CN115814854B - 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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- CN115814854B CN115814854B CN202211437800.0A CN202211437800A CN115814854B CN 115814854 B CN115814854 B CN 115814854B CN 202211437800 A CN202211437800 A CN 202211437800A CN 115814854 B CN115814854 B CN 115814854B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 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 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000008053 sultones Chemical class 0.000 claims abstract description 7
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 28
- 238000000926 separation method Methods 0.000 claims description 28
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- -1 2,2' -biphenol compound Chemical class 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 150000001875 compounds Chemical class 0.000 claims description 7
- 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
- 239000000203 mixture Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 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
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-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
- 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
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 210000003298 dental enamel Anatomy 0.000 description 6
- 238000010309 melting process Methods 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005406 washing Methods 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
- 238000012544 monitoring process Methods 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
- 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
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 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
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 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
- 239000012527 feed solution Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 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
- 229920000642 polymer Polymers 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
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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; the method is environment-friendly, does not generate waste water, has simple process and low equipment requirement, and is convenient for realizing industrialization. The catalyst comprises a main catalyst and an auxiliary catalyst; the main catalyst comprises polyethylene glycol, inorganic acid, sultone, silicate, organosilane and oxidant; the auxiliary catalyst comprises elemental iodine, alcohol and molecular sieve. The purity of the 2,2' -biphenol prepared by the catalyst is more than or equal to 99.5%, and the total yield can reach more than 90%.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a catalyst for preparing 2,2' -biphenol, a preparation method and application thereof.
Background
At present, 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 also can be used for sulfur chloride cold vulcanization products (such as medical gloves and condoms) and the like. Since the polymer has excellent heat resistance, it can be used as a modified monomer for polyester, polyurethane, polycarbonate, polysulfone, epoxy resin and the like to produce excellent engineering plastics, composite materials and the like.
The compound has the following preparation methods, for example, U.S. 2244244A 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 reaction temperature is high, the product is easy to coke, and the viscosity of the material is high, so that the requirement on equipment is high. As disclosed in US6410238a, biphenyl compounds are subjected to multi-step reactions such as sulfonation, alkali fusion and the like to prepare target products, and the method has a large amount of strong acid and alkali wastewater and is not environment-friendly.
The prior art (J.org.chem.1987, 52, 1881-1884) discloses a process for the preparation of Nafion-H+ as a catalyst for the removal of tert-butyl groups, which is expensive and not readily available.
CN105348047a discloses that tert-butyl diphenol is used as raw material, and when the reaction is completed, the product is cooled, crystallized, filtered and separated. The product melting point is around 110℃and the aftertreatment described in the patent examples is not possible in the absence of solvents.
CN105967980a discloses that using biphenol compounds as raw materials and noble metal palladium compounds as catalysts, the process is costly and the use of oxidants in the reaction presents explosion risks.
In view of the above reasons, the invention overcomes various disadvantages in the above method, and develops a catalyst with good catalytic effect, low reaction temperature, high yield and good quality. The environment-friendly, low equipment requirement and convenient realization of the industrialized preparation method of the 2,2' -biphenol.
Disclosure of Invention
In view of the problems existing 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, meanwhile, the supported catalyst and the reaction solvent can be directly recycled, the recycling effect is good, the environment is friendly, no waste water is generated, the process is simple, the equipment requirement is low, and the industrialization is convenient to realize.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a catalyst for preparing 2,2' -biphenol, the catalyst comprising a main catalyst and a cocatalyst;
the main catalyst comprises polyethylene glycol, inorganic acid, sultone, silicate, organosilane and oxidant;
The auxiliary catalyst comprises elemental iodine, alcohol and molecular sieve.
The catalyst provided by the invention realizes the high-efficiency dealkylation effect by adopting a mode of matching a specific main catalyst and an auxiliary catalyst, is beneficial to the high-efficiency preparation of the catalyst for the 2,2 '-biphenol, and the purity of the 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 structural formula of the 2,2' -biphenol is as follows:
In the present invention, the polyethylene glycol has a molecular weight of 200 to 600, and may be, for example, 200, 300, 400, 500 or 600, etc., but is not limited to the values recited, and other values not recited in the range are equally 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 sultone comprises 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 1 or a combination of at least 2 of Oxone, 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.
In a preferred embodiment of the present invention, the inorganic acid may be present 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%, etc., but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned ranges are equally applicable.
Preferably, the mass concentration of the oxidizing agent is 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 non-recited values within this range are equally applicable.
Preferably, the mass ratio of polyethylene glycol, inorganic acid, sultone, silicate, 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), for example 0.01:1:0.5:0.01:0.001:0.001、0.05:1:1:0.1:0.02:0.01、0.03:1:0.75:0.05:0.01:0.005、0.04:1:0.6:0.03:0.015:0.007 or 0.02:1:0.9:0.07:0.018:0.003, etc., but not limited to the recited values, other non-recited values in the range are equally applicable.
Preferably, the mass ratio of elemental iodine to alcohol to molecular sieve in the cocatalyst is 1 (0.01-0.1): (0.05-0.3), such as 1:0.01:0.05、1:0.02:0.05、1:0.04:0.05、1:0.06:0.05、1:0.08:0.05、1:0.1:0.05、1:0.1:0.1、1:0.1:0.15、1:0.1:0.2、1:0.1:0.25、 or 1:0.1:0.3, but not limited to the recited values, other non-recited values within the range are equally applicable.
In a second aspect, the present invention provides a process for the preparation of a catalyst according to the first aspect, the process comprising a main catalyst preparation and a cocatalyst preparation;
The preparation of the main catalyst comprises the steps of proportioning according to a formula, and 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 auxiliary catalyst comprises the steps of proportioning according to a formula, sequentially carrying out a second mixing reaction, alcohol separation and second drying to obtain the auxiliary catalyst.
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℃40℃or the like, but not limited to the values recited, and other values not recited in the above range are equally applicable.
Preferably, the time of the first mixing reaction is 2-5h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h or 5h, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the reflux time is 10-20h, for example, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h or 20h, etc., but not limited to the recited values, other non-recited values within this range are equally applicable.
Preferably, the amount of methanol in the methanol reflux is 4 to 6 times the mass of polyethylene glycol, and may be, 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, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the methanol is refluxed for 4-5h, for example, 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5h, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the first drying mode is vacuum drying.
The temperature of the first drying is preferably 50 to 60 ℃, and may be, for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, or the like, but is not limited to the values recited, and other values not recited in the range are equally 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℃50℃or the like, but not limited to the values recited, and other values not recited in the above range are equally applicable.
Preferably, the time of the second mixing reaction is 1-3h, for example, 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h or 3h, etc., but not limited to the recited values, other non-recited values within this range are equally applicable.
Preferably, the alcohol separation is carried out by distillation to separate the alcohol from the material.
Preferably, the second drying mode is vacuum drying.
Preferably, the temperature of the second drying is 50 to 70 ℃, for example, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, or 70 ℃, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises main catalyst preparation and auxiliary catalyst preparation;
The preparation of the main catalyst comprises the steps of proportioning according to a formula, and sequentially carrying out first mixing reaction, reflux, solid-liquid separation, methanol reflux, 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 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 is refluxed for 4-5 hours; the first drying mode is vacuum drying; the temperature of the first drying is 50-60 ℃;
The preparation of the auxiliary catalyst comprises the steps of proportioning according to a formula, sequentially carrying out a second mixing reaction, alcohol separation and second drying to obtain the auxiliary catalyst; 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 distillation; the second drying mode is vacuum drying; the second drying temperature is 50-70 ℃.
In a third aspect, the present invention provides a use of the catalyst of the first aspect, comprising the preparation of 2,2' -biphenol using the catalyst, comprising in particular:
mixing the 2,2 '-biphenol compound containing alkyl substituent, a solvent and a catalyst, performing a first reaction, and then performing solid-liquid separation and cooling separation to obtain the 2,2' -biphenol solid.
In the invention, the structural formula of the 2,2' -biphenol compound containing the alkyl substituent is as follows:
Wherein R 1-R4 is independently selected from 1 of tertiary carbon alkyl, isopropyl or hydrogen; r 1'-R4' are each independently selected from 1 of tertiary carbon alkyl, isopropyl or hydrogen.
In the invention, the filter cake after the solid-liquid separation in the reaction in the preparation process of the 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 the liquid phase obtained in the cooling separation process, stirring is carried out for 1h at 80-100 ℃, the active carbon is filtered, the obtained feed liquid can be directly used as a solvent of the next batch without treatment, and the mass ratio of the addition of the active carbon to the 2,2' -biphenol compound containing alkyl substituent is (1-2): 100, thereby realizing the secondary utilization of the solvent in the feed liquid.
In a preferred embodiment of the present invention, the mass ratio of the main catalyst and the alkyl substituent of the catalyst in the mixture is (0.1-0.5): 1, for example 0.1:1、0.12:1、0.14:1、0.16:1、0.18:1、0.2:1、0.22:1、0.24:1、0.26:1、0.28:1、0.3:1、0.32:1、0.34:1、0.36:1、0.38:1、0.4:1、0.42:1、0.44:1、0.46:1、0.48:1 or 0.5:1, but the present invention is not limited to the values recited, and other values not recited in the above range are equally applicable.
Preferably, the mass ratio of the cocatalyst to the alkyl substituent of the catalyst in the mixture is (0.01-0.05): 1, for example 0.01:1、0.012:1、0.014:1、0.016:1、0.018:1、0.02:1、0.022:1、0.024:1、0.026:1、0.028:1、0.03:1、0.032:1、0.034:1、0.036:1、0.038:1、0.04:1、0.042:1、0.044:1、0.046:1、0.048:1 or 0.05:1, but not limited to the values recited, other non-recited values within this range are equally applicable.
Preferably, the solvent comprises 1 or a combination of at least 2 of benzene, toluene, xylene, ortho-xylene, meta-xylene, or para-xylene.
The solvent is preferably added in an amount of 10 to 50 times the molar amount of the 2,2' -biphenol compound having an alkyl substituent, 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, etc., but not limited to the recited values, and other non-recited values within this range are equally 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℃55℃or the like, but not limited to the values recited, and other values not recited in the above range are equally applicable.
Preferably, the time of the first reaction is 12-48h, for example, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h or 48h, etc., but not limited to the recited values, other non-recited values within this range are equally applicable.
Preferably, the temperature reduction separation is to reduce the temperature of the liquid phase obtained by the solid-liquid separation to-10 ℃ to 5 ℃ for separation, for example, -10 ℃, -9 ℃, -8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃, 0 ℃,1 ℃,2 ℃,3 ℃,4 ℃ or 5 ℃ and the like, but the temperature reduction separation is not limited to the recited values, and other non-recited values in the range are equally 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 can be directly recycled. No process waste water is generated, and the environment is friendly. The total yield of the 2,2' -biphenol is more than 90.0% and the purity is more than 99.5% (HPLC).
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The embodiment provides a preparation method of a catalyst, which specifically comprises the following steps:
to a 2000L enamel reactor equipped with a push-type stirrer and a thermometer, a polyglycol compound (32 kg, molecular weight 400), 6% diluted 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) were sequentially added, mixed and reacted at room temperature for 5 hours, refluxed for 15 hours, cooled to room temperature, filtered and separated, the obtained filter cake and methanol (400 kg) were refluxed for 4 hours, cooled to room temperature, filtered and separated, the filter cake was washed with methanol (40 kg) for 2 times, and the obtained solid was dried under vacuum at 50 ℃ to obtain 80kg of main catalyst.
600.0Kg of anhydrous isopropanol and 25.4kg of iodine are sequentially added into a 1000L enamel reactor provided with a push-type stirring thermometer, stirred and dissolved at 25 ℃, 55kg of ZSM-5 molecular sieve is added, and stirred and adsorbed for 3 hours at 25 ℃. The isopropanol is distilled off under the condition of temperature and pressure rise, and the obtained solid is dried in vacuum at 50 ℃ to obtain the auxiliary catalyst.
Application example 1
To a 2000L enamel reactor equipped with a propeller stirrer, a thermometer, a condenser and a water separator, 2' -biphenol compound (205.3 kg) containing alkyl substituent (wherein R 1、R3、R1'、R3 ' is H, R 2、R4、R2'、R4 ' is tert-butyl), toluene (1500 kg), a main catalyst (41.1 kg) and a cocatalyst (4.1 kg) were added, the mixture was heated to 45℃and the reaction was continued at this temperature, and the reaction was continued for 1 hour until the raw material was completely reacted by monitoring with high performance liquid chromatography. Filtering out the catalyst, washing the catalyst with toluene (120 kg), merging the solvent phases, recovering part of the solvent under reduced pressure, recycling the solvent, cooling the rest materials in the kettle to 0 ℃, continuously stirring for 30 minutes at the temperature, filtering, adding active carbon (2.5 kg) into the filtered mother liquor, stirring for 1h at 100 ℃, cooling to room temperature, filtering to remove the active carbon, and continuously recycling the mother liquor as the solvent. The filter cake of the reaction solution which is cooled and filtered is dried to constant weight in vacuum at 60 ℃ to obtain 84.9kg of white solid powder 2,2' -biphenol, the yield is 91.2%, the purity is 99.7% (HPLC), and the 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 unchanged, the solvent type is changed to benzene (1200 kg), the catalyst is filtered after the reaction is finished, the catalyst is rinsed by benzene (100 kg), the solvent phases are combined, part of the solvent is recovered under reduced pressure, the recovered solvent is used mechanically, the temperature of the residual materials in the kettle is reduced to 5 ℃, the materials are continuously stirred for 30 minutes at the temperature, the materials are filtered, and the filter cake is dried to constant weight under vacuum at 60 ℃. Adding active carbon (3.0 kg) into the mother solution, stirring at 80deg.C for 1 hr, cooling to room temperature, filtering to remove active carbon, and using the mother solution as solvent. 84.3kg of 2,2' -biphenol as a white solid powder product were obtained in 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 unchanged, only the solvent type 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 recovered solvent is reused, the temperature of the residual materials in the kettle is reduced to 0 ℃, the materials are continuously stirred for 30 minutes at the temperature, the materials are filtered, and the filter cake is dried to constant weight under vacuum at 60 ℃. Adding active carbon (4.0 kg) into the mother solution, stirring at 100deg.C for 1 hr, cooling to room temperature, filtering to remove active carbon, and using the mother solution as solvent. 84.7kg of 2,2' -biphenol as a white solid powder product was obtained in 91.0% yield with a purity of 99.8% (HPLC), melting range (DSC): 108.5-112.5 ℃.
Application example 4
The catalyst preparation in this application example is as in example 1. To a 2000L enamel reactor equipped with a propeller stirrer, a thermometer, a condenser and a water separator, 2' -biphenol compound (205.3 kg) containing alkyl substituent (wherein R 1、R3、R1'、R3 ' is H, R 2、R4、R2'、R4 ' is tert-butyl), toluene (1200 kg), a main catalyst (30.8 kg) and a cocatalyst (4.1 kg) were added, the mixture was heated to 35℃and the reaction was continued at this temperature, and the reaction was monitored by HPLC until the raw material was completely reacted, and the reaction was continued for 1 hour. Filtering out the catalyst, washing the catalyst with toluene (120 kg), merging the solvent phases, recovering part of the solvent under reduced pressure, recycling the solvent, cooling the rest materials in the kettle to 0 ℃, continuously stirring for 30 minutes at the temperature, adding active carbon (3.0 kg) into the filtered mother liquor, stirring for 1h at 80 ℃, cooling to room temperature, filtering to remove the active carbon, and continuously recycling the mother liquor as the solvent. The filter cake of the reaction solution which is cooled and filtered is dried to constant weight in vacuum at 60 ℃ to obtain 86.1kg of white solid powder of 2,2' -biphenol, the yield is 92.5%, the purity is 99.8% (HPLC), and the melting range (DSC): 108.5-112.5 ℃.
Application example 5
The catalyst preparation in this application example is as in example 1. Adding 2,2 '-biphenol compound (205.3 kg (wherein R 1、R3、R1'、R3' is H, R 2、R4、R2'、R4 'is tert-butyl), benzene (1200 kg), main catalyst (30.8 kg) and catalyst (4.1 kg) containing alkyl substituent into 2000L enamel reactor with push stirring, thermometer, condenser and water separator, heating to 35 deg.C, continuing to react at this temperature, monitoring the reaction until the raw material is completely reacted by high performance liquid chromatography, continuing to react for 1 hr, filtering out catalyst, washing the catalyst with benzene (100 kg), mixing solvent phase, recovering part of solvent under reduced pressure, recovering solvent, cooling the rest material in the reactor to 5 deg.C, stirring for 30 min, filtering, adding active carbon (3.0 kg), stirring at 80 deg.C for 1 hr, cooling to room temperature, filtering to remove active carbon, continuing to use the filtered filter cake at 60 deg.C, vacuum drying to constant weight to obtain white solid powder 2,2' -biphenol 85.0kg, 91.3%, 99.7% (DSC-108) with purity of the final product at the temperature of 5.7% (DSC-108).
Application example 6
The catalyst preparation in this application example is as in example 1. To a 2000L enamel reactor equipped with a propeller stirrer, a thermometer, a condenser and a water separator, 2' -biphenol compound (163.2 kg) containing alkyl substituent (wherein R 1、R3、R4、R1'、R3'、R4 ' is H, R 2、R2 ' is tert-amyl), paraxylene (1600 kg), a main catalyst (50.0 kg) and a cocatalyst (2.5 kg) were added, the mixture was heated to 45℃and the reaction was continued at this temperature, and the reaction was continued for 1 hour after monitoring the reaction until the raw material was completely reacted by high performance liquid chromatography. Filtering out the catalyst, washing the catalyst with paraxylene (150 kg), merging benzene phases, recovering benzene under reduced pressure, cooling the rest materials in the kettle to 0 ℃, continuously stirring for 30 minutes at the temperature, adding active carbon (2.5 kg) into the filtered mother liquor, stirring for 1h at 100 ℃, cooling to room temperature, filtering to remove the active carbon, and continuously using the mother liquor as a solvent. The filter cake of the reaction solution which is cooled and filtered is dried to constant weight in vacuum at 60 ℃ to obtain 83.0kg of white solid powder of 2,2' -biphenol, 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 filtered feed solution were repeatedly used as the reaction solvent three times, and the results of the three times were:
| Number of solvent applications | Yield is good | Purity (HPLC) | Melting range (DSC) |
| New solvents | 91.2％ | 99.7％ | 108.5-112.4℃ |
| Repeating the solvent once | 92.4％ | 99.6％ | 108.5-112.4℃ |
| Repeating the solvent twice | 92.5％ | 99.5％ | 108.4-112.4℃ |
| The solvent is repeated three times | 92.5％ | 99.5％ | 108.4-112.4℃ |
From the example data, the solvent can be used repeatedly at least 3 times, the yield is more than 92%, the purity is more than 99% (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 repeatedly used three times, and the results of the three uses were:
| number of times of catalyst application | Yield is good | Purity (HPLC) | Melting range (DSC) |
| Novel catalyst | 91.2％ | 99.7％ | 108.5-112.4℃ |
| Disposable catalyst sleeve | 90.6％ | 99.7％ | 108.5-112.4℃ |
| Secondary catalyst sleeve | 90.4％ | 99.6％ | 108.5-112.4℃ |
| The catalyst is applied for 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 is replaced by an equivalent amount of ethyl methylsulfonate. The yield of the obtained 2,2' -biphenol is 30.3%, the purity is 93.3%, and the melting process is 103.6-105.1 ℃.
Application example 10
The difference from application example 1 is only that (3-mercaptopropyl) trimethoxysilane is not added. The yield of the obtained 2,2' -biphenol 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 was added. The yield of the obtained 2,2' -biphenol is 48.3%, the purity is 95.7%, and the melting process is 105.3-106.8 ℃.
Application example 12
The difference from example 1 is only 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 the obtained 2,2' -biphenol is 83.2%, the purity is 99.1%, and the melting process is 108.1-110.2 ℃.
Application example 13
The difference from application example 1 is only that no cocatalyst was added. The yield of the obtained 2,2' -biphenol is 76.2%, the purity is 98.1%, and the melting process is 107.1-109.2 ℃.
Application example 14
The only difference from application example 1 is that elemental iodine was sublimated to potassium iodate. The yield of the obtained 2,2' -biphenol is 83.6%, the purity is 98.2%, and the melting process is 107.5-109.1 ℃.
Application example 15
The difference from application example 1 is only that the cocatalyst was added in an equivalent amount to the main catalyst. The yield of the obtained 2,2' -biphenol is 85.7%, the purity is 98.5%, and the melting process is 107.9-109.7 ℃.
The data of application examples show that the catalyst can be used repeatedly at least three times without changing the product performance, has good recycling performance, can ensure the yield to be more than 90 percent, the purity to be more than 99 percent (HPLC), the melting range to be between 108 and 112 ℃, and the product quality reaches the standard.
It is stated that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e., it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (30)
1. A catalyst for preparing 2,2' -biphenol, characterized in that the catalyst comprises a main catalyst and an auxiliary catalyst;
the main catalyst comprises polyethylene glycol, inorganic acid, sultone, silicate, organosilane and oxidant;
the auxiliary catalyst comprises elemental iodine, alcohol and a molecular sieve;
the mass ratio of polyethylene glycol, inorganic acid, sultone, silicate, 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;
the mass ratio of the elemental iodine to the alcohol to the molecular sieve in the auxiliary catalyst is 1 (0.01-0.1) to 0.05-0.3.
2. The catalyst for preparing 2,2' -biphenol according to claim 1, wherein the inorganic acid comprises 1 or a combination of at least 2 of hydrochloric acid, hydrobromic acid or sulfuric acid.
3. The catalyst for preparing 2,2' -biphenol according to claim 1, wherein the sultone comprises 1 or a combination of at least 2 of 1, 3-propane sultone, 1, 4-butane sultone or 1, 5-pentane sultone.
4. The catalyst for preparing 2,2' -biphenol of claim 1 wherein the silicate comprises 1 or a combination of at least 2 of methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate, or butyl orthosilicate.
5. The catalyst for preparing 2,2' -biphenol according to claim 1, wherein the silane comprises 1 or a combination of at least 2 of trimethylsilane, tri-n-hexylmethylsilane, or (3-mercaptopropyl) trimethoxysilane.
6. The catalyst for preparing 2,2' -biphenol according to claim 1, wherein the oxidizing agent comprises 1 or a combination of at least 2 of Oxone, hydrogen peroxide or m-chloroperoxybenzoic acid.
7. The catalyst for preparing 2,2' -biphenol of claim 1 wherein the alcohol comprises 1 or a combination of at least 2 of isopropanol, n-propanol, n-butanol, or isobutanol.
8. The catalyst for preparing 2,2' -biphenol according to claim 1, wherein the molecular sieve comprises a ZSM-5 molecular sieve and/or a ZSM-11 molecular sieve.
9. The catalyst for preparing 2,2' -biphenol according to claim 1, wherein the mass concentration of the inorganic acid is 3 to 10%.
10. The catalyst for preparing 2,2' -biphenol according to claim 1, wherein the mass concentration of the oxidizing agent is 15 to 35%.
11. A method for preparing the catalyst for preparing 2,2' -biphenol according to claim 1, wherein the preparation method comprises main catalyst preparation and auxiliary catalyst preparation;
The preparation of the main catalyst comprises the steps of proportioning according to a formula, and 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 auxiliary catalyst comprises the steps of proportioning according to a formula, sequentially carrying out a second mixing reaction, alcohol separation and second drying to obtain the auxiliary catalyst.
12. The method of claim 11, wherein the temperature of the first mixing reaction is 20-40 ℃.
13. The method of claim 11, wherein the first mixing reaction is for a period of time ranging from 2 to 5 hours.
14. The method of claim 11, wherein the reflux time is 10 to 20 hours.
15. The method of claim 11, wherein the amount of methanol in the methanol reflux is 4 to 6 times the mass of polyethylene glycol.
16. The process of claim 11, wherein the methanol is refluxed for a period of 4 to 5 hours.
17. The method of claim 11, wherein the first drying is vacuum drying.
18. The method of claim 11, wherein the first drying temperature is 50-60 ℃.
19. The method of claim 11, wherein the temperature of the second mixing reaction is 20-45 ℃.
20. The method of claim 11, wherein the second mixing reaction is for a period of 1 to 3 hours.
21. The method of claim 11, wherein the alcohol separation is performed by distillation.
22. The method of claim 11, wherein the second drying is vacuum drying.
23. The method of claim 11, wherein the second drying temperature is 50-70 ℃.
24. The method of claim 11, wherein the method of preparation comprises a main catalyst preparation and a cocatalyst preparation;
The preparation of the main catalyst comprises the steps of proportioning according to a formula, and sequentially carrying out first mixing reaction, reflux, solid-liquid separation, methanol reflux, 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 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 is refluxed for 4-5 hours; the first drying mode is vacuum drying; the temperature of the first drying is 50-60 ℃;
The preparation of the auxiliary catalyst comprises the steps of proportioning according to a formula, sequentially carrying out a second mixing reaction, alcohol separation and second drying to obtain the auxiliary catalyst; 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 distillation; the second drying mode is vacuum drying; the second drying temperature is 50-70 ℃.
25. Use of a catalyst according to any one of claims 1 to 10 for the preparation of 2,2 '-biphenol, characterized in that the use comprises the preparation of 2,2' -biphenol with the catalyst, in particular comprising:
Mixing a2, 2 '-biphenol compound containing an alkyl substituent, a solvent and a catalyst, performing a first reaction, and performing solid-liquid separation and cooling separation to obtain a2, 2' -biphenol solid;
The mass ratio of the main catalyst of the catalyst and the 2,2' -biphenol compound of the alkyl substituent in the mixing is (0.1-0.5): 1;
The mass ratio of the cocatalyst of the catalyst to the 2,2' -biphenol compound of the alkyl substituent in the mixture is (0.01-0.05): 1.
26. The use according to claim 25 wherein the solvent comprises 1 or a combination of at least 2 of benzene, toluene, ortho-xylene, meta-xylene or para-xylene.
27. The use according to claim 25, wherein the solvent is added in an amount of 10 to 50 times the molar amount of the 2,2' -biphenol compound of the alkyl substituent.
28. The use according to claim 25, wherein the temperature of the first reaction is 25-55 ℃.
29. The use according to claim 25, wherein the time of the first reaction is 12-48 hours.
30. The use according to claim 25, wherein the separation by cooling is carried out by cooling the liquid phase obtained by the solid-liquid separation to-10 ℃ to 5 ℃.
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