CN116640048B - 一种4,4’-联苯二酚的制备方法 - Google Patents
一种4,4’-联苯二酚的制备方法 Download PDFInfo
- Publication number
- CN116640048B CN116640048B CN202310611866.5A CN202310611866A CN116640048B CN 116640048 B CN116640048 B CN 116640048B CN 202310611866 A CN202310611866 A CN 202310611866A CN 116640048 B CN116640048 B CN 116640048B
- Authority
- CN
- China
- Prior art keywords
- tert
- biphenol
- butylphenol
- reaction
- finished
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 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 claims abstract description 23
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006722 reduction reaction Methods 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 15
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 13
- -1 copper salt Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 6
- 239000000543 intermediate Substances 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 11
- LYQIPMLFCQTVQK-UHFFFAOYSA-N 3,5-ditert-butyl-4-(2,6-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1C1=C(C(C)(C)C)C=C(O)C=C1C(C)(C)C LYQIPMLFCQTVQK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- YDYGHEJNKMWUNG-UHFFFAOYSA-N 3,5-ditert-butyl-4-(2-tert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=CC(O)=CC=C1C1=C(C(C)(C)C)C=C(O)C=C1C(C)(C)C YDYGHEJNKMWUNG-UHFFFAOYSA-N 0.000 claims description 8
- RLHCTHBNUUCRSY-UHFFFAOYSA-N 3-tert-butyl-4-(2-tert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=CC(O)=CC=C1C1=CC=C(O)C=C1C(C)(C)C RLHCTHBNUUCRSY-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- RUISNDKLNVFPBQ-UHFFFAOYSA-N CC(C1=NC=CN1C)N.Br Chemical compound CC(C1=NC=CN1C)N.Br RUISNDKLNVFPBQ-UHFFFAOYSA-N 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- IPKOOFMMRKTNNW-UHFFFAOYSA-N Br.NC(CC)C1=NC=CN1C Chemical compound Br.NC(CC)C1=NC=CN1C IPKOOFMMRKTNNW-UHFFFAOYSA-N 0.000 claims description 3
- TTZKLWTVYHPJRY-UHFFFAOYSA-N CCCCN1C(C(CC)N)=NC=C1.Br Chemical compound CCCCN1C(C(CC)N)=NC=C1.Br TTZKLWTVYHPJRY-UHFFFAOYSA-N 0.000 claims description 3
- QEKLKJFSTUZMKC-UHFFFAOYSA-N [Cl-].NC(CC)C1=[N+](C=CN1)C Chemical compound [Cl-].NC(CC)C1=[N+](C=CN1)C QEKLKJFSTUZMKC-UHFFFAOYSA-N 0.000 claims description 3
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 3
- YWLPVKUWECUAFQ-UHFFFAOYSA-N 3-methyl-2-propyl-1h-imidazol-3-ium;chloride Chemical compound [Cl-].CCCC=1NC=C[N+]=1C YWLPVKUWECUAFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- DECWYWSYTFTUAV-UHFFFAOYSA-N 1-methyl-2-propylimidazole Chemical compound CCCC1=NC=CN1C DECWYWSYTFTUAV-UHFFFAOYSA-N 0.000 claims 1
- VFRSADQPWYCXDG-LEUCUCNGSA-N ethyl (2s,5s)-5-methylpyrrolidine-2-carboxylate;2,2,2-trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.CCOC(=O)[C@@H]1CC[C@H](C)N1 VFRSADQPWYCXDG-LEUCUCNGSA-N 0.000 claims 1
- 238000004817 gas chromatography Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HPPRSWZVMYOJNY-UHFFFAOYSA-N 3-methyl-2-propyl-1H-imidazol-3-ium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCc1[nH]cc[n+]1C HPPRSWZVMYOJNY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- BETUWOAMGRRBME-UHFFFAOYSA-N 3-methyl-2-propyl-1H-imidazol-3-ium 2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CCCc1[nH]cc[n+]1C BETUWOAMGRRBME-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- VPONMBLTGNYMND-UHFFFAOYSA-N azane copper(1+) Chemical compound N.N.N.N.[Cu+] VPONMBLTGNYMND-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种4,4’‑联苯二酚的制备方法,属于有机合成技术领域。制备方法包括:将2,6‑二叔丁基苯酚与2‑叔丁基苯酚加入到有机溶液中,然后加入铜盐/离子液体催化剂,升温回流,通入空气进行氧化偶联反应;氧化偶联反应结束后,通入氮气,继续保持回流,进行还原反应;还原反应结束后,降温到室温过滤,得到中间体;将得到的中间体再加入到有机溶剂中,然后加入含磺酸基离子液体催化剂;升温回流,进行脱异丁烯反应,反应结束后降温,过滤,得到4,4’‑联苯二酚。本发明得到的4,4’‑联苯二酚纯度高,气相色谱检测纯度>99.90%,满足所有对4,4’‑联苯二酚高纯度的要求。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种4,4’-联苯二酚的制备方法。
背景技术
4,4’-联苯二酚(CAS NO.92-88-6)可作为橡胶防老剂、塑料抗氧剂、石油制品稳定剂。同时,由于其独特的联苯结构,具有优异的耐热性,高纯度的4,4’-联苯二酚,在化工行业中作为主原料或改性单体广泛用于制备性能优良的聚酯、聚氨酯、聚砜、环氧树酯、液晶高分子工程塑料等。目前,4,4’-联苯二酚在国内外需求量逐年上升,不过高纯度的4,4’-联苯二酚,我国还主要依赖于进口。
国内外报道合成4,4’-联苯二酚的工艺有很多,例如采用2,6-二叔丁基苯酚为原料,在催化剂的作用下进行氧化偶联再还原得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚,然后再脱异丁烯得到4,4’-联苯二酚(如公开号为CN113416119A、CN113956135A、CN112142570A的中国专利);采用对卤代苯酚或对硼酸类取代物苯酚直接偶联的方法(如公开号为CN 113912478A、CN111533645A、CN115466165A、CN114181046A、CN108715574A的中国专利)。其中,采用2,6-二叔丁基苯酚为原料的方法是工业化生产的主要技术路线。
目前,国内有多家生产2,6-二叔丁基苯酚产品的企业,2,6-二叔丁基苯酚本身就是一种优异的抗氧剂,使用非常广泛。根据报道,2,6-二叔丁基苯酚是使用苯酚与异丁烯为原料,在酚基铝催化下制备的。不过同时也会伴随着副产物2,4-二叔丁基苯酚和2-叔丁基苯酚的产生。然而,2,4-二叔丁基苯酚也可以单独作为抗氧剂使用。但是,如何将2-叔丁基苯酚更好的使用也成为摆在面前的问题。
发明内容
本发明的目的是针对以上工艺的不足以及2-叔丁基苯酚更好的使用,提供一种高纯度4,4’-联苯二酚的制备方法,本发明以2,6-二叔丁基苯酚与2-叔丁基苯酚为混合原料,在铜盐/离子液体催化下进行氧化偶联和还原反应得到混合中间体,混合中间体再在含磺酸基离子液体催化下脱异丁烯制备4,4’-联苯二酚。
本发明提供一种4,4’-联苯二酚的制备方法,包括如下步骤:
1)在室温条件下,将2,6-二叔丁基苯酚与2-叔丁基苯酚加入到有机溶液中,得到2,6-二叔丁基苯酚与2-叔丁基苯酚的有机溶液;
2)向步骤1)所得有机溶液中加入铜盐/离子液体催化剂,均匀混合后即为反应体系;
3)升温到110℃-165℃回流,通入空气进行氧化偶联反应,同时分馏出生成的水;
4)氧化偶联反应结束后,通入氮气,继续保持回流,进行还原反应;
5)还原反应结束后,降温到室温过滤,得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚、3,5,3’–三叔丁基-4,4’-联苯二酚、3,3’–二叔丁基-4,4’-联苯二酚中间体;
6)将步骤5)得到的中间体再加入到有机溶剂中,得到有机溶液;
7)向步骤6)所得的有机溶液中加入磺酸基离子液体催化剂;
8)升温到110℃-165℃回流,进行脱异丁烯反应,反应结束后降温到25℃-35℃,过滤,得到产品4,4’-联苯二酚。
本发明所述一种4,4’-联苯二酚的制备方法,采用反应方程式表示为:
进一步地,上述步骤1)中,所述2,6-二叔丁基苯酚与2-叔丁基苯酚的重量比例为10:(1-3),优选为10:2。
进一步地,上述步骤1)中,所述2,6-二叔丁基苯酚和2-叔丁基苯酚的混合物与有机溶剂的重量比例为1:(3-6),优选为1:4。
进一步地,上述步骤1)和步骤6)中,所述有机溶剂为甲苯、二甲苯、均三甲苯中的一种,优选为二甲苯。
进一步地,上述步骤2)中,所述铜盐为氯化铜或溴化铜,优选为氯化铜。
进一步地,上述步骤2)中,所述离子液体为1-胺乙基-3-甲基咪唑溴盐、1-胺丙基-3-甲基咪唑氯盐、1-胺丙基-3-甲基咪唑溴盐、1-胺丙基-3-丁基咪唑溴盐中的一种,优选为1-胺乙基-3-甲基咪唑溴盐。
进一步地,上述步骤2)中,所述铜盐与离子液体的摩尔比为1:(2-4),优选为1:2.5。
进一步地,上述步骤2)中,所述铜盐与2,6-二叔丁基苯酚和2-叔丁基苯酚的有机溶液的重量比为(2-6):1000,优选为3:1000。
进一步地,上述步骤6)中,所述中间体与有机溶剂的重量比为1:(3-7),优选为1:5。
进一步地,上述步骤7)中,所述磺酸基离子液体为1-磺酸丙基-3-甲基咪唑氯盐、1-磺酸丙基-3-甲基咪唑三氟甲磺酸盐、1-磺酸丙基-3-甲基咪唑三氟乙酸盐中的一种,优选为1-磺酸丙基-3-甲基咪唑三氟甲磺酸盐。
进一步地,上述步骤3)中,所述反应时间为1-5h,优选为3h;上述步骤4)中,所述反应时间为5-9h,优选为7h;上述步骤8)中,所述反应时间为3-6h,优选为4h。
本发明的有益效果如下:
1.本发明技术路线采用2,6-二叔丁基苯酚与2-叔丁基苯酚为混合原料,技术路线简单,降低了成本,并且提高了2-叔丁基苯酚的利用率。
2.采用铜盐/氨基离子液体,氧化还原一体催化剂,氨和铜离子络合,生成铜氨离子,其中氨提供孤对电子,铜离子提供空电子轨道,铜是四配位的离子,和氨反应生成的四氨合铜离子,所铜和氨络合力很强,络合后的铜氨络合物在此反应的溶剂中全部溶解达到均相,因此氨基会完全的络合铜离子达到均相催化,提高催化效果,降低中间体中催化剂的残留,且原料廉价易得。
3.脱异丁烯采用磺酸基离子液体,离子液体由带正电的离子和带负电的离子组成,具有良好的热稳定性和化学稳定性,易与其它物质分离,可以循环利用,蒸汽压非常小,不挥发,在使用、储藏中不会蒸发散失,可以循环使用,因此可以避免使用其他类磺酸催化剂过程中,催化剂的挥发、分解等问题,降低了催化剂的用量,大大降低副反应及杂质的生成,提高了产品收率及纯度。
4.本发明路线最终产品4,4’-联苯二酚纯度高,气相色谱检测纯度>99.90%,满足所有对4,4’-联苯二酚高纯度的要求。
附图说明
图1为实施例1产物的1H-NMR谱图;
图2为实施例1产物的气相色谱谱图。
具体实施方式
采用实施例的方式对本发明进行例证说明。实施例中所描述的具体的物料配比、工艺条件及其结果仅起到说明本发明的作用,而本发明不应当也不会受到实施例的限制。
实施例1
在室温条件下,将2,6-二叔丁基苯酚(103.2g,0.5mol)与2-叔丁基苯酚(20.6g)入到二甲苯(495.2g)中,然后加入氯化铜(0.37g)、1-胺乙基-3-甲基咪唑溴盐(1.42g);升温到138度回流,通入空气进行氧化偶联反应,同时分馏出生成的水,回流反应3h;氧化反应结束后,通入氮气,继续保持回流7h,进行还原反应;还原反应结束后,降温到室温过滤,得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚、3,5,3’–三叔丁基-4,4’-联苯二酚、3,3’–二叔丁基-4,4’-联苯二酚中间体。将得到中间体在加入到二甲苯中,加入1-磺酸丙基-3-甲基咪唑三氟甲磺酸盐催化剂;升温到138度回流,进行脱异丁烯反应,反应结束后降温到25度,过滤,得到产品4,4’-联苯二酚,气相色谱检测纯度99.98%(如图2)。如图1所示,1H-NMR数据如下:1H NMR(400MHz,DMSO-d6)δ:6.80(d,2H),7.37(d,2H),9.39(s,1H)。
实施例2
在室温条件下,将2,6-二叔丁基苯酚(103.2g,0.5mol)与2-叔丁基苯酚(10.3g)入到甲苯(340.5g)中,然后加入氯化铜(0.23g),1-胺丙基-3-甲基咪唑氯盐(0.59g);升温到110度回流,通入空气进行氧化偶联反应,同时分馏出生成的水,回流反应5h;氧化反应结束后,通入氮气,继续保持回流9h,进行还原反应;还原反应结束后,降温到室温过滤,得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚、3,5,3’–三叔丁基-4,4’-联苯二酚、3,3’–二叔丁基-4,4’-联苯二酚中间体。将得到中间体在加入到甲苯中,加入1-磺酸丙基-3-甲基咪唑三氟甲磺酸盐催化剂;升温到110度回流,进行脱异丁烯反应,反应结束后降温到30度,过滤,得到产品4,4’-联苯二酚,气相色谱检测纯度99.94%。
实施例3
在室温条件下,将2,6-二叔丁基苯酚(103.2g,0.5mol)与2-叔丁基苯酚(30.9g)入到均三甲苯(804.6g)中,然后加入溴化铜(0.81g),1-胺丙基-3-甲基咪唑溴盐(3.19g);升温到165度回流,通入空气进行氧化偶联反应,同时分馏出生成的水,回流反应4h;氧化反应结束后,通入氮气,继续保持回流5h,进行还原反应;还原反应结束后,降温到室温过滤,得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚、3,5,3’–三叔丁基-4,4’-联苯二酚、3,3’–二叔丁基-4,4’-联苯二酚中间体。将得到中间体在加入到均三甲苯中,加入1-磺酸丙基-3-甲基咪唑氯盐催化剂;升温到165度回流,进行脱异丁烯反应,反应结束后降温到35度,过滤,得到产品4,4’-联苯二酚,气相色谱检测纯度99.92%。
实施例4
在室温条件下,将2,6-二叔丁基苯酚(103.2g,0.5mol)与2-叔丁基苯酚(20.6g)入到二甲苯(619g)中,然后加入氯化铜(0.25g),1-胺丙基-3-丁基咪唑溴盐(1.95g);升温到138度回流,通入空气进行氧化偶联反应,同时分馏出生成的水,回流反应1h;氧化反应结束后,通入氮气,继续保持回流5h,进行还原反应;还原反应结束后,降温到室温过滤,得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚、3,5,3’–三叔丁基-4,4’-联苯二酚、3,3’–二叔丁基-4,4’-联苯二酚中间体。将得到中间体在加入到二甲苯中,加入1-磺酸丙基-3-甲基咪唑三氟乙酸盐催化剂;升温到138度回流,进行脱异丁烯反应,反应结束后降温到30度,过滤,得到产品4,4’-联苯二酚,气相色谱检测纯度99.95%。
对比例1
在室温条件下,将2,6-二叔丁基苯酚(103.2g,0.5mol)与2-叔丁基苯酚(20.6g)入到二甲苯(495.2g)中,然后加入氯化铜(0.37g);升温到138度回流,通入空气进行氧化偶联反应,同时分馏出生成的水,回流反应3h;氧化反应结束后,通入氮气,继续保持回流7h,进行还原反应;还原反应结束后,降温到室温过滤,得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚、3,5,3’–三叔丁基-4,4’-联苯二酚、3,3’–二叔丁基-4,4’-联苯二酚中间体。将得到中间体在加入到二甲苯中,加入1-磺酸丙基-3-甲基咪唑三氟甲磺酸盐催化剂;升温到138度回流,进行脱异丁烯反应,反应结束后降温到25度,过滤,得到产品4,4’-联苯二酚,气相色谱检测纯度98.91%。
对比例1中,氧化还原反应未加入离子液体,铜盐催化剂会有微量残留在中间体中,影响4,4’-联苯二酚纯度。
对比例2
在室温条件下,将2,6-二叔丁基苯酚(103.2g,0.5mol)与2-叔丁基苯酚(20.6g)入到二甲苯(495.2g)中,然后加入氯化铜(0.37g),1-胺乙基-3-甲基咪唑溴盐(1.42g);升温到138度回流,通入空气进行氧化偶联反应,同时分馏出生成的水,回流反应3h;氧化反应结束后,通入氮气,继续保持回流7h,进行还原反应;还原反应结束后,降温到室温过滤,得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚、3,5,3’–三叔丁基-4,4’-联苯二酚、3,3’–二叔丁基-4,4’-联苯二酚中间体。将得到中间体在加入到二甲苯中,加入甲基磺酸催化剂;升温到138度回流,进行脱异丁烯反应,反应结束后降温到25度,过滤,得到产品4,4’-联苯二酚,气相色谱检测纯度98.89%。
对比例2中,脱异丁烯反应加入甲基磺酸,由于甲基磺酸的分解或挥发,造成副产或脱异丁烯不完全,从而影响4,4’-联苯二酚产品纯度。
以上实施例描述了本发明的基本原理、主要特征及优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (8)
1.一种4,4’-联苯二酚的制备方法,其特征在于,包括如下步骤:
1)在室温条件下,将2,6-二叔丁基苯酚与2-叔丁基苯酚加入到有机溶剂中,得到2,6-二叔丁基苯酚与2-叔丁基苯酚的有机溶液;
2)向步骤1)所得有机溶液中加入铜盐/离子液体催化剂,均匀混合后即为反应体系;
3)升温到110℃-165℃回流,通入空气进行氧化偶联反应,同时分馏出生成的水;
4)氧化偶联反应结束后,通入氮气,继续保持回流,进行还原反应;
5)还原反应结束后,降温到室温过滤,得到3,5,3’,5’-四叔丁基-4,4’-联苯二酚、3,5,3’ –三叔丁基-4,4’-联苯二酚、3,3’ –二叔丁基-4,4’-联苯二酚中间体;
6)将步骤5)得到的中间体再加入到有机溶剂中,得到有机溶液;
7)向步骤6)所得的有机溶液中加入磺酸基离子液体催化剂;
8)升温到110℃-165℃回流,进行脱异丁烯反应,反应结束后降温到25℃-35℃,过滤,得到产品4,4’-联苯二酚;
步骤2)中所述铜盐为氯化铜或溴化铜,所述离子液体为1-胺乙基-3-甲基咪唑溴盐、1-胺丙基-3-甲基咪唑氯盐、1-胺丙基-3-甲基咪唑溴盐、1-胺丙基-3-丁基咪唑溴盐中的一种;
步骤7)中所述磺酸基离子液体为1-磺酸丙基-3-甲基咪唑氯盐、1-磺酸丙基-3-甲基咪唑三氟甲磺酸盐、1-磺酸丙基-3-甲基咪唑三氟乙酸盐中的一种。
2.根据权利要求1所述的一种4,4’-联苯二酚的制备方法,其特征在于:步骤1)中,所述2,6-二叔丁基苯酚与2-叔丁基苯酚的重量比例为10:(1-3)。
3.根据权利要求1所述的一种4,4’-联苯二酚的制备方法,其特征在于:步骤1)中,所述2,6-二叔丁基苯酚和2-叔丁基苯酚的混合物与有机溶剂的重量比例为1:(3-6)。
4.根据权利要求1所述的一种4,4’-联苯二酚的制备方法,其特征在于:步骤1)和步骤6)中,所述有机溶剂为甲苯、二甲苯、均三甲苯中的一种。
5.根据权利要求1所述的一种4,4’-联苯二酚的制备方法,其特征在于:步骤2)中,所述铜盐与离子液体的摩尔比为1:(2-4)。
6.根据权利要求1所述的一种4,4’-联苯二酚的制备方法,其特征在于:步骤2)中,所述铜盐与2,6-二叔丁基苯酚和2-叔丁基苯酚的有机溶液的重量比为(2-6):1000。
7.根据权利要求1所述的一种4,4’-联苯二酚的制备方法,其特征在于:步骤6)中,所述中间体与有机溶剂的重量比为1:(3-7)。
8.根据权利要求1所述的一种4,4’-联苯二酚的制备方法,其特征在于:步骤3)中,所述反应时间为1-5h;步骤4)中,所述反应时间为5-9h;步骤8)中,所述反应时间为3-6h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310611866.5A CN116640048B (zh) | 2023-05-29 | 2023-05-29 | 一种4,4’-联苯二酚的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310611866.5A CN116640048B (zh) | 2023-05-29 | 2023-05-29 | 一种4,4’-联苯二酚的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116640048A CN116640048A (zh) | 2023-08-25 |
CN116640048B true CN116640048B (zh) | 2023-10-24 |
Family
ID=87622469
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310611866.5A Active CN116640048B (zh) | 2023-05-29 | 2023-05-29 | 一种4,4’-联苯二酚的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116640048B (zh) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4447656A (en) * | 1981-03-09 | 1984-05-08 | The Dow Chemical Company | Solvent system for oxidative coupling process |
JPH04346955A (ja) * | 1991-05-24 | 1992-12-02 | Mitsubishi Petrochem Co Ltd | t−ブチルビフェノール組成物の製造方法 |
JPH09136858A (ja) * | 1995-11-14 | 1997-05-27 | Shindengen Electric Mfg Co Ltd | ジフェノキノン化合物、その製造方法、及びそのジフェノキノン化合物を用いた電子写真感光体 |
WO2004018401A1 (en) * | 2002-08-26 | 2004-03-04 | Wiley Organics, Inc. | Preparation of biphenols by oxidative coupling of alkylphenols using a recyclable copper catalyst |
CN102659525A (zh) * | 2012-05-18 | 2012-09-12 | 四川宝利丰科技有限公司 | 一种3,3’,5,5’-四烷基-4,4’-联苯二酚的制备方法 |
CN112142570A (zh) * | 2020-09-22 | 2020-12-29 | 威海金泓高分子有限公司 | 一种对羟基联苯二酚的制备方法 |
-
2023
- 2023-05-29 CN CN202310611866.5A patent/CN116640048B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4447656A (en) * | 1981-03-09 | 1984-05-08 | The Dow Chemical Company | Solvent system for oxidative coupling process |
JPH04346955A (ja) * | 1991-05-24 | 1992-12-02 | Mitsubishi Petrochem Co Ltd | t−ブチルビフェノール組成物の製造方法 |
JPH09136858A (ja) * | 1995-11-14 | 1997-05-27 | Shindengen Electric Mfg Co Ltd | ジフェノキノン化合物、その製造方法、及びそのジフェノキノン化合物を用いた電子写真感光体 |
WO2004018401A1 (en) * | 2002-08-26 | 2004-03-04 | Wiley Organics, Inc. | Preparation of biphenols by oxidative coupling of alkylphenols using a recyclable copper catalyst |
CN102659525A (zh) * | 2012-05-18 | 2012-09-12 | 四川宝利丰科技有限公司 | 一种3,3’,5,5’-四烷基-4,4’-联苯二酚的制备方法 |
CN112142570A (zh) * | 2020-09-22 | 2020-12-29 | 威海金泓高分子有限公司 | 一种对羟基联苯二酚的制备方法 |
Non-Patent Citations (2)
Title |
---|
Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity;Yexenia Nieves-Quinones等;《Journal of the American Chemical Society》;第141卷(第25期);第10016-10032页 * |
蒋忠良等.4,4′-联苯二酚的合成研究.《同济大学学报(自然科学版)》.2002,(第07期),第904-906页. * |
Also Published As
Publication number | Publication date |
---|---|
CN116640048A (zh) | 2023-08-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN116640048B (zh) | 一种4,4’-联苯二酚的制备方法 | |
EP4238957A1 (en) | System for manufacturing phthalonitrile-based compound and method for manufacturing phthalonitrile-based compound using same | |
CN107488108B (zh) | 一种氯代苯氧乙酸或氯代苯酚的合成方法 | |
CN112608258A (zh) | 一种亚砜氧化法合成4,4’-二氯二苯砜的方法 | |
CN115974663B (zh) | 三氟甲基酮类化合物的制备方法及其应用 | |
CN110922385A (zh) | 一种无溶剂化环己酮-苯甲醛氧化制备ε-己内酯的方法 | |
CN103319296B (zh) | 一种四甲基联苯的制备方法 | |
CN104250219A (zh) | 一种叔丁基丙烯酰胺磺酸的生产方法 | |
CN112876359B (zh) | 一种2,6-萘二甲酸二甲酯的制备方法 | |
WO2022198850A1 (zh) | 一种丙二醇苯醚的高选择性合成方法 | |
CN105669413A (zh) | 一种微波辐射制备2-甲基-1,4-萘醌的方法 | |
CN113149827A (zh) | 一种利用端炔与二氧化碳合成炔酸的方法 | |
CN113402358A (zh) | 环丙基溴的一种新合成方法 | |
CN112724021A (zh) | 一种4,4’-二硝基二苯醚的制备方法 | |
CN102120726B (zh) | 一种制备(2e)-2-氰基-3-(3,4-二羟基-5-硝基苯)-n,n-二乙基-2-丙烯酰胺的新方法 | |
CN108976125B (zh) | 一种碳酸二甲酯与乙醇发生酯交换反应制备碳酸甲乙酯的方法 | |
JP6016787B2 (ja) | Co気相法を用いたシュウ酸エステルの製造方法 | |
CN101786955B (zh) | 一种甲醇气相氧化羰基化一步法合成碳酸二甲酯工艺 | |
CN106748671B (zh) | 一种由2-溴-4-甲基苯酚合成2-烷氧基-4-甲基苯酚的方法 | |
CN105693519A (zh) | 一种对苯二甲酸二酯的低熔点混合物的制备方法 | |
CN112279764A (zh) | 一种3-乙氧基丙酸乙酯的制备方法 | |
EP2991965B1 (en) | Process for equilibrium-limited reactions | |
CN102391129A (zh) | 一种2,7-二硝基芴酮的制取方法 | |
CN112321525B (zh) | 一种一步法合成3,4-双(4’-氨基呋咱-3’-基)氧化呋咱的方法 | |
CN103626667B (zh) | 一种催化加氢制备3,3',4,4'-四氨基二苯醚盐酸盐的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |