苯胺类橡胶防老剂的制备方法 - Google Patents
一种二苯胺类橡胶防老剂的制备方法 Download PDFInfo
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- CN107522623A CN107522623A CN201710767072.2A CN201710767072A CN107522623A CN 107522623 A CN107522623 A CN 107522623A CN 201710767072 A CN201710767072 A CN 201710767072A CN 107522623 A CN107522623 A CN 107522623A
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- Prior art keywords
- catalyst
- reaction
- diphenylamines
- solvent
- weight
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003112 inhibitor Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- 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 15
- 238000000034 method Methods 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 16
- 239000011592 zinc chloride Substances 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002608 ionic liquid Substances 0.000 claims description 12
- -1 positive third class Chemical group 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical group CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229940106691 bisphenol a Drugs 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 238000013021 overheating Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims 2
- ZFMFIBDSZCASNS-UHFFFAOYSA-N 2-pentylbenzene-1,4-diol Chemical group CCCCCC1=CC(O)=CC=C1O ZFMFIBDSZCASNS-UHFFFAOYSA-N 0.000 claims 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 7
- 230000029936 alkylation Effects 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- UWWSCTFWINAKSF-UHFFFAOYSA-N CC(C)(c1ccccc1)c(cc1)ccc1Nc1ccc(C(C)(C)P=C)cc1 Chemical compound CC(C)(c1ccccc1)c(cc1)ccc1Nc1ccc(C(C)(C)P=C)cc1 UWWSCTFWINAKSF-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000286904 Leptothecata Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000003974 aralkylamines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical group CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01J31/0285—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 also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- 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
- B01J31/0292—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 immobilised on a substrate
- B01J31/0295—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 immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- 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
Landscapes
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种二苯胺类橡胶防老剂的制备方法，通过将Lewis酸性离子液体负载在分子筛表面，制备成固载催化剂，用于二苯胺的烷基化反应。该方法能够以在收率、纯度、催化剂寿命等方面较现有技术均具有显著地进步。
Description
技术领域
本发明属于有机合成化学橡胶添加剂领域，涉及二苯胺类橡胶防老剂的制备，具体设计烷基化二苯胺类橡胶防老剂的制备。
背景技术
橡胶及其制品在长期使用过程中会出现粘化、龟裂、脆化，其物理机械性能随之降低，从而对于产品的使用产生不利影响，这种现象在橡胶领域称之为老化。发生老化的主要原因除了橡胶本身的优劣之外，最主要的原因是橡胶通常使用的环境较为恶劣，通常作为轮胎以及强力的缓冲件，往往处于高压力、高温等环境下，物理上使橡胶处老化；另外最主要的来自于自然界的紫外、臭氧、强光、水等的综合作用使得橡胶化学老化。一旦橡胶老化严重，其性能大大降低，甚至毫无利用价值。因此，人们向橡胶制品中添加各种化学物质以阻止老化的进程，从而延长橡胶及其制品的贮存期和使用寿命，其中最主要的就是防老剂(抗氧化剂)。主要的防老剂有酚类、苯胺类等。每种防老剂都有其特点和局限。
二苯胺类防老剂是用途最广、综合性能最优的一类防老剂。二苯胺自身具有防老性能，但是由于其剧毒、不稳定、易挥发等缺点，往往被修饰、进一步深加工之后使用，或者直接制备其类似结构的衍生物用作防老剂。
例如专利CN200910104093.1使用芳烷基胺I与酚类II化合物在有机溶剂中与氯乙酰氯和碱的条件下，在50-150℃温度下制备合成N-芳烷基苯胺类III化合物。
专利CN201010162177.3使用混合芳基胺与对苯二酚在磷酸三乙酯或无水三氯化铁催化下，在180-320℃、0.1-1.5MPa条件下制备得到防老剂混合二芳基对本二胺。这类防老剂在苯环两端引入增溶性基团，增大其与橡胶的增溶性，降低喷霜性，长效性好。专利CN201110437968.7页通过三氯化铁催化4-羟基二苯胺、2’-甲基-4-羟基二苯胺与邻甲苯胺制备类似的防老剂DTPD。
专利CN201110033026.2使用4-氨基二苯胺和甲基异丁基酮为原料，在0-1Mpa、100-200℃条件下缩合后进行催化加氢，蒸馏得到防老剂4020。即缩合还原烃基化，是4020类防老剂常见的方法。研究主要放在方法的工业化、以及简单易行和高效性、催化剂上。
防老剂4020是最常见二苯胺类防老剂，其具有高效低毒耐溶剂的特点，对于臭氧、屈挠老化具有很好的防护性能。
防老剂KY-405是另外一种常见的二苯胺类防老剂，针对热、光、臭氧所引起的老化；主要防老原理也都是在两端苯环上引入增溶等基团，增加其余橡胶的溶解性，又降低其喷霜性，使其发挥更大的防老性能。现有技术中合成此类防老剂直接通过二苯胺与烯烃的烷基化反应制备，这类技术最主要技术在于催化剂，催化剂活性、抗积碳、活性维持等是技术的关键。US4163757、US2943112、US4263456、CN101353445等专利都是通过常规的活性白土或改性活性白土为催化剂进行制备。US3496230、CN102584601等通过三氯化铝或固载的三氯化铝进行催化，这属于常规的付克烷基化催化剂。活性白土依然存在反应温度过高、容易导致积碳；三氯化铝本身非常敏感，遇到水分即开始水解冒烟，释放出氯化氢，即使固载后仍然不能解决其敏感、对于使用条件苛刻的弊端。而且上述专利鲜有提到催化剂的循环问题。专利CN105503617使α-烯烃与二苯胺在固体酸(经过酸处理)催化剂的作用下反应，获得目标产物；其目的在于获得单烷基化防老剂，虽然其认为单烷基化的防老剂性能更好，但是没有给出防老剂的活性测试。类似KY-405双烷基化的二苯胺类防老剂仍然是市场最广泛和公认最佳防老剂，单烷基化虽然增加单位重量二苯胺的比重，但是其同样降低其溶解性，或者性能更接近二苯胺本身，防老剂本身是一个综合性能的体现。在实践中，双烷基化二苯胺仍然是销量最大、应用最广的防老剂。
本发明就是要解决现有白土、三氯化铝等催化剂存在的上述问题，提出一种活性、选择性以及循环性能等综合性能较好的催化剂和KY-405制备方法。
发明内容
针对现有技术中制备二苯胺类防老剂的不足之处，本发明提供一种活性和选择性较高，催化剂寿命长的催化剂以及其催化制备KY-405的方法。
正如现有技术采用的高活性催化剂三氯化铝，其本身是最原始、活性高的烷基化催化剂，如上所述三氯化铝极易吸湿水解失活，在使用过程中对于操作条件较为严苛，而且对于设备腐蚀严重。与其类似的路易斯酸还有氯化锌ZnCl2、氯化铁FeCl3、氯化铜CuCl2等。
为了解决AlCl3的各种弊端，现有技术存在将其制备成离子液体的阴离子，同样具有路易斯酸的催化活性，但是实际上却仍然存在吸湿、易变质的问题。但是ZnCl2较AlCl3虽然Lewis酸性有所降低，但是其性质稳定，吸湿性能较AlCl3低，在正常使用过程中对于环境和条件的要求不高。
如现有技术所述，二苯胺的烷基化容易导致多烷基化，而均匀的双烷基化(一个苯环一个烷基)是本领域的追求。普通的催化剂(活性白土、AlCl3)并不能很好地解决多烷基化的问题。由于分子筛的具有多种尺度的孔道结构，其对于产物具有一定择形性能，例如在甲苯歧化领域，通过控制合理尺寸的孔道分子筛，可以高选择性地合成对二甲苯，而降低其他位置烷基化的副产物。分子筛自身也被常用作烷基化的固体酸催化剂。
将Lewis酸性离子液体与分子筛结合，可以实现有机-无机的结合，使得有机分子可以更容易接近催化活性位点，实现微观界面的均相化。
因此，本发明通过采用如下的技术方案，实现了二苯胺类的烷基化，并且催化剂活性和寿命达到预期。
具体方案如下：
A催化剂的制备
氯代烷基-三烷氧基硅Cl-(CH2)n-Si-(O-R1)3与叔胺N(R2)3反应在合适溶剂中合适温度下生成氯阴离子的季铵盐离子液体，根据需要的比例加入无水ZnCl2，合成(ZnCl2)m阴离子的离子液体；原理上氯化锌最多可以形成Zn3Cl7 -阴离子，实际上通常最大量使用2.5倍。
烷氧基硅烷-ZnCl2阴离子的离子液体与分子筛在溶剂中回流，制备成分子筛固载的烷氧基硅烷-ZnCl2阴离子离子液体。
反应式
其中，氯代烷基Cl-(CH2)n-Si-(O-R1)3中
n＝1-12的整数，优选2-5，更优选2-3，最优选2；
R1各自独立选自C1-8的直链或支链的烷基，优选甲基、乙基、正丙级、异丙基、正丁基、叔丁基、异丁基，更优选甲基、乙基，最优选乙基；
其中，叔胺N(R2)3中
R2各自独立选自C1-8的直链或支链的烷基，优选甲基、乙基、正丙级、异丙基、正丁基、叔丁基、异丁基，更优选甲基、乙基，最优选乙基；R2可选的所有烷基可以各自独立地进一步被一个或多个羟基、氰基、硝基、氨基、C1-8的直链或支链的烷基取代；
叔胺与硅烷的投料比为摩尔量1:1～2，优选1:1～1.5，更优选1:1-1.2，最优选1:1；
制备氯离子季铵盐的步骤，溶剂可以是乙醇、二氯乙烷、氯仿、二氯甲烷、THF、甲苯、DMSO；该步骤温度可以是室温至溶剂回流温度，优选60～100℃，更优选80℃；该步骤时间可以是6～24h，优选12h；
其中，(ZnCl2)m阴离子的离子液体中
m是加入ZnCl2与离子液体前体Cl离子的当量倍数，m＝1～2.5的任意数值，优选1.2～2，更优选1.8～2，最优选2；该步骤温度可以是室温至溶剂回流温度，优选60～100℃，更优选80℃；该步骤时间可以是6～24h，优选12h；溶剂与制备氯离子季铵盐的步骤相同。
其中，离子液体的负载量为载体分子筛重量的10～30％，优选10-20％，更优选15-20％，最优选15％；
其中，分子筛可以是本领域常见的分子筛，目前分子筛的研究非常成熟，很多分子筛的生产已经商业化，优选介孔分子筛，如MCM-41，SBA-15，Al、Cu、Fe掺杂的MCM-41，Al、Cu、Fe掺杂的SBA-15(掺杂的MCM-41被研究较为成熟，依据现有技术可以制备例如J Phys ChemB.2005Feb 24；109(7):2645-56；Journal of Industrial and Engineering Chemistry第26卷,25June 2015,322–332等或者直接购买)；
固载溶剂可以是常规对于该反应惰性的溶剂，如二氯甲烷、氯仿、DMSO、乙醇、二氯乙烷等；
固载温度优选室温～100℃，更有选室温～80℃，最优选60～80℃。
B催化反应
二苯胺、催化剂、烯烃在合适的溶剂或无溶剂体、合适的阻聚剂或无阻聚剂、一定温度下系下反应，检测二苯胺完全反应后，停止反应，分离产物。
反应式
应当可以理解氨基是邻对位定位基，由于苯环邻位的位阻效应，竞争反应中对位较容易被烷基化，而且分子筛孔道空间的尺寸的限制以及择形效应，都促使生成对位烷基化的二苯胺衍生物，因此主要产物应当为预期的对位烷基化的二苯胺衍生物。
其中，烯烃可以根据实际需要进行调整，例如根据产品结构选择不同结构烯烃，如α-甲基苯乙烯、苯乙烯、直链或支链的脂肪族C2-12烯烃如壬烯、庚烯、异丁烯等；优选α-甲基苯乙烯、苯乙烯，更优选α-甲基苯乙烯；烯烃的用量没有严格要求，以二苯胺完全反应为准，优选二苯胺摩尔量的1-1.5倍，更优选1-1.2倍，最优选1.2倍；
如果采用溶剂，可以为环己烷、甲基环己烷、甲苯、石油醚等，优选环己烷、甲基环己烷、甲苯，更优选环己烷；溶剂的用量没有严格的限定，以可以顺利反应又不影响反应进程为准，根据实际需要添加，优选二苯胺重量的0.8-2倍，更优选1-2倍，最优选1倍；
催化剂的用量为二苯胺重量的10～20％，优选10～15％，更优选10％。
反应温度没有严格限定，以可以发生反应，又兼顾反应效率和副产物等因素，根据实际需要进行调节，例如100～160℃，优选100～150℃，更优选120～130℃，最优选125℃；
反应优选在惰性气氛条件下进行，例如氮气、氩气，优选氮气；
反应中如果采用阻聚剂，可以是本领域常规的烯烃阻聚剂，酚类、醌类、无机阻聚剂等，如2,4-二甲基-6-叔丁基苯酚、甲基对苯二酚、对叔丁基邻苯二酚、2，5-二叔戊基对苯二酚、双酚A；
其用量为二苯胺重量的0.2～0.8％，优选0.2～0.5％，更有选0.3～0.5％。
其他说明：上述所有百分数的范围，例如10～20％等同于10％～20％。
本发明达到的有益效果：催化剂活性、选择性都维持在较高水平，寿命长，循环9次后仍能维持较高催化水平。
附图说明
附图1为分子筛负载离子液体后的孔道示意图。
具体实施方式
实施例1催化剂的制备
A烧瓶中加入Cl-(CH2)1-Si-(O-Et)3即氯甲基三乙氧基硅烷10.6g，Et3N即三乙胺5.2g，甲苯50ML，80℃回流6h；然后不分离，直接向烧瓶中加入13.6g无水氯化锌；回流过夜；
B同时进行：大三口烧瓶加入196g介孔分子筛MCM-41以及200ML甲苯，回流管配置分水器和无水氯化钙干燥管，80℃回流6h；
C将A体系不冷却直接倒入B体系，继续80℃回流24h；
D抽滤得到固体，真空干燥(少量溶剂并不会影响催化剂活性)，即得到MCM-41负载的三乙胺-ZnCl2离子液体的催化剂Cata.1，氯化锌m约为2，负载量约为15％。
参照(1)可以制备m＝2，n＝2的Cata.2；m＝1.5，n＝2的Cata.3；m＝2，n＝2，分子筛为介孔SBA-15的Cata.4。
实施例2催化反应
三口烧瓶中加入二苯胺16.9g，Cata.1催化剂2.0g和20ML甲苯，加入0.04g甲基对苯二酚，氮气置换烧瓶中空气并且在氮气保护下搅拌升温至60℃溶解后滴加α-甲基苯乙烯25g，持续滴加持续升温，直至125℃，滴加时间30min，然后保温125℃继续反应，薄板层析检测反应，直至二苯胺反应完全；冷却至室温后，过滤出固体催化剂以循环使用，母液减压蒸干，冷却、干燥得到白色固体即4,4'-双(α,α-二甲基苄基)二苯胺38.5g；纯度96.0％熔点99～101℃；HPLC结果显示主峰位置与4,4'-双(α,α-二甲基苄基)二苯胺标准样品相同，即本发明主要产品为4,4'-双(α,α-二甲基苄基)二苯胺及KY405。
实施例3-5参照实施例2相同步骤可以测试催化剂Cata.2-4，结果见下表。
上述实施例实验结果可以看出，本发明催化剂较好地解决了催化剂活性、催化剂寿命问题，降低生产成本，提高了生产効率。虽然催化剂在循环9次出现一定的活性降低，但是属于合理预期范围内。
此外，申请人进一步对于载体、Lewis酸种类、叔胺种类等多种条件进行选择得到与本文一致的结论和效果。
同样，对于烯烃的拓展，也取得与本文主旨一致的结论和效果。
应当理解，以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本发明的保护范围之内。
Claims (6)
1.一种二苯胺类橡胶防老剂的制备方法，其特征在于，包括如下步骤：
催化剂的制备：
A：烧瓶中加入Cl-(CH2)n-Si-(O-R1)3，叔胺N(R2)3，溶剂A1，60～100℃反应6～24h；然后不分离，直接向烧瓶中加入相当于Cl-(CH2)1-Si-(O-Et)3摩尔量m倍的无水氯化锌；继续保温反应；
B：同时进行：大三口烧瓶加入介孔分子筛以及溶剂B1，回流管配置分水器和无水氯化钙干燥管，60～100℃反应6～24h；
C：将A体系不冷却、不分离直接倒入B体系，继续60～100℃反应24h；
D：抽滤得到固体，真空干燥，即得到介孔分子筛负载的ZnCl2离子液体的催化剂；
其中步骤A的Cl-(CH2)n-Si-(O-R1)3中
n＝1-12的整数；
R1各自独立选自C1-8的直链或支链的烷基；
其中步骤A的叔胺N(R2)3中
R2各自独立选自C1-8的直链或支链的烷基；R2可以进一步被一个或多个羟基、氰基、硝基、氨基、C1-8的直链或支链的烷基取代；
其中步骤A的叔胺N(R2)3与Cl-(CH2)n-Si-(O-R1)3的投料比为摩尔量1:1～2；
其中步骤A和B的溶剂A1和B1选自乙醇、二氯乙烷、氯仿、二氯甲烷、THF、甲苯、DMSO；
其中步骤A的m＝1～2.5的任意数值；
其中步骤B的介孔分子筛选自MCM-41，SBA-15，Al、Cu、Fe掺杂的MCM-41，Al、Cu、Fe掺杂的SBA-15
其中，离子液体的负载量为载体分子筛重量的10～30％；
催化反应：
三口烧瓶中加入二苯胺，步骤D所得到催化剂和溶剂E1，加入阻聚剂，氮气置换烧瓶中空气并且在氮气保护下搅拌升温至60～100℃溶解后滴加烯烃，持续滴加持续升温，直至100～160℃，滴加时间10～60min，然后保温100～160℃继续反应，薄板层析检测反应，直至二苯胺反应完全；冷却至室温后，过滤出固体催化剂以循环使用，母液减压蒸干，冷却、干燥得到产品；
其中，溶剂E1选自环己烷、甲基环己烷、甲苯、石油醚；烯烃选自α-甲基苯乙烯、苯乙烯、直链或支链的脂肪族C2-12烯烃；阻聚剂选自2,4-二甲基-6-叔丁基苯酚、甲基对苯二酚、对叔丁基邻苯二酚、2，5-二叔戊基对苯二酚、双酚A；
其中，催化剂的用量为二苯胺重量的10～20％；阻聚剂用量为二苯胺重量的0.2～0.8％。
2.根据权利要求1所述的方法，
n＝2～5；
R1和R2各自独立为甲基、乙基、正丙级、异丙基、正丁基、叔丁基、异丁基；
N(R2)3与Cl-(CH2)n-Si-(O-R1)3的投料比为摩尔量1:1～1.5；
m＝1.2～2；
离子液体的负载量为载体分子筛重量的10-20％。
3.根据权利要求2所述的方法，
n＝2～3；
R1和R2各自独立为甲基、乙基；
N(R2)3与Cl-(CH2)n-Si-(O-R1)3的投料比为摩尔量1:1-1.2；
m＝1.8～2；
离子液体的负载量为载体分子筛重量的15-20％。
4.根据权利要求3所述的方法，
n＝2；
R1和R2各自独立为乙基；
N(R2)3与Cl-(CH2)n-Si-(O-R1)3的投料比为摩尔量1:1
m＝2；
离子液体的负载量为载体分子筛重量的15％。
5.根据权利要求1所述方法，溶剂E1为甲苯，阻聚剂为甲基对苯二酚。
6.根据权利要求1所述方法中制备得到的催化剂在二苯胺烷基化反应中的应用。
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| CN108329215A (zh) * | 2018-04-10 | 2018-07-27 | 李新君 | 一种苯乙烯基化二苯胺防老剂的制备方法 |
| CN113502062A (zh) * | 2021-07-19 | 2021-10-15 | 安徽省奥佳建材有限公司 | 一种抗氧化复合防水卷材材料 |
| CN113912500A (zh) * | 2020-07-10 | 2022-01-11 | 华东理工大学 | 一种利用微通道反应器制备胺类化合物的方法 |
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| CN105777552A (zh) * | 2014-12-23 | 2016-07-20 | 中国石油天然气股份有限公司 | 固态烷基化二苯胺的制备方法 |
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| CN105777552A (zh) * | 2014-12-23 | 2016-07-20 | 中国石油天然气股份有限公司 | 固态烷基化二苯胺的制备方法 |
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| CN108329215A (zh) * | 2018-04-10 | 2018-07-27 | 李新君 | 一种苯乙烯基化二苯胺防老剂的制备方法 |
| CN108329215B (zh) * | 2018-04-10 | 2020-09-11 | 新昌县勤勉生物医药科技有限公司 | 一种苯乙烯基化二苯胺防老剂的制备方法 |
| CN113912500A (zh) * | 2020-07-10 | 2022-01-11 | 华东理工大学 | 一种利用微通道反应器制备胺类化合物的方法 |
| CN113502062A (zh) * | 2021-07-19 | 2021-10-15 | 安徽省奥佳建材有限公司 | 一种抗氧化复合防水卷材材料 |
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