CN115814854A - Catalyst for preparing 2,2' -biphenol and preparation method and application thereof - Google Patents
Catalyst for preparing 2,2' -biphenol and preparation method and application thereof Download PDFInfo
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- CN115814854A CN115814854A CN202211437800.0A CN202211437800A CN115814854A CN 115814854 A CN115814854 A CN 115814854A CN 202211437800 A CN202211437800 A CN 202211437800A CN 115814854 A CN115814854 A CN 115814854A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- 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 12
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- -1 silicate ester Chemical class 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 150000008053 sultones Chemical class 0.000 claims abstract description 7
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 40
- 238000000926 separation method Methods 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 238000007792 addition Methods 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- MUIDDQWFOHFBAF-UHFFFAOYSA-N trihexyl(methyl)silane Chemical compound CCCCCC[Si](C)(CCCCCC)CCCCCC MUIDDQWFOHFBAF-UHFFFAOYSA-N 0.000 claims description 2
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- 238000001914 filtration Methods 0.000 description 20
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 239000012452 mother liquor Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 9
- 210000003298 dental enamel Anatomy 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PLUBXMRUUVWRLT-UHFFFAOYSA-N Ethyl methanesulfonate Chemical compound CCOS(C)(=O)=O PLUBXMRUUVWRLT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002941 palladium compounds 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
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to a catalyst for preparing 2,2' -biphenol, a preparation method and application thereof, and the catalyst has the advantages of low reaction temperature, high product purity and high yield; the supported catalyst and the reaction solvent can be directly recycled, and the recycling effect is good; environment-friendly, does not generate wastewater, has simple process and low equipment requirement, is convenient to realize industrialization, and the like. The catalyst comprises a main catalyst and an auxiliary catalyst; the main catalyst comprises polyethylene glycol, inorganic acid, sultone, silicate ester, organosilane and an oxidant; the cocatalyst comprises elemental iodine, alcohol and a molecular sieve. The 2,2' -biphenol prepared by the catalyst has the purity of more than or equal to 99.5 percent and the total yield of more than 90 percent.
Description
Technical Field
The invention relates to the field of fine chemical engineering, and in particular relates to a catalyst for preparing 2,2' -biphenol, a preparation method and application thereof.
Background
At present, 2,2' -biphenol is used as an important organic intermediate, can be used as a rubber antioxidant and a plastic antioxidant, can be used for colorless vulcanized rubber products, rubber products for food packaging and medical latex products, and can also be used for sulfur chloride cold vulcanized products (such as medical gloves and condoms) and the like. In the synthesis of high polymers, the polymers are excellent in heat resistance, and therefore can be used as modified monomers for polyesters, polyurethanes, polycarbonates, polysulfones, epoxy resins, and the like to produce excellent engineering plastics, composite materials, and the like.
The compound has the following preparation methods, for example, US2244244A discloses that dibenzofuran is used as a raw material, the reaction temperature is above 250 ℃, solid potassium hydroxide is used as a ring-opening reagent, the product is easy to coke due to high reaction temperature, and the material viscosity is high and has high requirements on equipment. For example, US6410238A discloses that biphenyl compounds are subjected to multi-step reactions such as sulfonation and alkali fusion to prepare target products, and the method has a large amount of strong acid and strong alkali waste water and is not environment-friendly.
The prior art (J.Org.chem.1987, 52, 1881-1884) discloses a preparation method for removing tert-butyl by using Nafion-H + as a catalyst, and the catalyst used in the method is expensive and is not easy to obtain.
CN105348047A discloses the use of tert-butyl diphenol as a starting material, cooling crystallization after the reaction is completed, filtration to separate the product. The melting point of the product is about 110 ℃, and the post-treatment effect described in the patent examples cannot be realized under the solvent-free condition.
CN105967980A discloses that diphenol compounds are used as raw materials, noble metal palladium compounds are used as catalysts, the method is high in cost, and an oxidant used in the reaction has explosion risks.
In view of the reasons, the invention overcomes various defects in the method and develops the catalyst with good catalytic effect, low reaction temperature, high yield and good quality. The preparation method is environment-friendly, has low equipment requirement and is convenient for realizing the industrialized preparation method of 2,2' -biphenol.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a catalyst for preparing 2,2' -biphenol, a preparation method and application thereof, and the catalyst has the advantages of low reaction temperature, high product purity and high yield, and meanwhile, the supported catalyst and the reaction solvent can be directly recycled, so that the recycling effect is good, the catalyst is environment-friendly, no wastewater is generated, the process is simple, the equipment requirement is low, and the industrialization is convenient to realize.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst for the preparation of 2,2' -biphenol, said catalyst comprising a procatalyst and a cocatalyst;
the main catalyst comprises polyethylene glycol, inorganic acid, sultone, silicate ester, organosilane and an oxidant;
the cocatalyst comprises elemental iodine, alcohol and a molecular sieve.
The catalyst provided by the invention realizes an efficient dealkylation effect by adopting a specific main catalyst and auxiliary catalyst matching mode, is beneficial to the efficient preparation of 2,2 '-biphenol available catalyst, the purity of 2,2' -biphenol prepared by adopting the catalyst is more than or equal to 99.5%, and the total yield can reach more than 90%.
In the invention, the 2,2' -biphenol has the following structural formula:
in the present invention, the molecular weight of the polyethylene glycol is 200 to 600, and may be, for example, 200, 300, 400, 500 or 600, but is not limited to the values listed, and other values not listed in the range are also applicable.
As a preferred embodiment of the present invention, the inorganic acid includes 1 or a combination of at least 2 of hydrochloric acid, hydrobromic acid, or sulfuric acid.
Preferably, the sultones comprise 1 or a combination of at least 2 of 1,3-propane sultone, 1,4-butane sultone, or 1,5-pentane sultone.
Preferably, the silicate comprises 1 or a combination of at least 2 of methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate, or butyl orthosilicate.
Preferably, the silane comprises 1 or a combination of at least 2 of trimethylsilane, tri-n-hexylmethylsilane, or (3-mercaptopropyl) trimethoxysilane.
Preferably, the oxidizing agent comprises a combination of 1 or at least 2 of Oxone, hydrogen peroxide or m-chloroperoxybenzoic acid.
Preferably, the alcohol comprises a combination of 1 or at least 2 of isopropanol, n-propanol, n-butanol or isobutanol.
Preferably, the molecular sieve comprises a ZSM-5 molecular sieve and/or a ZSM-11 molecular sieve.
In a preferred embodiment of the present invention, the inorganic acid may be used in a mass concentration of 3 to 10%, for example, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%, but not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the oxidizing agent is present in a mass concentration of 15-35%, for example 15%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, or 35%, etc., but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the mass ratio of polyethylene glycol, inorganic acid, sultone, silicate, organosilane and oxidant in the procatalyst is (0.01-0.05): 1 (0.5-1): 0.01-0.1): 0.001-0.02, (0.001-0.01) and can be, for example, 0.01.
Preferably, the mass ratio of elemental iodine, alcohol and molecular sieve in the cocatalyst is 1 (0.01-0.1): 0.05-0.3), and can be, for example, 1.
In a second aspect, the present invention provides a method for preparing a catalyst as described in the first aspect, the method comprising preparing a procatalyst and preparing a cocatalyst;
the preparation of the main catalyst comprises the steps of preparing materials according to a formula, and then sequentially carrying out first mixing reaction, reflux, solid-liquid separation, methanol reflux, solid-liquid separation and first drying to obtain the main catalyst;
the preparation of the cocatalyst comprises the steps of preparing materials according to a formula, and then sequentially carrying out second mixing reaction, alcohol separation and second drying to obtain the cocatalyst.
In a preferred embodiment of the present invention, the temperature of the first mixing reaction is 20 to 40 ℃, and may be, for example, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃ or 40 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the first mixing reaction time is 2 to 5 hours, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the refluxing time is 10 to 20 hours, and may be, for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, 17 hours, 17.5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours or 20 hours, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the amount of methanol used in the methanol reflux is 4 to 6 times the mass of the polyethylene glycol, for example, 4 times, 4.2 times, 4.4 times, 4.6 times, 4.8 times, 5 times, 5.2 times, 5.4 times, 5.6 times, 5.8 times, or 6 times, but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the methanol reflux time is 4 to 5 hours, for example, 4 hours, 4.1 hours, 4.2 hours, 4.3 hours, 4.4 hours, 4.5 hours, 4.6 hours, 4.7 hours, 4.8 hours, 4.9 hours, or 5 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the first drying mode is vacuum drying.
Preferably, the temperature of the first drying is 50 to 60 ℃, for example, 50 ℃, 51 ℃,52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or 60 ℃ and the like, but is not limited to the enumerated values, and other values not enumerated within this range are also applicable.
In a preferred embodiment of the present invention, the temperature of the second mixing reaction is 20 to 45 ℃ and may be, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, but is not limited to the values listed above, and other values not listed in the range are also applicable.
Preferably, the time of the second mixing reaction is 1 to 3 hours, and for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, or 3 hours, etc., are possible, but not limited to the values recited, and other values not recited in the range are also applicable.
Preferably, the alcohol separation is to separate the alcohol in the material by distillation.
Preferably, the second drying mode is vacuum drying.
Preferably, the temperature of the second drying is 50-70 ℃, for example, 50 ℃,52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃ or 70 ℃, but not limited to the enumerated values, and other values not enumerated in this range are also applicable.
As a preferable technical scheme, the preparation method comprises the steps of preparing a main catalyst and preparing an auxiliary catalyst;
the preparation of the main catalyst comprises the steps of preparing materials according to a formula, and then sequentially carrying out first mixing reaction, backflow, solid-liquid separation, methanol backflow, solid-liquid separation and first drying to obtain the main catalyst; the temperature of the first mixing reaction is 20-40 ℃; the time of the first mixing reaction is 2-5h; the refluxing time is 10-20h; the dosage of the methanol in the methanol reflux is 4-6 times of the mass of the polyethylene glycol; the methanol refluxing time is 4-5h; the first drying mode is vacuum drying; the temperature of the first drying is 50-60 ℃;
the preparation of the cocatalyst comprises the steps of preparing materials according to a formula, and then sequentially carrying out second mixing reaction, alcohol separation and second drying to obtain the cocatalyst; the temperature of the second mixing reaction is 20-45 ℃; the time of the second mixing reaction is 1-3h; the alcohol separation is to separate the alcohol in the material by adopting a distillation mode; the second drying mode is vacuum drying; the temperature of the second drying is 50-70 ℃.
In a third aspect, the invention provides a use of the catalyst of the first aspect, the use comprising the preparation of 2,2' -biphenol using the catalyst, specifically comprising:
mixing 2,2 '-biphenyldiphenol compound containing alkyl substituent, solvent and catalyst, carrying out first reaction, and then carrying out solid-liquid separation and cooling separation to obtain 2,2' -biphenyldiol solid.
In the invention, the 2,2' -biphenyldiphenol compound containing alkyl substituent has the following structural formula:
in the formula, R 1 -R 4 1 selected from tertiary alkyl, isopropyl alkyl and hydrogen respectively and independently; r 1 '-R 4 ' are each independently selected from 1 of tertiary carbon alkyl, isopropyl or hydrogen.
In the invention, a filter cake obtained after solid-liquid separation in the reaction in the preparation process of 2,2' -biphenol solid can be returned to be used as a catalyst in the next reaction after being washed.
In the invention, active carbon is added into a liquid phase obtained in the process of cooling and separating, the liquid phase is stirred for 1h at the temperature of 80-100 ℃, the active carbon is filtered, the obtained feed liquid can be directly used as a solvent of the next batch without being processed, and the mass ratio of the added amount of the active carbon to the 2,2' -biphenyldiol compound containing alkyl substituent groups is (1-2): 100, so that the secondary utilization of the solvent in the feed liquid is realized.
As a preferred embodiment of the present invention, the mass ratio of the main catalyst and the alkyl-substituted 2,2' -biphenyldiphenol compound in the mixed catalyst is (0.1 to 0.5) 1, and for example, 0.1.
Preferably, the mass ratio of the cocatalyst of the catalyst and the alkyl-substituted 2,2' -biphenyldiphenol compound in the mixture is (0.01-0.05): 1, for example, can be 0.01.
Preferably, the solvent comprises 1 or a combination of at least 2 of benzene, toluene, xylene, o-xylene, m-xylene, or p-xylene.
Preferably, the amount of the solvent added is 10 to 50 times, for example, 10 times, 12 times, 14 times, 16 times, 18 times, 20 times, 22 times, 24 times, 26 times, 28 times, 30 times, 32 times, 34 times, 36 times, 38 times, 40 times, 42 times, 44 times, 46 times, 48 times, or 50 times the molar amount of the 2,2' -biphenyldiphenol compound as an alkyl substituent, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
In a preferred embodiment of the present invention, the temperature of the first reaction is 25 to 55 ℃ and may be, for example, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or 55 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the first reaction time is 12 to 48 hours, for example, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, 40 hours, 42 hours, 44 hours, 46 hours or 48 hours, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the separation is carried out by reducing the temperature of the liquid phase obtained by the solid-liquid separation to-10 ℃ to 5 ℃, and examples thereof include-10 ℃, 9 ℃, 8 ℃, 7 ℃, 6 ℃,5 ℃,4 ℃,3 ℃,2 ℃,1 ℃, 0 ℃,2 ℃,3 ℃,4 ℃ and 5 ℃, but are not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst has the advantages of good effect, low reaction temperature, difficult coking, simple operation and convenient industrialization.
(2) The catalyst, the catalyst and the reaction solvent provided by the invention can be directly recycled. No process waste water is generated, and the method is environment-friendly. The total yield of 2,2' -biphenol is above 90.0%, and the purity is above 99.5% (HPLC).
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
This example provides a preparation method of a catalyst, which includes:
a polyglycol compound (32 kg, molecular weight 400), 6% dilute hydrochloric acid (1200 kg), 1,3-propane sultone (900 kg), methyl orthosilicate (60 kg), (3-mercaptopropyl) trimethoxysilane (8 kg) and 30% hydrogen peroxide (80 kg) are sequentially added into a 2000L enamel reactor provided with a push type stirring thermometer, mixed and reacted for 5 hours at room temperature, then refluxed for 15 hours, cooled to room temperature, filtered and separated, the obtained filter cake and methanol (400 kg) are refluxed for 4 hours, cooled to room temperature, filtered and separated, the filter cake is washed for 2 times by methanol (40 kg), and the obtained solid is dried in vacuum at 50 ℃ to obtain 80kg of the main catalyst.
A1000L enamel reactor equipped with a push type stirrer and a thermometer is sequentially added with 600.0kg of anhydrous isopropanol and 25.4kg of iodine, stirred and dissolved at 25 ℃, then added with 55kg of ZSM-5 molecular sieve, stirred and adsorbed for 3 hours at 25 ℃. Heating and decompressing to distill the isopropanol, and vacuum-drying the obtained solid at 50 ℃ to obtain the cocatalyst.
Application example 1
Into a 2000L enamel reactor equipped with a propeller stirrer, thermometer, condenser and water separator, 2,2' -biphenyldiphenol compound (205.3 kg) containing alkyl substituent (R in the formula) 1 、R 3 、R 1 ’、R 3 ' is H, R 2 、R 4 、R 2 ’、R 4 T-butyl, toluene (1500 kg), main catalyst (41.1 kg) and cocatalyst (4.1 kg) were heated to 45 ℃ and the reaction was continued at this temperature, monitored by high performance liquid chromatography until the reaction of the starting materials was complete, and continued for 1 hour. Filtering out the catalyst, rinsing the catalyst with toluene (120 kg), merging solvent phases, recovering part of the solvent under reduced pressure, recycling the solvent for reuse, cooling the residual materials in the kettle to 0 ℃, continuously stirring for 30 minutes at the temperature, filtering, adding activated carbon (2.5 kg) into the filtered mother liquor, stirring for 1 hour at 100 ℃, cooling to room temperature, filtering to remove the activated carbon, and continuously reusing the mother liquor as the solvent. The filter cake after the reaction solution cooling and filtration is dried in vacuum at 60 ℃ to constant weight to obtain white solid powder 2,2' -biphenol 84.9kg, yield 91.2%, purity 99.7% (HPLC), melting range (DSC): 108.5-112.4 ℃.
Application example 2
In the application example, the catalyst is prepared as in example 1, under the condition that other preparation conditions are not changed, the type of the solvent is changed, the solvent is changed into benzene (1200 kg), the catalyst is filtered after the reaction is finished, the catalyst is rinsed with benzene (100 kg), the solvent phases are combined, part of the solvent is recovered under reduced pressure, the solvent is recovered and reused, the temperature of the residual materials in the kettle is reduced to 5 ℃, the temperature is kept for stirring for 30 minutes, the filtration is carried out, and the filter cake is dried in vacuum at 60 ℃ to constant weight. Adding activated carbon (3.0 kg) into the mother liquor, stirring for 1h at 80 ℃, cooling to room temperature, filtering to remove the activated carbon, and continuously using the mother liquor as a solvent. 84.3kg of white solid product 2,2' -biphenol is obtained with a yield of 90.5% and a purity of 99.8% (HPLC), melting range (DSC): 108.5-112.5 ℃.
Application example 3
In the application example, the catalyst is prepared as in example 1, under the condition that other preparation conditions are not changed, the type of the solvent is changed, the solvent is changed into dimethylbenzene (1600 kg), the catalyst is filtered after the reaction is finished, the catalyst is rinsed with dimethylbenzene (150 kg), the solvent phases are combined, part of the solvent is recovered under reduced pressure, the solvent is recovered and reused, the temperature of the residual materials in the kettle is reduced to 0 ℃, the temperature is kept for stirring for 30 minutes, then the filtration is carried out, and the filter cake is dried in vacuum at 60 ℃ to constant weight. Adding activated carbon (4.0 kg) into the mother liquor, stirring for 1h at 100 ℃, cooling to room temperature, filtering to remove the activated carbon, and continuously using the mother liquor as a solvent. 84.7kg of white solid product 2,2' -biphenol are obtained with a yield of 91.0% and a purity of 99.8% (HPLC), melting range (DSC): 108.5-112.5 ℃.
Application example 4
The catalyst preparation in this application example was as in example 1. Into a 2000L enamel reactor equipped with a propeller stirrer, thermometer, condenser and water separator, 2,2' -biphenyldiphenol compound (205.3 kg) containing alkyl substituent (R in the formula) 1 、R 3 、R 1 ’、R 3 ' is H, R 2 、R 4 、R 2 ’、R 4 The' is tert-butyl), toluene (1200 kg), a main catalyst (30.8 kg) and an auxiliary catalyst (4.1 kg), the mixture is heated to 35 ℃, the reaction is continued at the temperature, the reaction is monitored by a high performance liquid chromatography until the raw materials are completely reacted, and the reaction is continued for 1 hour. Filtering out the catalyst, rinsing the catalyst with toluene (120 kg), merging solvent phases, recovering part of the solvent under reduced pressure, recycling the solvent, cooling the residual materials in the kettle to 0 ℃, continuously stirring at the temperature for 30 minutes, filtering mother liquor, adding activated carbon (3.0 kg), stirring at 80 ℃ for 1 hour, cooling to room temperature, filtering to remove the activated carbon, and continuously recycling the mother liquor as the solvent. The filter cake after the reaction solution cooling and filtration is dried in vacuum at 60 ℃ to constant weight to obtain white solid powder 2,2' -biphenyl diphenol 86.1kg with yield 92.5% and purity 99.8% (HPLC), melting range (DSC): 108.5-112.5 ℃.
Application example 5
The catalyst preparation in this application example was as in example 1. A2000L enamel reactor equipped with a propeller stirrer, thermometer, condenser, and water separator was charged with 2,2' -biphenyldiphenol compound (205.3 kg (R in the formula) 1 、R 3 、R 1 ’、R 3 ' is H, R 2 、R 4 、R 2 ’、R 4 ' is tert-butyl group), benzene (1200 kg), main catalyst (30.8 kg), catalyst (4.1 kg), heated to 35 deg.C, and continued at this temperatureAnd (3) reacting at the temperature, monitoring the reaction by using a high performance liquid chromatography until the reaction of the raw materials is complete, and continuing the reaction for 1 hour. Filtering out the catalyst, rinsing the catalyst with benzene (100 kg), merging solvent phases, recovering part of the solvent under reduced pressure, recycling the solvent for reuse, cooling the residual materials in the kettle to 5 ℃, continuously stirring at the temperature for 30 minutes, filtering mother liquor, adding activated carbon (3.0 kg), stirring at 80 ℃ for 1 hour, cooling to room temperature, filtering to remove the activated carbon, and continuously using the mother liquor as the solvent for reuse. The filter cake obtained by cooling and filtering the reaction liquid is dried in vacuum at 60 ℃ to constant weight to obtain white solid powder 2,2' -biphenol 85.0kg, the yield is 91.3%, the purity is 99.7% (HPLC), and the melting range (DSC): 108.5-112.4 ℃.
Application example 6
The catalyst in this application example was prepared as in example 1. Into a 2000L enamel reactor equipped with a propeller stirrer, thermometer, condenser and water separator, 2,2' -biphenyldiphenol compound (163.2 kg) containing alkyl substituent (R in the formula) 1 、R 3 、R 4 、R 1 ’、R 3 ’、R 4 ' is H, R 2 、R 2 T-amyl group, p-xylene (1600 kg), a main catalyst (50.0 kg) and an auxiliary catalyst (2.5 kg), heating to 45 ℃, continuing the reaction at the temperature, monitoring the reaction by using a high performance liquid chromatography until the raw materials are completely reacted, and continuing the reaction for 1 hour. Filtering out the catalyst, rinsing the catalyst with p-xylene (150 kg), merging benzene phases, recovering benzene under reduced pressure, cooling the residual materials in the kettle to 0 ℃, continuously stirring at the temperature for 30 minutes, then adding activated carbon (2.5 kg) into the filtered mother liquor, stirring at 100 ℃ for 1 hour, cooling to room temperature, filtering to remove the activated carbon, and continuously recycling the mother liquor as a solvent. The filter cake obtained by cooling and filtering the reaction solution is dried in vacuum at 60 ℃ to constant weight to obtain white solid powder 2,2' -biphenol 83.0kg, the yield is 89.2%, the purity is 99.7% (HPLC), and the melting range (DSC): 108.4-112.4 ℃.
Application example 7
The other steps were the same as in application example 1 except that the recovered solvent and the filtrate were used repeatedly as the reaction solvent three times, and the results of the three times were:
| number of times of solvent application | Yield of | Purity (HPLC) | Melting range (DSC) |
| Novel solvent | 91.2％ | 99.7％ | 108.5-112.4℃ |
| The solvent is repeatedly used for one time | 92.4％ | 99.6％ | 108.5-112.4℃ |
| Solvent is repeatedly used twice | 92.5％ | 99.5％ | 108.4-112.4℃ |
| Solvent is repeated three times | 92.5％ | 99.5％ | 108.4-112.4℃ |
The data of the embodiment show that the solvent can be repeatedly used for at least 3 times, the yield is more than 92 percent, the purity is more than 99 percent (HPLC), the melting range is between 108 and 112 ℃, and the product quality reaches the standard.
Application example 8
The other steps were the same as in application example 1, except that the catalyst was used repeatedly three times, and the results of three times of use were:
| number of times of catalyst application | Yield of | Purity (HPLC) | Melting range (DSC) |
| Novel catalyst | 91.2％ | 99.7％ | 108.5-112.4℃ |
| Once application of catalyst | 90.6％ | 99.7％ | 108.5-112.4℃ |
| Secondary application of catalyst | 90.4％ | 99.6％ | 108.5-112.4℃ |
| Using catalyst three times | 90.1％ | 99.6％ | 108.5-112.4℃ |
Application example 9
The difference from application example 1 is that 1,3-propane sultone was replaced with an equal amount of ethyl methanesulfonate. The yield of 2,2' -biphenol obtained is 30.3%, the purity is 93.3%, and the melting range is 103.6-105.1 ℃.
Application example 10
The only difference from application example 1 is that (3-mercaptopropyl) trimethoxysilane was not added. The yield of 2,2' -biphenol obtained is 52.6%, the purity is 96.8%, and the melting range is 106.2-107.4 ℃.
Application example 11
The only difference from example 1 is that no methyl orthosilicate is added. The yield of 2,2' -biphenol is 48.3%, the purity is 95.7%, and the melting range is 105.3-106.8 ℃.
Application example 12
The only difference from example 1 is that the mass ratio of methyl orthosilicate to (3-mercaptopropyl) trimethoxysilane is 1:3, i.e. 180kg of (3-mercaptopropyl) trimethoxysilane are added, the mass of methyl orthosilicate being 60kg. The yield of 2,2' -biphenol is 83.2%, the purity is 99.1%, and the melting range is 108.1-110.2 ℃.
Application example 13
The only difference from application example 1 is that no cocatalyst was added. The yield of 2,2' -biphenol is 76.2%, the purity is 98.1%, and the melting range is 107.1-109.2 ℃.
Application example 14
The only difference from application example 1 is that elemental iodine is sublimated to potassium iodate. The yield of 2,2' -biphenol obtained is 83.6%, the purity is 98.2%, and the melting range is 107.5-109.1 ℃.
Application example 15
The only difference from application example 1 is that the same amount of cocatalyst as the procatalyst was added. The yield of 2,2' -biphenol obtained is 85.7%, the purity is 98.5%, and the melting range is 107.9-109.7 ℃.
The data of the application example show that the catalyst can be repeatedly used at least three times, the product performance is not changed, the catalyst has good recycling performance, the yield can be ensured to be more than 90%, the purity is more than 99% (HPLC), the melting range is 108-112 ℃, and the product quality reaches the standard.
It is to be noted that the present invention is described by the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the detailed structural features, that is, it is not meant to imply that the present invention must be implemented by relying on the detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A catalyst for preparing 2,2' -biphenol, which is characterized by comprising a main catalyst and an auxiliary catalyst;
the main catalyst comprises polyethylene glycol, inorganic acid, sultone, silicate ester, organosilane and an oxidant;
the cocatalyst comprises elemental iodine, alcohol and a molecular sieve.
2. The catalyst of claim 1 for the preparation of 2,2' -biphenol, wherein the inorganic acid comprises 1 or a combination of at least 2 of hydrochloric, hydrobromic or sulfuric acid;
preferably, the sultones comprise 1 or a combination of at least 2 of 1,3-propane sultone, 1,4-butane sultone, or 1,5-pentane sultone;
preferably, the silicate comprises 1 or a combination of at least 2 of methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate, or butyl orthosilicate;
preferably, the silane comprises 1 or a combination of at least 2 of trimethylsilane, tri-n-hexylmethylsilane, or (3-mercaptopropyl) trimethoxysilane;
preferably, the oxidizing agent comprises Oxone, 1 or a combination of at least 2 of hydrogen peroxide or m-chloroperoxybenzoic acid;
preferably, the alcohol comprises 1 or a combination of at least 2 of isopropanol, n-propanol, n-butanol or isobutanol;
preferably, the molecular sieve comprises a ZSM-5 molecular sieve and/or a ZSM-11 molecular sieve.
3. The catalyst of claim 1 or 2 for the preparation of 2,2' -biphenol, wherein the mass concentration of the inorganic acid is 3-10%;
preferably, the mass concentration of the oxidant is 15-35%;
preferably, the mass ratio of polyethylene glycol, inorganic acid, sultone, silicate ester, organosilane and oxidant in the main catalyst is (0.01-0.05): 1 (0.5-1): 0.01-0.1): 0.001-0.02): 0.001-0.01;
preferably, the mass ratio of the elementary iodine, the alcohol and the molecular sieve in the cocatalyst is 1 (0.01-0.1) to (0.05-0.3).
4. A process for preparing a catalyst of any one of claims 1 to 3 for use in the preparation of 2,2' -biphenol, said process comprising procatalyst preparation and cocatalyst preparation;
the preparation of the main catalyst comprises the steps of preparing materials according to a formula, and then sequentially carrying out first mixing reaction, backflow, solid-liquid separation, methanol backflow, solid-liquid separation and first drying to obtain the main catalyst;
the preparation of the cocatalyst comprises the steps of preparing materials according to a formula, and then sequentially carrying out second mixing reaction, alcohol separation and second drying to obtain the cocatalyst.
5. The method of claim 4, wherein the first mixing reaction is performed at a temperature of 20 to 40 ℃;
preferably, the time of the first mixing reaction is 2-5h;
preferably, the refluxing time is 10-20h;
preferably, the amount of the methanol in the methanol reflux is 4-6 times of the mass of the polyethylene glycol;
preferably, the refluxing time of the methanol is 4-5h;
preferably, the first drying mode is vacuum drying;
preferably, the temperature of the primary drying is 50 to 60 ℃.
6. The method according to claim 4 or 5, wherein the temperature of the second mixing reaction is 20 to 45 ℃;
preferably, the time of the second mixing reaction is 1-3h;
preferably, the alcohol separation is to separate the alcohol in the material by adopting a distillation mode;
preferably, the second drying mode is vacuum drying;
preferably, the temperature of the second drying is 50 to 70 ℃.
7. The method according to any one of claims 4 to 6, wherein the method comprises preparation of a procatalyst and preparation of a cocatalyst;
the preparation of the main catalyst comprises the steps of preparing materials according to a formula, and then sequentially carrying out first mixing reaction, backflow, solid-liquid separation, methanol backflow, solid-liquid separation and first drying to obtain the main catalyst; the temperature of the first mixed reaction is 20-40 ℃; the time of the first mixing reaction is 2-5h; the reflux time is 10-20h; the dosage of the methanol in the methanol reflux is 4-6 times of the mass of the polyethylene glycol; the methanol refluxing time is 4-5h; the first drying mode is vacuum drying; the temperature of the primary drying is 50-60 ℃;
the preparation of the cocatalyst comprises the steps of preparing materials according to a formula, and then sequentially carrying out second mixing reaction, alcohol separation and second drying to obtain the cocatalyst; the temperature of the second mixed reaction is 20-45 ℃; the time of the second mixing reaction is 1-3h; the alcohol separation is to separate the alcohol in the material by adopting a distillation mode; the second drying mode is vacuum drying; the temperature of the second drying is 50-70 ℃.
8. Use of a catalyst according to any one of claims 1 to 3 for the preparation of 2,2 '-biphenol, said use comprising the preparation of 2,2' -biphenol using said catalyst, in particular comprising:
mixing 2,2 '-biphenyldiphenol compound containing alkyl substituent, solvent and catalyst, carrying out first reaction, and then carrying out solid-liquid separation and cooling separation to obtain 2,2' -biphenyldiol solid.
9. The use of claim 8, wherein the mass ratio of the procatalyst of the catalyst in the mixture to the alkyl-substituted 2,2' -biphenyldiphenol compound is (0.1-0.5): 1;
preferably, the mass ratio of the cocatalyst of the catalyst to the alkyl substituent 2,2' -biphenyldiphenol compound in the mixture is (0.01-0.05): 1;
preferably, the solvent comprises 1 or a combination of at least 2 of benzene, toluene, xylene, o-xylene, m-xylene, or p-xylene;
preferably, the addition amount of the solvent is 10 to 50 times of the molar amount of the 2,2' -biphenyldiphenol compound with the alkyl substituent.
10. The use according to claim 8 or 9, wherein the temperature of the first reaction is between 25 ℃ and 55 ℃;
preferably, the time of the first reaction is 12-48h;
preferably, the temperature reduction separation is to reduce the temperature of a liquid phase obtained by solid-liquid separation to-10-5 ℃ for separation.
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