CN113929594A - Synthetic method of p-cyanophenol - Google Patents
Synthetic method of p-cyanophenol Download PDFInfo
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- CN113929594A CN113929594A CN202111224014.8A CN202111224014A CN113929594A CN 113929594 A CN113929594 A CN 113929594A CN 202111224014 A CN202111224014 A CN 202111224014A CN 113929594 A CN113929594 A CN 113929594A
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- phosphoric acid
- cyanophenol
- long
- synthesizing
- solvent
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- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000010189 synthetic method Methods 0.000 title description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 178
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000011521 glass Substances 0.000 claims abstract description 52
- 239000007787 solid Substances 0.000 claims abstract description 49
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 claims abstract description 40
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 claims abstract description 40
- 239000000945 filler Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 22
- 238000004381 surface treatment Methods 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 42
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 39
- 238000002791 soaking Methods 0.000 claims description 37
- 229920001187 thermosetting polymer Polymers 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 36
- 239000011248 coating agent Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 32
- 238000012644 addition polymerization Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- 239000005543 nano-size silicon particle Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 230000032050 esterification Effects 0.000 claims description 22
- 238000005886 esterification reaction Methods 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 239000004005 microsphere Substances 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 20
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 20
- 239000005011 phenolic resin Substances 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 229920001568 phenolic resin Polymers 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- 230000005587 bubbling Effects 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 13
- -1 sodium alkoxide Chemical class 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 6
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical group O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 52
- 229960002216 methylparaben Drugs 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XUIMIQQOPSSXEZ-RNFDNDRNSA-N silicon-32 atom Chemical compound [32Si] XUIMIQQOPSSXEZ-RNFDNDRNSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 description 1
- 239000005489 Bromoxynil Substances 0.000 description 1
- 239000005747 Chlorothalonil Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- SCKHCCSZFPSHGR-UHFFFAOYSA-N cyanophos Chemical compound COP(=S)(OC)OC1=CC=C(C#N)C=C1 SCKHCCSZFPSHGR-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for synthesizing p-cyanophenol, which comprises the following steps: adding a solid phosphoric acid catalyst into a reaction bed layer of a fixed bed reactor, dissolving methyl p-hydroxybenzoate in a solvent, feeding the methyl p-hydroxybenzoate and water into the fixed bed reactor, introducing ammonia gas into the reactor, controlling the temperature of the reactor to be 300-500 ℃ and the pressure to be more than 0.06MPa, continuously discharging, and rectifying and purifying to obtain the finished product of the p-cyanophenol. The synthesis method of the p-cyanophenol provided by the invention comprehensively improves the reaction yield and the conversion rate through the preparation of the solid phosphoric acid catalyst, the surface treatment of the glass ball filler and the improvement of the phosphoric acid solution.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of p-cyanophenol.
Background
P-cyanophenol of the formula C7H5NO, molecular weight 119.12, CAS registry number 767-00-0, white needles in bench scaleThe crystal is a light yellow crystal or crystalline powder in industrial production, the melting point of the crystal is 110-113 ℃, the boiling point is 146 ℃/2mmHg, and the crystal is easy to dissolve in hot water and slightly soluble in ice water; dissolving in organic solvent such as methanol, diethyl ether, acetone, chloroform, etc.
The paracyanophenol is an extremely important fine organic chemical raw material and intermediate, and is widely used for synthesizing various medicines, spices, pesticides, liquid crystal materials, buffering agents and the like; particularly, as an intermediate of agricultural chemicals, cyanophenyl agricultural chemicals such as "niclosonitrile", "cyanophos", "bromoxynil", "hydroxyfenapyr" and "chlorothalonil" can be produced.
Chinese patent CN105418455A discloses a preparation method of p-hydroxybenzonitrile, which comprises the following steps: adding a filler and a catalyst into a fixed bed reactor, dissolving a raw material of methyl p-hydroxybenzoate in an organic solvent pyridine, and adding the methyl p-hydroxybenzoate and water into the fixed bed reactor together, wherein the reaction temperature is 300-400 ℃, and the reaction pressure is 0-0.1 KPa. The synthesis method does not fully exert the promoting effect of the catalyst and the filler on the reaction yield and the conversion rate, and causes the final reaction result to be unsatisfactory.
In summary, how to design a synthetic method of p-cyanophenol, which can effectively improve the reaction yield and the conversion rate, is a problem which needs to be solved urgently at present.
Disclosure of Invention
The present invention is directed to solving the above problems, and an object of the present invention is to provide a method for synthesizing p-cyanophenol, which comprehensively improves reaction yield and conversion rate by preparing a solid phosphoric acid catalyst, treating the surface of a glass bead filler, and improving a phosphoric acid solution.
The invention realizes the purpose through the following technical scheme, and a synthetic method of p-cyanophenol comprises the following specific steps:
adding a solid phosphoric acid catalyst into a reaction bed layer of a fixed bed reactor, dissolving methyl p-hydroxybenzoate in a solvent, feeding the methyl p-hydroxybenzoate and water into the fixed bed reactor, introducing ammonia gas into the reactor, controlling the temperature of the reactor to be 300-500 ℃ and the pressure to be more than 0.06MPa, continuously discharging, and rectifying and purifying to obtain the finished product of the p-cyanophenol.
The preparation method of the solid phosphoric acid catalyst comprises the following steps:
(1) placing maleic anhydride, 1/2 long-chain alcohol and silicon dioxide microspheres in a reaction container together, uniformly mixing, heating the container to 100 ℃ and 110 ℃, dropwise adding the remaining mixed solution of 1/2 long-chain alcohol and a catalyst under the stirring condition, and after dropwise adding, keeping the temperature and stirring for reacting for 6-8 hours to obtain an esterification product;
(2) dissolving sodium vinylsulfonate in deionized water, mixing the deionized water with an initiator uniformly, dropwise adding the mixture into the esterification product obtained in the step (1) at the temperature of 70-75 ℃ under the stirring condition, and carrying out heat preservation and stirring reaction for 4-6 hours after dropwise adding to obtain an addition polymerization product;
(3) filtering and drying the addition polymerization product, soaking in a phosphoric acid solution at normal temperature and normal pressure for 1-2h, filtering to remove redundant liquid, drying at the temperature of 100 ℃ and 110 ℃ for 30-60min, and then transferring into a resistance furnace to roast for 3-5h to obtain the solid phosphoric acid catalyst.
Further, the mass ratio of the methyl p-hydroxybenzoate to the solid phosphoric acid catalyst is 1: (0.1-0.3), wherein the mass ratio of methyl p-hydroxybenzoate, solvent and water is 1: (4-6): (0.4-0.8), the flow rate of ammonia gas is 3-4L/min, and the solvent is pyridine.
Further, the mass ratio of maleic anhydride, long-chain alcohol, sodium vinylsulfonate and silica microspheres is 1: (2.4-3): (1-1.4): (10-30).
Further, the catalyst in the step (1) is concentrated sulfuric acid, and the adding amount of the concentrated sulfuric acid is 3-5% of the total amount of maleic anhydride and long-chain alcohol; the initiator in the step (2) is benzophenone or benzoyl peroxide, and the addition amount of the initiator is 0.12-0.2% of the sodium vinyl sulfonate.
Further, the baking conditions of the resistance furnace in the step (3) are as follows: roasting at 300 ℃ for 30-50min at 200-.
Furthermore, a glass ball filler is also filled in the fixed bed reactor, the height of the filler is 30-40cm, and the surface treatment method of the glass ball comprises the following steps:
s1, soaking the barite powder in 3-6 times of sodium bicarbonate solution for 1-3h, and then evaporating under reduced pressure to remove water to obtain pretreated barite powder;
s2, uniformly mixing the thermosetting resin, the curing agent, the silane coupling agent and the barite powder pretreated in the step S1 to prepare a coating, spraying the coating to the surface of the cleaned and dried glass ball, wherein the spraying thickness is 50-100 mu m, and heating and curing;
and S3, repeatedly soaking the glass balls with the solidified surfaces in 40-60% hydrofluoric acid solution for 2-4 times, each time for 10-20min, washing with clear water after soaking each time, and finally drying to obtain the glass balls with the treated surfaces.
Further, the mass concentration of the sodium bicarbonate solution in the step S1 is 5-8%; the coating in the step S2 comprises 5-10 parts of pretreated barite powder, 20-30 parts of thermosetting resin, 2-4 parts of curing agent and 0.3-0.8 part of silane coupling agent, wherein the curing agent is sulfonic acid, and the heating curing temperature is 150-170 ℃.
Further, the thermosetting resin is a modified phenolic resin, and the preparation method of the modified phenolic resin comprises the following steps:
mixing thermosetting phenolic resin with a solvent, dropwise adding bromine under the stirring condition, heating to 40-50 ℃, stirring for reacting for 4-6h, evaporating water of the obtained product, stirring for reacting with long-chain sodium alkoxide at room temperature for 2-4h, washing and drying the obtained product, dropwise adding a mixed solution of long-chain carboxylic acid and a catalyst, reacting for 5-6h at 110-120 ℃, and removing the solvent to obtain the modified phenolic resin.
Further, the solvent is diethylene glycol monobutyl ether or ethylene glycol monobutyl ether, the catalyst is concentrated sulfuric acid, the adding amount of the catalyst is 2-3%, and the molar ratio of the thermosetting phenolic resin to bromine to long-chain sodium alkoxide to long-chain carboxylic acid is 1: (1-1.2): (1-1.5): (1-1.3).
Further, in the step (3) of preparing the solid phosphoric acid catalyst, the phosphoric acid solution comprises 60-70% of phosphoric acid, 8-12% of pretreated nano silicon powder and 18-32% of water;
the pretreatment method of the nano silicon powder comprises the following steps: soaking the nano silicon powder in silicone oil for 1-2h, taking out and drying;
bubbling is carried out in the dipping process, and the bubbling gas quantity is 0.3-0.6L/min.
The invention has the beneficial effects that:
(1) because the polarity of the reaction raw material, namely the methylparaben, is small, the methylparaben is difficult to adsorb on the surface of a solid phosphoric acid catalyst to perform catalytic reaction during the reaction, the lipophilicity of the silicon dioxide microsphere is poor, and the dispersibility of the silicon dioxide microsphere is poor, the silicon dioxide microsphere is subjected to surface modification, so that a macromolecular compound with one end containing sodium sulfonate and the other end containing long-chain ester group is compounded on the surface of the silicon dioxide microsphere, the phosphoric acid can be adsorbed on one end of the sodium sulfonate when the silicon dioxide microsphere carries the phosphoric acid, and the methylparaben in the reaction system can be adsorbed on one end of the long-chain ester group, the combination of the methylparaben, the silicon dioxide microsphere and the phosphoric acid in the reaction system is enhanced, the catalytic reaction is promoted, and the reaction yield is improved;
(2) when the surface modification is carried out on the silicon dioxide microspheres, the silicon dioxide is directly added into the reaction raw materials and sequentially participates in esterification and addition polymerization, so that the silicon dioxide microspheres can be tightly and uniformly combined with surface modified polymers, and compared with the method of synthesizing the polymers and then compounding the polymers on the surfaces of the silicon dioxide microspheres in a mechanical mode, the method for modifying the surfaces of the silicon dioxide microspheres is not easy to cause the blockage of the pores of the microspheres, thereby influencing the subsequent loading of phosphoric acid;
(3) because the surface of the glass ball filler is smooth and has poor compatibility with the reaction raw materials of the invention, and is not beneficial to mass transfer, the invention carries out surface treatment on the glass ball, not only forms a porous coating, but also improves the compatibility of the filler and the reaction raw materials through the treatment of the coating;
(4) before the acid etching is carried out on the glass ball, firstly, a thin coating is sprayed on the surface of the glass ball, then, the coating is heated and cured, and the coating contains sodium bicarbonate, so that a porous membrane is formed on the surface of the glass ball after the coating is cured, and finally, hydrofluoric acid is used for soaking, so that the hydrofluoric acid can carry out the acid etching on the glass ball through a plurality of pores without causing the acid etching on the glass ball outside the pores, the size of the pores is increased, and the reaction raw materials can fully react on the surface of the glass ball;
(5) in order to prevent hydrofluoric acid from corroding the coating around the pores, the barite powder is added into the coating after being soaked in the sodium bicarbonate solution, so that a large amount of barite powder is distributed around the pores after the coating is solidified and formed into pores, and the barite powder has strong hydrofluoric acid resistance, so that the hydrofluoric acid can be effectively prevented from corroding the coating around the pores;
(6) in order to enhance the toughness of the surface coating of the glass balls and slow down the impact between the glass balls and the solid phosphoric acid catalyst, the phenolic resin is modified, and long chains are grafted on hydroxymethyl groups of the phenolic resin through halogenation and alkoxy substitution reactions in sequence, so that the toughness of the resin is comprehensively improved;
(7) because the silica microspheres and the glass sphere fillers are subjected to surface treatment, organic matters generated in the treatment process and added additives are easy to increase side reactions, and the reaction conversion rate and yield of the invention are influenced;
(8) in order to avoid the adsorption of the nano silicon powder on the phosphoric acid and influence the load of the phosphoric acid on the silicon dioxide microspheres, the nano silicon powder is subjected to silicone oil soaking pretreatment, so that the pretreated nano silicon powder can better disperse the phosphoric acid without adsorbing the phosphoric acid;
(9) in order to enhance the dispersion of the nano silicon powder when dipping phosphoric acid, the invention also carries out bubbling, thereby improving the dispersion of the phosphoric acid solution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a method for synthesizing p-cyanophenol, which comprises the following specific steps:
adding a solid phosphoric acid catalyst into a reaction bed layer of a fixed bed reactor, dissolving methyl p-hydroxybenzoate in a solvent, feeding the methyl p-hydroxybenzoate and water into the fixed bed reactor, introducing ammonia gas into the reactor, controlling the temperature of the reactor to be 300 ℃ and the pressure to be more than 0.06MPa, continuously discharging, and rectifying and purifying to obtain the finished product of the p-cyanophenol.
Wherein the mass ratio of the methyl p-hydroxybenzoate to the solid phosphoric acid catalyst is 1: 0.1, wherein the mass ratio of methyl p-hydroxybenzoate, solvent and water is 1: 4: 0.4, the flow of ammonia gas is 3L/min, and the solvent is pyridine.
The preparation method of the solid phosphoric acid catalyst comprises the following steps:
(1) placing maleic anhydride, 1/2 long-chain alcohol and silicon dioxide microspheres into a reaction container, uniformly mixing, heating the container to 100 ℃, dropwise adding the mixed solution of the residual 1/2 long-chain alcohol and concentrated sulfuric acid under the stirring condition, and keeping the temperature and stirring for reacting for 8 hours after dropwise adding to obtain an esterification product;
(2) dissolving sodium vinylsulfonate in deionized water, uniformly mixing with an initiator, dropwise adding the mixture into the esterification product obtained in the step (1) at 70 ℃ under the stirring condition, and carrying out heat preservation stirring reaction for 6 hours after dropwise adding to obtain an addition polymerization product;
(3) and filtering and drying the addition polymerization product, soaking the addition polymerization product in a phosphoric acid solution at normal temperature and normal pressure for 1 hour, filtering out redundant liquid, drying the addition polymerization product at 100 ℃ for 60 minutes, and transferring the addition polymerization product into a resistance furnace to roast the addition polymerization product for 5 hours to obtain the solid phosphoric acid catalyst.
The mass ratio of maleic anhydride, long-chain alcohol, sodium vinylsulfonate and silica microspheres is 1: 2.4: 1: 10.
in the step (1), the adding amount of the concentrated sulfuric acid is 3 percent of the total amount of the maleic anhydride and the long-chain alcohol; the initiator in the step (2) is benzophenone, and the addition amount of the benzophenone is 0.12 percent of the sodium vinyl sulfonate.
The roasting conditions of the resistance furnace in the step (3) are as follows: roasting at 200 deg.C for 50min, roasting at 320 deg.C for 90min, roasting at 480 deg.C for 80min, roasting at 300 deg.C for 30min, and roasting at 560 deg.C for 50 min.
Example 2
On the basis of the embodiment 1, the embodiment also provides a synthetic method of p-cyanophenol, a fixed bed reactor is also filled with glass ball filler, the height of the filler is 30cm, and the surface treatment method of the glass balls comprises the following steps:
s1, soaking the barite powder in 3 times of sodium bicarbonate solution (the mass concentration is 8%) for 1 hour, and then evaporating under reduced pressure to remove water to obtain pretreated barite powder;
s2, uniformly mixing the thermosetting resin, the sulfonic acid curing agent, the silane coupling agent and the barite powder obtained by the pretreatment in the step S1 to prepare a coating, spraying the coating onto the surface of the cleaned and dried glass ball, wherein the spraying thickness is 50 microns, and heating to 150 ℃ for curing;
and S3, repeatedly soaking the glass ball with the solidified surface in 40% hydrofluoric acid solution for 4 times, each time for 20min, washing with clear water after each soaking, and finally drying to obtain the glass ball with the treated surface.
The coating in step S2 contains 5 parts of pretreated barite powder, 20 parts of thermosetting resin, 2 parts of curing agent, and 0.3 part of silane coupling agent.
The rest is the same as in example 1.
Example 3
On the basis of embodiment 2, this embodiment also discloses a method for synthesizing p-cyanophenol, where the thermosetting resin is a modified phenolic resin, and the method for preparing the modified phenolic resin is as follows:
mixing thermosetting phenolic resin with a solvent, then dropwise adding bromine under the stirring condition, heating to 40 ℃, stirring and reacting for 6 hours, evaporating water of the obtained product, stirring and reacting with long-chain sodium alkoxide at room temperature for 2 hours, washing and drying the obtained product, then dropwise adding a mixed solution of long-chain carboxylic acid and concentrated sulfuric acid, reacting for 6 hours at 110 ℃, and then removing the solvent to obtain the modified phenolic resin.
The solvent is diethylene glycol monobutyl ether, the adding amount of concentrated sulfuric acid is 2%, and the molar ratio of the thermosetting phenolic resin, bromine, long-chain sodium alkoxide and long-chain carboxylic acid is 1: 1: 1: 1.
the rest is the same as in example 2.
Example 4
On the basis of example 1, this example also provides a method for synthesizing p-cyanophenol, in step (3) of the preparation method of the solid phosphoric acid catalyst, the phosphoric acid solution includes 60% phosphoric acid, 8% pretreated nano silicon powder, and 32% water, and bubbling is performed during the dipping process, and the amount of bubbling gas is 0.3L/min.
The pretreatment method of the nano silicon powder comprises the following steps: and soaking the nano silicon powder in the silicone oil for 1 hour, taking out and drying.
The rest is the same as in example 1.
Example 5
The embodiment provides a method for synthesizing p-cyanophenol, which comprises the following specific steps:
adding a solid phosphoric acid catalyst into a reaction bed layer of a fixed bed reactor, dissolving methyl p-hydroxybenzoate in a solvent, feeding the methyl p-hydroxybenzoate and water into the fixed bed reactor, introducing ammonia gas into the reactor, controlling the temperature of the reactor to be 300 ℃ and the pressure to be more than 0.06MPa, continuously discharging, and rectifying and purifying to obtain the finished product of the p-cyanophenol.
Wherein the mass ratio of the methyl p-hydroxybenzoate to the solid phosphoric acid catalyst is 1: 0.1, wherein the mass ratio of methyl p-hydroxybenzoate, solvent and water is 1: 4: 0.4, the flow of ammonia gas is 3L/min, and the solvent is pyridine.
The preparation method of the solid phosphoric acid catalyst comprises the following steps:
(1) placing maleic anhydride, 1/2 long-chain alcohol and silicon dioxide microspheres into a reaction container, uniformly mixing, heating the container to 100 ℃, dropwise adding the mixed solution of the residual 1/2 long-chain alcohol and concentrated sulfuric acid under the stirring condition, and keeping the temperature and stirring for reacting for 8 hours after dropwise adding to obtain an esterification product;
(2) dissolving sodium vinylsulfonate in deionized water, uniformly mixing with an initiator, dropwise adding the mixture into the esterification product obtained in the step (1) at 70 ℃ under the stirring condition, and carrying out heat preservation stirring reaction for 6 hours after dropwise adding to obtain an addition polymerization product;
(3) and filtering and drying the addition polymerization product, soaking the addition polymerization product in a phosphoric acid solution at normal temperature and normal pressure for 1 hour, filtering out redundant liquid, drying the addition polymerization product at 100 ℃ for 60 minutes, and transferring the addition polymerization product into a resistance furnace to roast the addition polymerization product for 5 hours to obtain the solid phosphoric acid catalyst.
The mass ratio of maleic anhydride, long-chain alcohol, sodium vinylsulfonate and silica microspheres is 1: 2.4: 1: 10.
in the step (1), the adding amount of the concentrated sulfuric acid is 3 percent of the total amount of the maleic anhydride and the long-chain alcohol; the initiator in the step (2) is benzophenone, and the addition amount of the benzophenone is 0.12 percent of the sodium vinyl sulfonate.
The roasting conditions of the resistance furnace in the step (3) are as follows: roasting at 200 deg.C for 50min, roasting at 320 deg.C for 90min, roasting at 480 deg.C for 80min, roasting at 300 deg.C for 30min, and roasting at 560 deg.C for 50 min.
In the step (3), the phosphoric acid solution comprises 60% of phosphoric acid, 8% of pretreated nano silicon powder and 32% of water, and bubbling is carried out in the dipping process, wherein the bubbling gas amount is 0.3L/min.
The pretreatment method of the nano silicon powder comprises the following steps: and soaking the nano silicon powder in the silicone oil for 1 hour, taking out and drying.
The fixed bed reactor is also filled with glass ball filler, the height of the filler is 30cm, and the surface treatment method of the glass balls comprises the following steps:
s1, soaking the barite powder in 3 times of sodium bicarbonate solution (the mass concentration is 8%) for 1 hour, and then evaporating under reduced pressure to remove water to obtain pretreated barite powder;
s2, uniformly mixing the thermosetting resin, the sulfonic acid curing agent, the silane coupling agent and the barite powder obtained by the pretreatment in the step S1 to prepare a coating, spraying the coating onto the surface of the cleaned and dried glass ball, wherein the spraying thickness is 50 microns, and heating to 150 ℃ for curing;
and S3, repeatedly soaking the glass ball with the solidified surface in 40% hydrofluoric acid solution for 4 times, each time for 20min, washing with clear water after each soaking, and finally drying to obtain the glass ball with the treated surface.
The coating in step S2 contains 5 parts of pretreated barite powder, 20 parts of thermosetting resin, 2 parts of curing agent, and 0.3 part of silane coupling agent.
The thermosetting resin is modified phenolic resin, and the preparation method of the modified phenolic resin comprises the following steps:
mixing thermosetting phenolic resin with a solvent, then dropwise adding bromine under the stirring condition, heating to 40 ℃, stirring and reacting for 6 hours, evaporating water of the obtained product, stirring and reacting with long-chain sodium alkoxide at room temperature for 2 hours, washing and drying the obtained product, then dropwise adding a mixed solution of long-chain carboxylic acid and concentrated sulfuric acid, reacting for 6 hours at 110 ℃, and then removing the solvent to obtain the modified phenolic resin.
The solvent is diethylene glycol monobutyl ether, the adding amount of concentrated sulfuric acid is 2%, and the molar ratio of the thermosetting phenolic resin, bromine, long-chain sodium alkoxide and long-chain carboxylic acid is 1: 1: 1: 1.
example 6
The embodiment provides a method for synthesizing p-cyanophenol, which comprises the following specific steps:
adding a solid phosphoric acid catalyst into a reaction bed layer of a fixed bed reactor, dissolving methyl p-hydroxybenzoate in a solvent, feeding the methyl p-hydroxybenzoate and water into the fixed bed reactor, introducing ammonia gas into the reactor, controlling the temperature of the reactor to be 400 ℃ and the pressure to be more than 0.06MPa, continuously discharging, and rectifying and purifying to obtain the finished product of the p-cyanophenol.
Wherein the mass ratio of the methyl p-hydroxybenzoate to the solid phosphoric acid catalyst is 1: 0.12, wherein the mass ratio of the methyl p-hydroxybenzoate, the solvent and the water is 1: 5: 0.6, the flow of ammonia gas is 3.5L/min, and the solvent is pyridine.
The preparation method of the solid phosphoric acid catalyst comprises the following steps:
(1) placing maleic anhydride, 1/2 long-chain alcohol and silicon dioxide microspheres into a reaction container, uniformly mixing, heating the container to 105 ℃, dropwise adding the mixed solution of the residual 1/2 long-chain alcohol and concentrated sulfuric acid under the stirring condition, and keeping the temperature and stirring for reaction for 7 hours after dropwise adding to obtain an esterification product;
(2) dissolving sodium vinylsulfonate in deionized water, uniformly mixing the deionized water with an initiator, dropwise adding the mixture into the esterification product obtained in the step (1) at 73 ℃ under the stirring condition, and carrying out heat preservation stirring reaction for 5 hours after dropwise adding to obtain an addition polymerization product;
(3) and filtering and drying the addition polymerization product, soaking the addition polymerization product in a phosphoric acid solution at normal temperature and normal pressure for 1.5h, filtering out redundant liquid, drying the addition polymerization product at 105 ℃ for 45min, and transferring the addition polymerization product into a resistance furnace to roast the addition polymerization product for 4h to obtain the solid phosphoric acid catalyst.
The mass ratio of maleic anhydride, long-chain alcohol, sodium vinylsulfonate and silica microspheres is 1: 2.7: 1.2: 20.
in the step (1), the adding amount of the concentrated sulfuric acid is 4 percent of the total amount of the maleic anhydride and the long-chain alcohol; the initiator in the step (2) is benzoyl peroxide, and the addition amount of the benzoyl peroxide is 0.16 percent of the sodium vinyl sulfonate.
The roasting conditions of the resistance furnace in the step (3) are as follows: roasting at 250 deg.C for 40min, roasting at 400 deg.C for 75min, roasting at 510 deg.C for 60min, roasting at 350 deg.C for 25min, and roasting at 580 deg.C for 40 min.
In the step (3), the phosphoric acid solution comprises 65% of phosphoric acid, 10% of pretreated nano silicon powder and 25% of water; bubbling was carried out during the impregnation with a bubbling gas amount of 0.45L/min.
The pretreatment method of the nano silicon powder comprises the following steps: and soaking the nano silicon powder in the silicone oil for 1.5h, taking out and drying.
The fixed bed reactor is also filled with glass ball filler, the height of the filler is 35cm, and the surface treatment method of the glass balls comprises the following steps:
s1, soaking the barite powder in 4.5 times of sodium bicarbonate solution (mass concentration is 6.5%) for 2 hours, and then evaporating under reduced pressure to remove water to obtain pretreated barite powder;
s2, uniformly mixing the thermosetting resin, the sulfonic acid curing agent, the silane coupling agent and the barite powder obtained by the pretreatment in the step S1 to prepare a coating, spraying the coating onto the surface of the cleaned and dried glass ball, wherein the spraying thickness is 75 microns, and heating to 160 ℃ for curing;
and S3, repeatedly soaking the glass ball with the solidified surface in 50% hydrofluoric acid solution for 3 times, each time for 15min, washing with clean water after soaking each time, and finally drying to obtain the glass ball with the treated surface.
The coating in step S2 contains 7.5 parts of pretreated barite powder, 25 parts of thermosetting resin, 3 parts of curing agent, and 0.55 part of silane coupling agent.
The thermosetting resin is modified phenolic resin, and the preparation method of the modified phenolic resin comprises the following steps:
mixing thermosetting phenolic resin with a solvent, then dropwise adding bromine under the stirring condition, heating to 45 ℃, stirring for reaction for 5 hours, evaporating water from the obtained product, stirring for reaction for 3 hours with long-chain sodium alkoxide at room temperature, washing and drying the obtained product, then dropwise adding a mixed solution of long-chain carboxylic acid and concentrated sulfuric acid, reacting for 5.5 hours at 115 ℃, and then removing the solvent to obtain the modified phenolic resin.
The solvent is ethylene glycol monobutyl ether, the adding amount of concentrated sulfuric acid is 2.5%, and the molar ratio of the thermosetting phenolic resin, bromine, long-chain sodium alkoxide and long-chain carboxylic acid is 1: 1.1: 1.2: 1.1.
example 7
The embodiment provides a method for synthesizing p-cyanophenol, which comprises the following specific steps:
adding a solid phosphoric acid catalyst into a reaction bed layer of a fixed bed reactor, dissolving methyl p-hydroxybenzoate in a solvent, feeding the methyl p-hydroxybenzoate and water into the fixed bed reactor, introducing ammonia gas into the reactor, controlling the temperature of the reactor to be 500 ℃ and the pressure to be more than 0.06MPa, continuously discharging, and rectifying and purifying to obtain the finished product of the p-cyanophenol.
Wherein the mass ratio of the methyl p-hydroxybenzoate to the solid phosphoric acid catalyst is 1: 0.3, the mass ratio of the methyl p-hydroxybenzoate, the solvent and the water is 1: 6: 0.8, the flow of ammonia gas is 4L/min, and the solvent is pyridine.
The preparation method of the solid phosphoric acid catalyst comprises the following steps:
(1) placing maleic anhydride, 1/2 long-chain alcohol and silicon dioxide microspheres in a reaction container together, uniformly mixing, heating the container to 110 ℃, dropwise adding the mixed solution of the residual 1/2 long-chain alcohol and concentrated sulfuric acid under the stirring condition, and keeping the temperature and stirring for reacting for 6 hours after dropwise adding to obtain an esterification product;
(2) dissolving sodium vinylsulfonate in deionized water, mixing the deionized water with an initiator uniformly, dropwise adding the mixture into the esterification product obtained in the step (1) at the temperature of 75 ℃ under the stirring condition, and carrying out heat preservation stirring reaction for 4 hours after dropwise adding to obtain an addition polymerization product;
(3) and filtering and drying the addition polymerization product, soaking the addition polymerization product in a phosphoric acid solution at normal temperature and normal pressure for 2 hours, filtering out redundant liquid, drying the addition polymerization product at 110 ℃ for 30 minutes, and transferring the addition polymerization product into a resistance furnace to roast the addition polymerization product for 3 hours to obtain the solid phosphoric acid catalyst.
The mass ratio of maleic anhydride, long-chain alcohol, sodium vinylsulfonate and silica microspheres is 1: 3: 1.4: 30.
in the step (1), the adding amount of the concentrated sulfuric acid is 5 percent of the total amount of the maleic anhydride and the long-chain alcohol; the initiator in the step (2) is benzophenone, and the addition amount of the benzophenone is 0.2% of the sodium vinyl sulfonate.
The roasting conditions of the resistance furnace in the step (3) are as follows: roasting at 300 deg.C for 30min, roasting at 450 deg.C for 60min, roasting at 450 deg.C for 40min, roasting at 400 deg.C for 20min, and roasting at 600 deg.C for 30 min.
In the step (3), the phosphoric acid solution comprises 70% of phosphoric acid, 12% of pretreated nano silicon powder and 18% of water; bubbling was carried out during the impregnation with a bubbling gas amount of 0.6L/min.
The pretreatment method of the nano silicon powder comprises the following steps: soaking the nano silicon powder in silicone oil for 2 hours, taking out and drying;
the fixed bed reactor is also filled with glass ball filler, the height of the filler is 40cm, and the surface treatment method of the glass balls comprises the following steps:
s1, soaking the barite powder in 6 times of sodium bicarbonate solution (mass concentration is 5%) for 3 hours, and then evaporating under reduced pressure to remove water to obtain pretreated barite powder;
s2, uniformly mixing the thermosetting resin, the sulfonic acid curing agent, the silane coupling agent and the barite powder obtained by the pretreatment in the step S1 to prepare a coating, spraying the coating onto the surface of the cleaned and dried glass ball, wherein the spraying thickness is 100 mu m, and heating to 170 ℃ for curing;
and S3, repeatedly soaking the glass ball with the solidified surface in 60% hydrofluoric acid solution for 2 times, 10min each time, washing with clear water after soaking each time, and finally drying to obtain the glass ball with the treated surface.
The coating in step S2 contains 10 parts of pretreated barite powder, 30 parts of thermosetting resin, 4 parts of curing agent, and 0.8 part of silane coupling agent.
The thermosetting resin is modified phenolic resin, and the preparation method of the modified phenolic resin comprises the following steps:
mixing thermosetting phenolic resin with a solvent, then dropwise adding bromine under the stirring condition, heating to 50 ℃, stirring for reacting for 4 hours, evaporating water of the obtained product, stirring for reacting for 4 hours with long-chain sodium alkoxide at room temperature, washing and drying the obtained product, then dropwise adding a mixed solution of long-chain carboxylic acid and concentrated sulfuric acid, reacting for 5 hours at 120 ℃, and then removing the solvent to obtain the modified phenolic resin.
The solvent is diethylene glycol monobutyl ether, the adding amount of concentrated sulfuric acid is 3%, and the molar ratio of the thermosetting phenolic resin, bromine, long-chain sodium alkoxide and long-chain carboxylic acid is 1: 1.2: 1.5: 1.3.
comparative example 1
The comparative example provides a method for synthesizing p-cyanophenol, which comprises the following specific steps:
adding a solid phosphoric acid catalyst into a reaction bed layer of a fixed bed reactor, dissolving methyl p-hydroxybenzoate in a solvent, feeding the methyl p-hydroxybenzoate and water into the fixed bed reactor, introducing ammonia gas into the reactor, controlling the temperature of the reactor to be 300 ℃ and the pressure to be more than 0.06MPa, continuously discharging, and rectifying and purifying to obtain the finished product of the p-cyanophenol.
Wherein the mass ratio of the methyl p-hydroxybenzoate to the solid phosphoric acid catalyst is 1: 0.1, wherein the mass ratio of methyl p-hydroxybenzoate, solvent and water is 1: 4: 0.4, the flow of ammonia gas is 3L/min, and the solvent is pyridine.
Comparative example 2
This comparative example differs from example 5 in that the preparation method of the solid phosphoric acid catalyst comprises the following steps:
(1) placing maleic anhydride and 1/2 long-chain alcohol into a reaction container, uniformly mixing, heating the container to 100 ℃, dropwise adding the mixed solution of the residual 1/2 long-chain alcohol and concentrated sulfuric acid under the stirring condition, and keeping the temperature and stirring for reacting for 8 hours after dropwise adding to obtain an esterification product;
(2) dissolving sodium vinylsulfonate in deionized water, uniformly mixing with an initiator, dropwise adding the mixture into the esterification product obtained in the step (1) at 70 ℃ under the stirring condition, and carrying out heat preservation stirring reaction for 6 hours after dropwise adding to obtain an addition polymerization product;
(3) soaking the silicon dioxide microspheres in a polyaddition product, filtering, drying the silicon dioxide microspheres, soaking in a phosphoric acid solution at normal temperature and normal pressure for 1h, filtering to remove redundant liquid, drying at 100 ℃ for 60min, and transferring into a resistance furnace to be roasted for 5h to obtain the solid phosphoric acid catalyst.
Comparative example 3
This comparative example differs from example 5 in that the preparation method of the solid phosphoric acid catalyst comprises the following steps:
(1) dissolving sodium vinylsulfonate in deionized water, mixing the deionized water with an initiator uniformly, dropwise adding the mixture into a mixture of maleic acid and silicon dioxide microspheres at 70 ℃ under the stirring condition, and keeping the temperature and stirring for reacting for 6 hours after dropwise adding to obtain an addition polymerization product;
(2) putting the polyaddition product obtained in the step (1) and 1/2 long-chain alcohol into a reaction container, uniformly mixing, heating the container to 100 ℃, dropwise adding the mixed liquid of the residual 1/2 long-chain alcohol and concentrated sulfuric acid under the stirring condition, and after dropwise adding, keeping the temperature and stirring for reaction for 8 hours to obtain an esterification product;
(3) and filtering and drying the esterification product, soaking the esterification product in a phosphoric acid solution at normal temperature and normal pressure for 1h, filtering out redundant liquid, drying the esterification product at 100 ℃ for 60min, and transferring the esterification product into a resistance furnace to roast the esterification product for 5h to obtain the solid phosphoric acid catalyst.
Comparative example 4
This comparative example differs from example 5 in that the solid phosphoric acid catalyst was prepared by the method of step (1) of: putting maleic anhydride, concentrated sulfuric acid and silica microspheres into a reaction container, uniformly mixing, then heating the container to 100 ℃, dropwise adding long-chain alcohol under stirring, and keeping the temperature and stirring for reacting for 8 hours after dropwise adding to obtain an esterification product.
Comparative example 5
The comparative example differs from example 5 in that the conditions for the electric resistance furnace calcination in step (3) of the preparation method of the solid phosphoric acid catalyst were: roasting at 320 deg.C for 90min, roasting at 480 deg.C for 80min, roasting at 300 deg.C for 30min, and roasting at 560 deg.C for 50 min.
Comparative example 6
The comparative example differs from example 5 in that the conditions for the electric resistance furnace calcination in step (3) of the preparation method of the solid phosphoric acid catalyst were: roasting at 200 deg.C for 50min, roasting at 480 deg.C for 80min, roasting at 300 deg.C for 30min, and roasting at 560 deg.C for 50 min.
Comparative example 7
The comparative example differs from example 5 in that the conditions for the electric resistance furnace calcination in step (3) of the preparation method of the solid phosphoric acid catalyst were: roasting at 200 deg.C for 50min, roasting at 320 deg.C for 90min, roasting at 300 deg.C for 30min, and roasting at 560 deg.C for 50 min.
Comparative example 8
The comparative example differs from example 5 in that the conditions for the electric resistance furnace calcination in step (3) of the preparation method of the solid phosphoric acid catalyst were: roasting at 200 deg.C for 50min, roasting at 320 deg.C for 90min, roasting at 480 deg.C for 80min, and roasting at 560 deg.C for 50 min.
Comparative example 9
The comparative example is different from example 6 in that the surface treatment method of the glass spheres is as follows: and (3) repeatedly soaking the glass ball in 50% hydrofluoric acid solution for 3 times, each time for 15min, washing with clear water after soaking each time, and finally drying to obtain the surface-treated glass ball.
Comparative example 10
This comparative example is different from example 6 in that the surface treatment method of glass spheres does not include step S1, and step S2 is: the thermosetting resin, the sulfonic acid curing agent, the silane coupling agent and the sodium bicarbonate powder are uniformly mixed to prepare a coating, then the coating is sprayed on the surface of the cleaned and dried glass ball, the spraying thickness is 75 mu m, and the coating is heated to 160 ℃ for curing.
Comparative example 11
The comparative example is different from example 6 in that the mass ratio of the sodium bicarbonate solution to the barite powder in step S1 of the glass bead surface treatment method is 2: 1.
Comparative example 12
The comparative example is different from example 6 in that the mass ratio of the sodium bicarbonate solution to the barite powder in step S1 of the glass bead surface treatment method is 7: 1.
Comparative example 13
This comparative example is different from example 6 in that the surface treatment method of glass spheres, step S2, was performed with a spray thickness of 40 μm.
Comparative example 14
This comparative example is different from example 6 in that the surface treatment method of glass spheres, step S2, was performed to a spray thickness of 110 μm.
Comparative example 15
This comparative example is different from example 6 in that the thermosetting resin is a thermosetting phenol resin in step S2 of the surface treatment method of glass spheres.
Comparative example 16
This comparative example is different from example 6 in that the thermosetting resin is an epoxy resin in step S2 of the surface treatment method of glass spheres.
Comparative example 17
This comparative example is different from example 6 in that the thermosetting resin is a urethane resin in step S2 of the surface treatment method of glass spheres.
Comparative example 18
The comparative example differs from example 6 in that the modified phenolic resin was prepared by the following method: mixing thermosetting phenolic resin with a solvent, then dropwise adding bromine under the stirring condition, heating to 45 ℃, stirring and reacting for 5 hours, evaporating water content of the obtained product, stirring and reacting with long-chain sodium alkoxide at room temperature for 3 hours, washing the obtained product with water, and drying to obtain the modified phenolic resin.
Comparative example 19
The comparative example differs from example 6 in that the modified phenolic resin was prepared by the following method: mixing thermosetting phenolic resin with a solvent, then dropwise adding bromine under the stirring condition, heating to 45 ℃, stirring and reacting for 5 hours, then dropwise adding a mixed solution of long-chain carboxylic acid and concentrated sulfuric acid, reacting for 5.5 hours at 115 ℃, and then removing the solvent to obtain the modified phenolic resin.
Comparative example 20
This comparative example differs from example 7 in that the phosphoric acid solution comprised 70% phosphoric acid and 30% water in step (3) of the method for preparing a solid phosphoric acid catalyst.
Comparative example 21
This comparative example is different from example 7 in that the impregnation process does not carry out bubbling in step (3) of the method for preparing a solid phosphoric acid catalyst.
Comparative example 22
The present comparative example is different from example 7 in that the phosphoric acid solution includes 70% phosphoric acid, 12% nano-silica powder, and 18% water in step (3) of the method for preparing a solid phosphoric acid catalyst.
First, the reaction result of synthesizing p-cyanophenol of the invention
Paracyanophenol was synthesized according to the methods of examples 1 to 7 and comparative examples 1 to 22 of the present invention, and the conversion rate (change in the content of methylparaben measured by GC area normalization) and yield of the reaction were calculated after the completion of the reaction, and the results are shown in Table 1.
Conversion = (mass of methyl paraben participating in reaction/mass of methyl paraben raw material) × 100%.
Yield = (actual yield of p-cyanophenol/theoretical yield of p-cyanophenol) × 100%.
TABLE 1
As is clear from the results in Table 1, the methods of examples 1 to 7 of the present invention resulted in the synthesis of p-cyanophenol in which the conversion of the starting material (methyl parahydroxybenzoate) was 85% or more and the reaction yields were 80% or more; especially, the conversion rate of the examples 5, 6 and 7 reaches 97-98%, the reaction yield reaches 94-95%, and the reaction efficiency is higher.
Of these, comparative example 1 was used as a prior art control, and it was found that the conversion and yield can be improved according to the synthesis method of the present invention as compared with comparative example 1 by examples 1 to 7.
Both the conversion and the yield of example 1 were increased compared to comparative example 1, but the spread was not large; on the basis of the example 1, the glass ball filler is additionally arranged in the example 2, and the modified phenolic resin is used for the surface treatment of the glass ball filler in the example 3, so that the conversion rate and the yield of the examples 2 and 3 slightly increase, and the difference from the example 1 is small; the organic substances and additives generated in the treatment processes of examples 1, 2 and 3 are likely to increase side reactions and inhibit the reaction, so that the conversion and yield of examples 1, 2 and 3 are not significantly improved.
Meanwhile, on the basis of example 1, in example 4, in order to reduce side reactions, nano silicon powder is added to the components of the phosphoric acid solution in the preparation process of the solid phosphoric acid catalyst, and as a result, the conversion rate and yield are obviously improved compared with example 1, which shows that the method in example 4 can obviously reduce the occurrence of side reactions. While the conversion and yield of examples 5-7 are optimal. The above comprehensive description shows that the nano silicon powder is added to the components of the phosphoric acid solution, so that the problem of side reaction in the embodiments 1, 2 and 3 can be solved simultaneously.
Comparative examples 2-8 changed the preparation method of the solid phosphoric acid catalyst compared to example 5; comparative examples 9-19 changed the surface treatment method of the glass bead filler compared to example 6; comparative examples 20 to 22 changed the composition of the phosphoric acid solution and the impregnation conditions compared to example 7; as a result, the conversion and yield of comparative examples 2 to 22 were reduced to different degrees, indicating that the conversion and yield could be improved only in combination by the process according to the invention.
The invention has the beneficial effects that: the synthesis method of the p-cyanophenol provided by the invention comprehensively improves the reaction yield and the conversion rate through the preparation of the solid phosphoric acid catalyst, the surface treatment of the glass ball filler and the improvement of the phosphoric acid solution.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and not intended to limit the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or some technical features thereof can be replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing p-cyanophenol is characterized in that: the method comprises the following specific steps:
adding a solid phosphoric acid catalyst into a reaction bed layer of a fixed bed reactor, dissolving methyl p-hydroxybenzoate in a solvent, feeding the methyl p-hydroxybenzoate and water into the fixed bed reactor, introducing ammonia gas into the reactor, controlling the temperature of the reactor to be 300-500 ℃ and the pressure to be more than 0.06MPa, continuously discharging, and rectifying and purifying to obtain a finished product of the p-cyanophenol;
the preparation method of the solid phosphoric acid catalyst comprises the following steps:
(1) placing maleic anhydride, 1/2 long-chain alcohol and silicon dioxide microspheres in a reaction container together, uniformly mixing, heating the container to 100 ℃ and 110 ℃, dropwise adding the remaining mixed solution of 1/2 long-chain alcohol and a catalyst under the stirring condition, and after dropwise adding, keeping the temperature and stirring for reacting for 6-8 hours to obtain an esterification product;
(2) dissolving sodium vinylsulfonate in deionized water, mixing the deionized water with an initiator uniformly, dropwise adding the mixture into the esterification product obtained in the step (1) at the temperature of 70-75 ℃ under the stirring condition, and carrying out heat preservation and stirring reaction for 4-6 hours after dropwise adding to obtain an addition polymerization product;
(3) filtering and drying the addition polymerization product, soaking in a phosphoric acid solution at normal temperature and normal pressure for 1-2h, filtering to remove redundant liquid, drying at the temperature of 100 ℃ and 110 ℃ for 30-60min, and then transferring into a resistance furnace to roast for 3-5h to obtain the solid phosphoric acid catalyst.
2. The method for synthesizing a p-cyanophenol according to claim 1, wherein: the mass ratio of the methyl p-hydroxybenzoate to the solid phosphoric acid catalyst is 1: (0.1-0.3), wherein the mass ratio of methyl p-hydroxybenzoate, solvent and water is 1: (4-6): (0.4-0.8), the flow rate of ammonia gas is 3-4L/min, and the solvent is pyridine.
3. The method for synthesizing a p-cyanophenol according to claim 1, wherein: the mass ratio of maleic anhydride, long-chain alcohol, sodium vinylsulfonate and silica microspheres is 1: (2.4-3): (1-1.4): (10-30).
4. The method for synthesizing a p-cyanophenol according to claim 1, wherein: the catalyst in the step (1) is concentrated sulfuric acid, and the adding amount of the concentrated sulfuric acid is 3-5% of the total amount of maleic anhydride and long-chain alcohol; the initiator in the step (2) is benzophenone or benzoyl peroxide, and the addition amount of the initiator is 0.12-0.2% of the sodium vinyl sulfonate.
5. The method for synthesizing a p-cyanophenol according to claim 1, wherein: the roasting conditions of the resistance furnace in the step (3) are as follows: roasting at 300 ℃ for 30-50min at 200-.
6. The method for synthesizing a p-cyanophenol according to claim 1, wherein: the fixed bed reactor is also filled with glass ball filler, the height of the filler is 30-40cm, and the surface treatment method of the glass ball comprises the following steps:
s1, soaking the barite powder in 3-6 times of sodium bicarbonate solution for 1-3h, and then evaporating under reduced pressure to remove water to obtain pretreated barite powder;
s2, uniformly mixing the thermosetting resin, the curing agent, the silane coupling agent and the barite powder pretreated in the step S1 to prepare a coating, spraying the coating to the surface of the cleaned and dried glass ball, wherein the spraying thickness is 50-100 mu m, and heating and curing;
and S3, repeatedly soaking the glass balls with the solidified surfaces in 40-60% hydrofluoric acid solution for 2-4 times, each time for 10-20min, washing with clear water after soaking each time, and finally drying to obtain the glass balls with the treated surfaces.
7. The method for synthesizing a p-cyanophenol according to claim 6, wherein: the mass concentration of the sodium bicarbonate solution in the step S1 is 5-8%; the coating in the step S2 comprises 5-10 parts of pretreated barite powder, 20-30 parts of thermosetting resin, 2-4 parts of curing agent and 0.3-0.8 part of silane coupling agent, wherein the curing agent is sulfonic acid, and the heating curing temperature is 150-170 ℃.
8. The method for synthesizing a p-cyanophenol according to claim 6, wherein: the thermosetting resin is modified phenolic resin, and the preparation method of the modified phenolic resin comprises the following steps:
mixing thermosetting phenolic resin with a solvent, dropwise adding bromine under the stirring condition, heating to 40-50 ℃, stirring for reacting for 4-6h, evaporating water of the obtained product, stirring for reacting with long-chain sodium alkoxide at room temperature for 2-4h, washing and drying the obtained product, dropwise adding a mixed solution of long-chain carboxylic acid and a catalyst, reacting for 5-6h at 110-120 ℃, and removing the solvent to obtain the modified phenolic resin.
9. The method for synthesizing a p-cyanophenol according to claim 8, wherein: the solvent is diethylene glycol monobutyl ether or ethylene glycol monobutyl ether, the catalyst is concentrated sulfuric acid, the adding amount of the catalyst is 2-3%, and the molar ratio of the thermosetting phenolic resin to bromine to long-chain sodium alkoxide to long-chain carboxylic acid is 1: (1-1.2): (1-1.5): (1-1.3).
10. The method for synthesizing a p-cyanophenol according to claim 1, wherein: in the step (3) of preparing the solid phosphoric acid catalyst, the phosphoric acid solution comprises 60-70% of phosphoric acid, 8-12% of pretreated nano silicon powder and 18-32% of water;
the pretreatment method of the nano silicon powder comprises the following steps: soaking the nano silicon powder in silicone oil for 1-2h, taking out and drying;
bubbling is carried out in the dipping process, and the bubbling gas quantity is 0.3-0.6L/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5476544A (en) * | 1977-11-26 | 1979-06-19 | Sumitomo Chem Co Ltd | Preparation of p-cyanophenol |
| CN106699601A (en) * | 2015-11-12 | 2017-05-24 | 中触媒新材料股份有限公司 | One-step synthetic method of p-(o-)hydroxybenzonitrile |
| CN106694023A (en) * | 2015-11-12 | 2017-05-24 | 中触媒新材料股份有限公司 | Catalyst for synthesizing p-hydroxybenzonitrile (2-hydroxybenzonitrile) and preparation method of catalyst |
| CN108745389A (en) * | 2018-06-06 | 2018-11-06 | 辽宁格瑞凯特科技有限公司 | A kind of preparation method for synthesizing the catalyst of p-HBN |
| CN111138318A (en) * | 2020-01-17 | 2020-05-12 | 盐城工学院 | Method for preparing p-hydroxybenzonitrile by using methyl p-hydroxybenzoate and urea |
-
2021
- 2021-10-21 CN CN202111224014.8A patent/CN113929594A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5476544A (en) * | 1977-11-26 | 1979-06-19 | Sumitomo Chem Co Ltd | Preparation of p-cyanophenol |
| CN106699601A (en) * | 2015-11-12 | 2017-05-24 | 中触媒新材料股份有限公司 | One-step synthetic method of p-(o-)hydroxybenzonitrile |
| CN106694023A (en) * | 2015-11-12 | 2017-05-24 | 中触媒新材料股份有限公司 | Catalyst for synthesizing p-hydroxybenzonitrile (2-hydroxybenzonitrile) and preparation method of catalyst |
| CN108745389A (en) * | 2018-06-06 | 2018-11-06 | 辽宁格瑞凯特科技有限公司 | A kind of preparation method for synthesizing the catalyst of p-HBN |
| CN111138318A (en) * | 2020-01-17 | 2020-05-12 | 盐城工学院 | Method for preparing p-hydroxybenzonitrile by using methyl p-hydroxybenzoate and urea |
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Application publication date: 20220114 |