CN114195635A - Synthesis method of o-trifluoromethyl benzoyl chloride - Google Patents
Synthesis method of o-trifluoromethyl benzoyl chloride Download PDFInfo
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- CN114195635A CN114195635A CN202111439287.4A CN202111439287A CN114195635A CN 114195635 A CN114195635 A CN 114195635A CN 202111439287 A CN202111439287 A CN 202111439287A CN 114195635 A CN114195635 A CN 114195635A
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- fluorination
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- MXIUWSYTQJLIKE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoyl chloride Chemical compound FC(F)(F)C1=CC=CC=C1C(Cl)=O MXIUWSYTQJLIKE-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000001308 synthesis method Methods 0.000 title description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 67
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 60
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000047 product Substances 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 229940078552 o-xylene Drugs 0.000 claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 125000002252 acyl group Chemical group 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims description 139
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 75
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 48
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 36
- 238000004821 distillation Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000012752 auxiliary agent Substances 0.000 claims description 31
- 239000008187 granular material Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000012043 crude product Substances 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 22
- 239000011698 potassium fluoride Substances 0.000 claims description 22
- 235000003270 potassium fluoride Nutrition 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 20
- JIJFXGFHPXLJME-UHFFFAOYSA-N 1-(dichloromethyl)-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(Cl)Cl JIJFXGFHPXLJME-UHFFFAOYSA-N 0.000 claims description 18
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 17
- 239000004698 Polyethylene Substances 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- ZDVRPKUWYQVVDX-UHFFFAOYSA-N 2-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=CC=C1C=O ZDVRPKUWYQVVDX-UHFFFAOYSA-N 0.000 claims description 15
- 238000005086 pumping Methods 0.000 claims description 15
- 238000005070 sampling Methods 0.000 claims description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 14
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 13
- 238000007334 copolymerization reaction Methods 0.000 claims description 13
- 239000011975 tartaric acid Substances 0.000 claims description 13
- 235000002906 tartaric acid Nutrition 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- LIHLSLRANKCHLV-KQQUZDAGSA-N [(e)-2-methylbut-2-enoyl] (e)-2-methylbut-2-enoate Chemical compound C\C=C(/C)C(=O)OC(=O)C(\C)=C\C LIHLSLRANKCHLV-KQQUZDAGSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 9
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- UXMNSLMVCBBGCW-UHFFFAOYSA-N 1-(dichloromethyl)-2-(trichloromethyl)benzene Chemical compound ClC(Cl)C1=CC=CC=C1C(Cl)(Cl)Cl UXMNSLMVCBBGCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 5
- 239000000413 hydrolysate Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000007858 starting material Substances 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 63
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 49
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 49
- 239000012295 chemical reaction liquid Substances 0.000 description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- UFJYKWQUTDGGPV-UHFFFAOYSA-N 1,2-bis(dichloromethyl)benzene Chemical compound ClC(Cl)C1=CC=CC=C1C(Cl)Cl UFJYKWQUTDGGPV-UHFFFAOYSA-N 0.000 description 2
- VQRBXYBBGHOGFT-UHFFFAOYSA-N 1-(chloromethyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1CCl VQRBXYBBGHOGFT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5093—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with elements other than metals or carbon
- C04B41/5096—Silicon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
- C07C45/43—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis of >CX2 groups, X being halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing o-trifluoromethyl benzoyl chloride, which takes o-xylene as a starting raw material and synthesizes the o-trifluoromethyl benzoyl chloride through chlorination, fluorination, hydrolysis, acyl chlorination and rectification reactions in turn. The method adopts low-toxicity matter color liquid o-xylene as a starting material, has high reaction safety, reduces by-products by improving the utilization rate of chlorine and hydrogen fluoride, and comprehensively improves the yield of the target product o-trifluoromethyl benzoyl chloride.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of o-trifluoromethyl benzoyl chloride.
Background
O-trifluoromethylbenzoyl chloride, also known as 2-trifluoromethylbenzoyl chloride, having the molecular formula C8H4ClF3O, molecular weight 208.565, CAS registry number 312-94-7, pure colorless transparent liquid, melting point-21.7 deg.C, boiling point 72 deg.C/7 mm Hg, specific gravity 1.419, easily soluble in organic solvent, slightly soluble in water.
O-trifluoromethyl benzoyl chloride is an intermediate of bactericide fluoroamide, Raney records a preparation method of 2-trifluoromethyl benzoyl chloride, takes o-methyl benzoic acid as a raw material, and the specific synthetic route is as follows:
the synthesis route has good selectivity and few byproducts, but the o-methylbenzoic acid raw material is white inflammable prismatic crystals or needle crystals at normal temperature, the melting point is 103-105 ℃, namely, when the o-methylbenzoic acid raw material is subjected to chlorination reaction, the o-methylbenzoic acid raw material needs to be fully reacted at a temperature of over 100 ℃ or dissolved in a solvent, the chlorination reaction is a violent exothermic reaction, the o-methylbenzoic acid raw material is extremely easy to explode at an over-high temperature or in an environment where the solvent exists, and great danger and inconvenience are brought to production. Therefore, another green and safe synthetic path needs to be found.
In summary, how to design a synthesis method of o-trifluoromethyl benzoyl chloride has high safety, mild reaction and high reaction yield, and is a problem which needs to be solved urgently at present.
Disclosure of Invention
The present invention aims to solve the above technical problems and provide a method for synthesizing o-trifluoromethylbenzoyl chloride, which uses o-xylene as a starting material, has high reaction safety, reduces by-products by improving the utilization rate of chlorine and hydrogen fluoride, and comprehensively improves the yield of the target product o-trifluoromethylbenzoyl chloride.
The invention realizes the purpose through the following technical scheme, and the method for synthesizing the o-trifluoromethyl benzoyl chloride specifically comprises the following steps:
(1) chlorination of
Adding o-xylene and a chlorination catalyst into a chlorination kettle, heating a jacket to 90-100 ℃, introducing dry chlorine into the chlorination kettle, stirring for reaction for 24 hours, sampling, and stopping the reaction when the content of 1- (dichloromethyl) -2- (trichloromethyl) benzene in a chlorination solution reaches 54-60% by gas chromatography analysis.
(2) Fluorination of
Pumping the chlorination liquid into a fluorination kettle, adding a fluorination auxiliary agent, introducing hydrogen fluoride, introducing steam into a jacket, heating to 80 ℃ for reaction for 6 hours, cooling coil pipe chilled water to 50 ℃ after the reaction is finished, and putting liquid in the kettle into a distillation kettle for reduced pressure distillation to obtain a 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product.
(3) Hydrolysis
Pumping the 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product into a hydrolysis kettle, adding water and a catalyst FeCl3Carrying out hydrolysis reaction at the normal pressure, wherein the reaction temperature is 120 ℃, sampling after 5h of reaction, stopping the reaction after detecting that no 1- (dichloromethyl) -2- (trifluoromethyl) benzene exists in the hydrolysate, and then carrying out reduced pressure distillation on the hydrolysate to obtain a crude product of o-trifluoromethylbenzaldehyde.
(4) Acyl chloride
Pumping the crude product of o-trifluoromethylbenzaldehyde into a reaction kettle, keeping the temperature of jacket steam, introducing dry chlorine gas at 80 ℃ for acyl chlorination reaction, sampling after 8h of reaction, transferring into a distillation kettle for reduced pressure distillation when no o-trifluoromethylbenzaldehyde is detected, and obtaining the crude product of o-trifluoromethylformyl chloride.
(5) Rectification
And transferring the crude o-trifluoromethyl formyl chloride into a rectifying tower, introducing steam into a rectifying kettle jacket, and obtaining the finished o-trifluoromethyl benzoyl chloride after the rectification is finished.
Further, the mass ratio of the o-xylene to the chlorination catalyst in the step (1) is 1: (0.02-0.03), the introduction amount of chlorine is 0.22-0.26mol/h, and the chlorination catalyst is N, N-dimethylformamide or azobisisobutyronitrile.
The distillation conditions in the step (2) are-0.09 MPa and 100 ℃, and the introduction amount of the hydrogen fluoride is 0.5-0.7 mol/h.
The distillation conditions in the steps (3) and (4) are 100-: (2-4), catalyst FeCl3The dosage of the composition is 0.1-0.3%.
The introduction amount of the chlorine in the step (4) is 0.13-0.18 mol/h.
The distillation conditions in the step (5) are-0.09 MPa and 100-120 ℃.
The invention also provides a ceramic ball used in the synthesis method of o-trifluoromethyl benzoyl chloride, when the reaction in the step (1) is started, the ceramic ball is added into a chlorination kettle, the adding amount of the ceramic ball is 10-20% of the mass of o-xylene, and the ceramic ball is made of porous ceramic and a modified TPU (thermoplastic polyurethane elastomer rubber) waterproof breathable film wrapped on the surface of the ceramic ball.
Further, the preparation method of the ceramic ball comprises the following steps:
s1, drying the porous ceramic, soaking the porous ceramic in silicone oil for 20-30min, filtering, and drying the obtained material in a centrifugal machine for 30-40min to obtain the pretreated porous ceramic;
s2, uniformly mixing the modified TPU, the nano silicon powder and the N, N-dimethylformamide, adding polyethylene glycol to prepare a coating liquid, spraying the coating liquid on the surface of the pretreated porous ceramic, immediately immersing the porous ceramic in deionized water for 2-3 days after spraying, and finally taking out and drying to obtain the finished ceramic ball.
Further, in the step S2, the mass ratio of the modified TPU, the nano silicon powder, the N, N-dimethylformamide and the polyethylene glycol is 1: (0.04-0.1): (3-5): (0.02-0.06).
Further, the porous ceramicHas a pore diameter of 10-50 μm, a particle diameter of 1-3mm, and an apparent porosity>60 percent; the volume weight distribution of the porous ceramic is as follows: 0.98-1.05 g/cm35-10% of the total weight of the composition, 1.1-1.2 g/cm315-25% of the total weight of the composition, 1.25-1.35g/cm320-40% of the total weight of the composition, 1.4-1.45g/cm38-15% of the total weight of the composition, 1.48-1.55g/cm3The balance is occupied.
According to the Archimedes principle, when the buoyancy is less than or equal to the gravity of the object, the object sinks or suspends, and when the volume of the object immersed in the liquid is unchanged, the buoyancy is only in positive correlation with the density of the liquid, so that the ceramic balls can be ensured to be in a suspended dispersion state only by controlling the mass-to-volume ratio (namely volume weight) of the ceramic balls to be equal to the density of the reaction liquid at different stages of the reaction, and the gas-phase and liquid-phase reactions can be better promoted.
The density of the ortho-xylene feed has been determined to be 0.95g/cm3(ii) a And the density of o-methylbenzyl chloride (monochlorinated product) is known to be 1.1. + -. 0.1 g/cm3(ii) a The density of o-dichlorobenzyl (dichloro product) was 1.2. + -. 0.1 g/cm3(ii) a The density of 1, 2-bis (dichloromethyl) benzene (tetrachloro product) was 1.442 g/cm3(ii) a The density of 1-dichloromethyl-2-trichloromethylbenzene (pentachlorinated product) is 1.5 +/-0.1 g/cm3. Therefore, the invention can better control the longitudinal position of the ceramic ball in the reaction liquid by controlling the volume weight distribution of the ceramic ball according to the component change in the chlorination reaction liquid.
The invention also provides a modified TPU material for preparing the ceramic balls, and the preparation method of the modified TPU material comprises the following steps:
a. uniformly mixing vinylamine and an initiator, then dropwise adding the tiglic anhydride, and stirring and reacting for 3-5h at the temperature of 80-100 ℃ to obtain a copolymerization product;
b. uniformly mixing polyethylene, the copolymerization product obtained in the step a and dicyclohexyl peroxydicarbonate, introducing the mixture into a double-screw extruder, extruding at the temperature of 140-;
c. uniformly mixing polyester type TPU granules and aromatic ester, and then introducing the mixture into a grinder with the temperature of 100-;
d. and uniformly mixing the granules I and the granules II, introducing the mixture into a double-screw extruder, and extruding at the temperature of 150-.
Further, in the step a, the mass ratio of vinylamine to tiglic anhydride is 1: (1.1-1.3), the initiator is azobisisobutyronitrile or azobisisoheptonitrile, and the amount of the initiator is 1-3% of the reaction raw material; in the step b, the mass ratio of the polyethylene to the copolymerization product to the dicyclohexyl peroxydicarbonate is 100: (5-10): (1-2); in the step c, the mass ratio of the polyester TPU granules to the aromatic ester is 1: (0.02-0.06); in the step d, the mass ratio of the first granules to the second granules is (0.1-0.3): 1.
the invention also provides a fluorination auxiliary agent used in the synthesis method of o-trifluoromethyl benzoyl chloride, and the mass ratio of the fluorination auxiliary agent to the chlorination liquid is (0.5-0.7): the preparation method of the fluorination auxiliary agent comprises the following steps:
A. uniformly mixing tartaric acid and water, adding activated carbon, dispersing for 1-2h in a dispersion machine with the speed of 400-500r/min, and drying to obtain pretreated activated carbon;
B. placing the pretreated activated carbon in a 1000-1200r/min airflow crusher, then simultaneously spraying aluminum chloride powder, sodium hydroxide powder and water, colliding at a high speed at 60-80 ℃, drying the obtained material, and heating to 160-180 ℃ to obtain activated carbon-based-alumina;
C. dissolving potassium fluoride in water, uniformly mixing, adding activated carbon-based-alumina, soaking for 1-3h, and drying at 110-120 ℃ for 5-6h to obtain the fluorination auxiliary agent.
Further, the molar ratio of tartaric acid to potassium fluoride is (0.3-0.5): 1, the mass ratio of the activated carbon to the potassium fluoride is 1: (0.4-0.6); in the step B, the molar ratio of the aluminum chloride powder to the sodium hydroxide powder is 1: (3-3.6).
The invention has the beneficial effects that:
(1) the invention takes o-xylene (low-toxicity colorless liquid) as a starting material, and synthesizes o-trifluoromethyl formyl chloride through chlorination, fluorination, hydrolysis, acyl chlorination and rectification in sequence, thereby providing another synthetic route with higher safety and milder reaction;
(2) because the invention takes ortho-xylene as raw materials to carry out chlorination reaction, the target product is 1-dichloromethyl-2-trichloromethyl benzene, therefore, while controlling the amount of chlorine gas introduced, it is also necessary to keep the utilization ratio of chlorine gas, can improve the content of the target product, reduce by-products, the invention adds ceramic balls into the chlorination reactor, the ceramic balls contain a large number of through holes, make the chlorine gas introduced into the chlorination reactor pass through the through holes of these ceramic balls slowly in the reaction liquid, cause the gas movement speed to slow down, has promoted the reaction of gas phase and liquid phase, thus has improved the utilization ratio of chlorine gas;
(3) according to the invention, silicone oil treatment is also carried out on the porous ceramic during the preparation of the ceramic ball, so that the smoothness degree in the pores of the porous ceramic is improved, and the stay of chlorine in the pores of the ceramic ball is reduced; the hydraulic pressure rises along with the increase of the density of the reaction liquid, and the waterproof and breathable film on the surface of the ceramic ball is extruded, so that the effect of continuously releasing chlorine in the ceramic ball is achieved, and the backlog of the chlorine in the ceramic ball is reduced;
(4) the ceramic ball is made of porous ceramic and the modified TPU waterproof breathable film wrapped on the surface of the porous ceramic, so that when the ceramic ball is in a reaction liquid, the reaction liquid cannot permeate into the ceramic ball, only chlorine gas is allowed to pass through, a movement channel is provided for the chlorine gas, the chlorine gas is prevented from being blocked by the liquid in pores, and after the waterproof breathable film is wrapped on the outer surface of the ceramic ball, the ceramic ball is favorably suspended and dispersed at different positions of the reaction liquid, and is more favorable for buffering the chlorine gas;
(5) because the density of the reaction liquid is gradually increased in the chlorination process, the longitudinal position of the ceramic ball in the reaction liquid is changed, the volume weight of the porous ceramic is specifically distributed according to the density of various chlorinated products of o-xylene, so that the ceramic ball can be uniformly suspended in the reaction liquid in the whole chlorination process;
(6) because a large amount of hydrogen chloride is generated in the chlorination reaction, hydrogen chloride is introduced into the ceramic ball in the reaction liquid, so that the improvement of the utilization rate of chlorine by the ceramic ball is influenced, a nonpolar component needs to be introduced into a waterproof breathable film of the ceramic ball, and the absorption of the nonpolar component to polar molecular hydrogen chloride is reduced, and the compatibility of the ceramic ball to nonpolar molecular chlorine can be enhanced by blending and modifying the TPU material and polyethylene;
(7) because the polar TPU material is incompatible with the non-polar polyethylene, the invention respectively carries out compatibilization treatment on the polyethylene and the TPU when preparing the modified TPU material, and the specific compatibilization method is that a copolymerization product is synthesized by vinylamine and cis-Zhi acid anhydride, the polarity and the reaction activity of the polyethylene are increased by adding the copolymer into the polyethylene, polyester type TPU granules and aromatic ester are mixed and ground to increase the non-polarity of the polyester type TPU granules, and then the compatibilized polyethylene and the TPU are blended, so that the compatibility of the polyester type TPU granules and the aromatic ester can be obviously enhanced, and the affinity of the waterproof breathable film to chlorine is improved;
(8) according to the invention, the fluorination auxiliary agent prepared by taking the activated carbon as the matrix and the potassium fluoride as the fluorination reaction promoter can improve the fluorination reaction speed, and the activated carbon matrix can adsorb part of hydrogen fluoride, so that the utilization rate of the hydrogen fluoride is improved, fluorinated byproducts are reduced, and the yield of a target product is improved;
(9) when the fluorination auxiliary agent is prepared, aluminum hydroxide is generated on the surface of the fluorination auxiliary agent through reaction and is heated to form gamma-type aluminum oxide, so that the surface activity of activated carbon can be enhanced, and the catalytic activity of potassium fluoride can be enhanced;
(10) when the fluorizating reagent is prepared, a nucleophilic reagent potassium fluoride is used as an active ingredient, tartaric acid is loaded on the surface of active carbon to form a porous alumina layer, and the tartaric acid can form a complex with potassium ions, so that the potassium ions are smaller and can rapidly permeate through the porous layer of the alumina to form a complex with the tartaric acid when the potassium fluoride is impregnated later, and the complex molecules are larger and cannot easily permeate through the alumina layer, so that the potassium ions are separated from the fluorine ions, and the nucleophilicity of the fluorine ions is enhanced.
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 o-trifluoromethyl benzoyl chloride, which specifically comprises the following steps:
(1) chlorination of
According to the mass ratio of 1: 0.02 adding o-xylene and N, N-dimethylformamide into a chlorination kettle, heating a jacket to 90 ℃, introducing dry chlorine into the chlorination kettle, wherein the introduction amount of the chlorine is 0.22mol/h, stirring for reacting for 24h, sampling, and stopping the reaction when the content of the 1- (dichloromethyl) -2- (trichloromethyl) benzene in the chlorination solution reaches 54% by gas chromatography analysis. The specific chlorination reaction route is as follows:
(2) fluorination of
Pumping the chlorination liquid into a fluorination kettle, adding a fluorination auxiliary agent, introducing hydrogen fluoride with the introduction amount of 0.5mol/h, introducing steam into a jacket, heating to 80 ℃ for reaction for 6h, cooling coil pipe chilled water to 50 ℃ after the reaction is finished, putting the liquid in the kettle into a distillation kettle for reduced pressure distillation under the distillation conditions of-0.09 MPa and 100 ℃ to obtain a 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product. The specific fluorination reaction route is as follows:
(3) hydrolysis
Pumping the 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product into a hydrolysis kettle, adding water and a catalyst FeCl3Carrying out hydrolysis reaction at the normal pressure, wherein the reaction temperature is 120 ℃, sampling after 5h of reaction, stopping the reaction after detecting that no 1- (dichloromethyl) -2- (trifluoromethyl) benzene exists in the hydrolysate, and then carrying out reduced pressure distillation on the hydrolysate at the temperature of 100 ℃ and under the pressure of-0.09 MPa to obtain a crude product of o-trifluoromethylbenzaldehyde; wherein, the molar ratio of the 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product to water is 1: catalyst FeCl3The amount of (B) is 0.1%. The specific hydrolysis reaction route is as follows:
(4) acyl chloride
Pumping the crude product of o-trifluoromethylbenzaldehyde into a reaction kettle, preserving heat by jacket steam, introducing dry chlorine gas at 80 ℃ for acyl chlorination reaction, wherein the introduction amount of the chlorine gas is 0.13mol/h, sampling after 8h of reaction, transferring the product into a distillation kettle for reduced pressure distillation at 100 ℃ and-0.09 MPa when no o-trifluoromethylbenzaldehyde is detected, and obtaining the crude product of o-trifluoromethylformyl chloride. The specific acyl chlorination reaction route is as follows:
(5) rectification
And transferring the crude o-trifluoromethyl formyl chloride into a rectifying tower, introducing steam into a rectifying kettle jacket, wherein the rectifying conditions are-0.09 MPa and 100 ℃, and obtaining the finished o-trifluoromethyl benzoyl chloride after the rectification is finished.
Example 2
On the basis of the example 1, the embodiment also provides a ceramic ball used in the synthesis method of o-trifluoromethyl benzoyl chloride, when the reaction in the step (1) is started, the ceramic ball is added into a chlorination kettle, the adding amount of the ceramic ball is 10 percent of the mass of o-xylene, and the ceramic ball is made into a breathable film by porous ceramic and modified TPU waterproof TPU wrapped on the surface of the ceramic ball.
The preparation method of the ceramic ball comprises the following steps:
s1, drying the porous ceramic, soaking the porous ceramic in silicone oil for 20min, filtering, and drying the obtained material in a centrifugal machine for 30min to obtain the pretreated porous ceramic;
s2, uniformly mixing the modified TPU, the nano silicon powder and the N, N-dimethylformamide, adding polyethylene glycol to prepare a coating liquid, spraying the coating liquid on the surface of the pretreated porous ceramic, immediately immersing the porous ceramic in deionized water for 2 days after spraying, and finally taking out and drying to obtain a finished ceramic ball, wherein the mass ratio of the modified TPU, the nano silicon powder, the N, N-dimethylformamide to the polyethylene glycol is 1: 0.04: 3: 0.02.
wherein the porous ceramic has a pore diameter of 10 μm, a particle diameter of 1mm, and an apparent porosity>60 percent; the volume weight distribution of the porous ceramic is as follows: 0.98g/cm35% of the total amount of the components, 1.1 g/cm315% of the total amount of the components is 1.25g/cm3Accounting for 40 percent, 1.4g/cm315% of the total amount of the components is 1.48g/cm3The balance is occupied.
The density of the ortho-xylene feed has been determined to be 0.95g/cm3(ii) a And the density of o-methylbenzyl chloride (monochlorinated product) is known to be 1.1. + -. 0.1 g/cm3(ii) a The density of o-dichlorobenzyl (dichloro product) was 1.2. + -. 0.1 g/cm3(ii) a The density of 1, 2-bis (dichloromethyl) benzene (tetrachloro product) was 1.442 g/cm3(ii) a The density of 1-dichloromethyl-2-trichloromethylbenzene (pentachlorinated product) is 1.5 +/-0.1 g/cm3. Therefore, according to the Archimedes principle, the invention can better control the longitudinal position of the ceramic ball in the reaction liquid by controlling the volume weight distribution of the ceramic ball according to the component change in the chlorination reaction liquid.
The rest is the same as in example 1.
Example 3
On the basis of embodiment 2, the present embodiment also provides a modified TPU material for preparing the above ceramic balls, and the preparation method of the modified TPU material comprises the following steps:
a. uniformly mixing vinylamine and azobisisobutyronitrile, then dropwise adding the tiglic anhydride, and stirring and reacting for 3 hours at 80 ℃ to obtain a copolymerization product, wherein the mass ratio of vinylamine to tiglic anhydride is 1: 1.1, the amount of the initiator is 1 percent of the reaction raw material;
b. according to the mass ratio of 100: 5: 1, uniformly mixing polyethylene, the copolymerization product obtained in the step a and dicyclohexyl peroxydicarbonate, introducing the mixture into a double-screw extruder, extruding the mixture at 140 ℃, and pelletizing to obtain pellets I;
c. according to the mass ratio of 1: 0.02 mixing the polyester type TPU granules and aromatic ester uniformly, and then introducing the mixture into a grinder with the temperature of 100 ℃ and the speed of 1000r/min for mixing and grinding for 30min to obtain granules II;
d. according to the mass ratio of 0.1: 1, uniformly mixing the granules I and the granules II, introducing the mixture into a double-screw extruder, and extruding at 150 ℃ to obtain a finished product.
The rest is the same as in example 2.
Example 4
On the basis of embodiment 1, this embodiment also provides a fluorination auxiliary used in the synthesis method of o-trifluoromethyl benzoyl chloride, where the mass ratio of the fluorination auxiliary to the chlorination solution is 0.5: the preparation method of the fluorination auxiliary agent comprises the following steps:
A. uniformly mixing tartaric acid and water, adding activated carbon, dispersing for 1h in a dispersion machine at 400r/min, and drying to obtain pretreated activated carbon;
B. putting the pretreated activated carbon in a 1000r/min jet mill, then simultaneously spraying aluminum chloride powder, sodium hydroxide powder and water, colliding at a high speed at 60 ℃, drying the obtained material, and heating to 160 ℃ to obtain activated carbon-based-alumina, wherein the molar ratio of the aluminum chloride powder to the sodium hydroxide powder is 1: 3;
C. dissolving potassium fluoride in water, uniformly mixing, adding activated carbon-alumina, soaking for 1h, and drying at 110 ℃ for 5h to obtain the fluorination auxiliary agent.
Wherein the molar ratio of tartaric acid to potassium fluoride is 0.3: 1, the mass ratio of the activated carbon to the potassium fluoride is 1: 0.4.
the rest is the same as in example 1.
Example 5
This example is a combination of example 3 and example 4.
Example 6
The embodiment provides a method for synthesizing o-trifluoromethyl benzoyl chloride, which specifically comprises the following steps:
(1) chlorination of
According to the mass ratio of 1: 0.025 adding o-xylene and azobisisobutyronitrile into a chlorination kettle, heating a jacket to 95 ℃, introducing dry chlorine into the chlorination kettle, wherein the introduction amount of the chlorine is 0.24mol/h, stirring for reaction for 24h, sampling, and stopping the reaction when the content of 1- (dichloromethyl) -2- (trichloromethyl) benzene in the chlorination liquid reaches 57% by gas chromatography analysis.
(2) Fluorination of
Pumping the chlorination liquid into a fluorination kettle, adding a fluorination auxiliary agent, introducing hydrogen fluoride with the introduction amount of 0.6mol/h, introducing steam into a jacket, heating to 80 ℃ for reaction for 6h, cooling coil pipe chilled water to 50 ℃ after the reaction is finished, putting the liquid in the kettle into a distillation kettle for reduced pressure distillation under the distillation conditions of-0.09 MPa and 100 ℃ to obtain a 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product.
(3) Hydrolysis
Pumping the 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product into a hydrolysis kettle, adding water and a catalyst FeCl3Carrying out hydrolysis reaction at the normal pressure, wherein the reaction temperature is 120 ℃, sampling after 5h of reaction, stopping the reaction after detecting that no 1- (dichloromethyl) -2- (trifluoromethyl) benzene exists in the hydrolysate, and then carrying out reduced pressure distillation on the hydrolysate at the temperature of 110 ℃ and the pressure of-0.09 MPa to obtain a crude product of o-trifluoromethylbenzaldehyde; wherein, the molar ratio of the 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product to water is 1: catalyst FeCl3The amount of (B) is 0.2%.
(4) Acyl chloride
Pumping the crude product of o-trifluoromethylbenzaldehyde into a reaction kettle, preserving heat by jacket steam, introducing dry chlorine gas at 80 ℃ for acyl chlorination reaction, wherein the introduction amount of the chlorine gas is 0.15mol/h, sampling after 8h of reaction, transferring the product into a distillation kettle for reduced pressure distillation at 110 ℃ and-0.09 MPa when no o-trifluoromethylbenzaldehyde exists, and obtaining the crude product of o-trifluoromethylformyl chloride;
(5) rectification
And transferring the crude o-trifluoromethyl benzoyl chloride product into a rectifying tower, introducing steam into a rectifying kettle jacket, wherein the rectifying conditions are-0.09 MPa and 110 ℃, and obtaining the finished o-trifluoromethyl benzoyl chloride product after the rectification is finished.
This example also provides a ceramic ball used in the synthesis method of o-trifluoromethyl benzoyl chloride, and the ceramic ball is added into the chlorination reactor at the beginning of the reaction in step (1), and the addition amount is 15% of the mass of o-xylene.
The preparation method of the ceramic ball comprises the following steps:
s1, drying the porous ceramic, soaking the porous ceramic in silicone oil for 25min, filtering, and drying the obtained material in a centrifugal machine for 35min to obtain the pretreated porous ceramic;
s2, uniformly mixing the modified TPU, the nano silicon powder and the N, N-dimethylformamide, adding polyethylene glycol to prepare a coating liquid, spraying the coating liquid on the surface of the pretreated porous ceramic, immediately immersing the porous ceramic in deionized water for 2.5 days after spraying, and finally taking out and drying to obtain a finished ceramic ball, wherein the mass ratio of the modified TPU, the nano silicon powder, the N, N-dimethylformamide to the polyethylene glycol is 1: 0.07: 4: 0.04.
wherein the porous ceramic has a pore diameter of 30 μm, a particle diameter of 2mm, and an apparent porosity>60 percent; the volume weight distribution of the porous ceramic is as follows: 1.01 g/cm37.5 percent, 1.15 g/cm3Accounting for 20 percent, 1.3g/cm3Accounting for 30 percent, 1.42g/cm311.5%, 1.51g/cm3The balance is occupied.
The embodiment also provides a modified TPU material for preparing the ceramic balls, and the preparation method of the modified TPU material comprises the following steps:
a. uniformly mixing vinylamine and azobisisoheptonitrile, then dropwise adding the tiglic anhydride, and stirring and reacting for 4 hours at 90 ℃ to obtain a copolymerization product, wherein the mass ratio of vinylamine to tiglic anhydride is 1: 1.2, the amount of the initiator is 2 percent of the reaction raw material;
b. according to the mass ratio of 100: 7.5: 1.5 uniformly mixing polyethylene, the copolymerization product obtained in the step a and dicyclohexyl peroxydicarbonate, introducing the mixture into a double-screw extruder, extruding the mixture at 150 ℃, and pelletizing to obtain pellets I;
c. according to the mass ratio of 1: 0.04 uniformly mixing the polyester type TPU granules with aromatic ester, and then introducing the mixture into a grinder with the temperature of 110 ℃ and the speed of 1300r/min for mixing and grinding for 45min to obtain granules II;
d. according to the mass ratio of 0.2: 1, uniformly mixing the granules I and the granules II, introducing the mixture into a double-screw extruder, and extruding at 160 ℃ to obtain a finished product.
The embodiment also provides a fluorination auxiliary agent used in the synthesis method of o-trifluoromethyl benzoyl chloride, wherein the mass ratio of the fluorination auxiliary agent to the chlorination solution is 0.6: the preparation method of the fluorination auxiliary agent comprises the following steps:
A. uniformly mixing tartaric acid and water, adding activated carbon, dispersing for 1.5h in a dispersion machine at 450r/min, and drying to obtain pretreated activated carbon;
B. putting the pretreated activated carbon in a 1100r/min jet mill, then simultaneously spraying aluminum chloride powder, sodium hydroxide powder and water, colliding at a high speed at 70 ℃, drying the obtained material, and heating to 170 ℃ to obtain activated carbon-based-alumina, wherein the molar ratio of the aluminum chloride powder to the sodium hydroxide powder is 1: 3.3;
C. dissolving potassium fluoride in water, uniformly mixing, adding activated carbon-alumina, soaking for 2h, and drying at 115 ℃ for 5.5h to obtain the fluorination auxiliary agent.
Wherein the molar ratio of tartaric acid to potassium fluoride is 0.4: 1, the mass ratio of the activated carbon to the potassium fluoride is 1: 0.5.
example 7
The embodiment provides a method for synthesizing o-trifluoromethyl benzoyl chloride, which specifically comprises the following steps:
(1) chlorination of
According to the mass ratio of 1: 0.03 adding o-xylene and N, N-dimethylformamide into a chlorination kettle, heating a jacket to 100 ℃, then introducing dry chlorine into the chlorination kettle, wherein the introduction amount of the chlorine is 0.26mol/h, stirring for reacting for 24h, sampling, and stopping the reaction when the content of the 1- (dichloromethyl) -2- (trichloromethyl) benzene in the chlorination solution reaches 60% by gas chromatography analysis.
(2) Fluorination of
Pumping the chlorination liquid into a fluorination kettle, adding a fluorination auxiliary agent, introducing hydrogen fluoride with the introduction amount of 0.7mol/h, introducing steam into a jacket, heating to 80 ℃ for reaction for 6h, cooling coil pipe chilled water to 50 ℃ after the reaction is finished, putting the liquid in the kettle into a distillation kettle for reduced pressure distillation under the distillation conditions of-0.09 MPa and 100 ℃ to obtain a 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product.
(3) Hydrolysis
Pumping the 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product into a hydrolysis kettle, adding water and a catalyst FeCl3Performing hydrolysis reaction at 120 deg.C under normal pressure for 5 hr, sampling, detecting, and hydrolyzingStopping reaction after no 1- (dichloromethyl) -2- (trifluoromethyl) benzene exists in the solution, and then carrying out reduced pressure distillation on the hydrolysate at the temperature of 120 ℃ and the pressure of-0.09 MPa to obtain a crude product of o-trifluoromethylbenzaldehyde; wherein, the molar ratio of the 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product to water is 1: catalyst FeCl3The amount of (B) is 0.3%.
(4) Acyl chloride
Pumping the crude product of o-trifluoromethylbenzaldehyde into a reaction kettle, preserving heat by jacket steam, introducing dry chlorine gas at 80 ℃ for acyl chlorination reaction, wherein the introduction amount of the chlorine gas is 0.18mol/h, sampling after 8h of reaction, transferring the product into a distillation kettle for reduced pressure distillation at 120 ℃ and-0.09 MPa when no o-trifluoromethylbenzaldehyde exists, and obtaining the crude product of o-trifluoromethylformyl chloride;
(5) rectification
And transferring the crude o-trifluoromethyl formyl chloride into a rectifying tower, introducing steam into a rectifying kettle jacket, wherein the rectifying conditions are-0.09 MPa and 120 ℃, and obtaining the finished o-trifluoromethyl benzoyl chloride after the rectification is finished.
This example also provides a ceramic ball used in the synthesis method of o-trifluoromethyl benzoyl chloride, and the ceramic ball is added into the chlorination reactor at the beginning of the reaction in step (1), and the addition amount is 20% of the mass of o-xylene.
The preparation method of the ceramic ball comprises the following steps:
s1, drying the porous ceramic, soaking the porous ceramic in silicone oil for 30min, filtering, and drying the obtained material in a centrifugal machine for 40min to obtain the pretreated porous ceramic;
s2, uniformly mixing the modified TPU, the nano silicon powder and the N, N-dimethylformamide, adding polyethylene glycol to prepare a coating liquid, spraying the coating liquid on the surface of the pretreated porous ceramic, immediately immersing the porous ceramic in deionized water for 3 days after spraying, and finally taking out and drying to obtain a finished ceramic ball, wherein the mass ratio of the modified TPU, the nano silicon powder, the N, N-dimethylformamide to the polyethylene glycol is 1: 0.1: 5: 0.06.
wherein the porous ceramic has a pore diameter of 50 μm, a particle diameter of 3mm, and an apparent porosity>60 percent; the volume weight distribution of the porous ceramic is as follows: 1.05 g/cm310%, 1.2 g/cm3Accounting for 25 percent, 1.35g/cm3Accounting for 20 percent, 1.45g/cm38% of the total amount of the components is 1.55g/cm3The balance is occupied.
The embodiment also provides a modified TPU material for preparing the ceramic balls, and the preparation method of the modified TPU material comprises the following steps:
a. uniformly mixing vinylamine and azobisisobutyronitrile, then dropwise adding the tiglic anhydride, and stirring and reacting for 5 hours at 100 ℃ to obtain a copolymerization product, wherein the mass ratio of vinylamine to tiglic anhydride is 1: 1.3, the amount of the initiator is 3 percent of the reaction raw material;
b. according to the mass ratio of 100: 10: 2, uniformly mixing polyethylene, the copolymerization product obtained in the step a and dicyclohexyl peroxydicarbonate, introducing the mixture into a double-screw extruder, extruding the mixture at 160 ℃, and pelletizing to obtain pellets I;
c. according to the mass ratio of 1: 0.06 mixing the polyester type TPU granules and aromatic ester uniformly, and then introducing the mixture into a grinder with the temperature of 120 ℃ and the speed of 1600r/min for mixing and grinding for 60min to obtain granules II;
d. according to the mass ratio of 0.3: 1, uniformly mixing the granules I and the granules II, introducing the mixture into a double-screw extruder, and extruding at 170 ℃ to obtain a finished product.
The embodiment also provides a fluorination auxiliary agent used in the synthesis method of o-trifluoromethyl benzoyl chloride, wherein the mass ratio of the fluorination auxiliary agent to the chlorination solution is 0.7: the preparation method of the fluorination auxiliary agent comprises the following steps:
A. uniformly mixing tartaric acid and water, adding activated carbon, dispersing for 2 hours in a dispersion machine at 500r/min, and drying to obtain pretreated activated carbon;
B. putting the pretreated activated carbon in a 1200r/min jet mill, then simultaneously spraying aluminum chloride powder, sodium hydroxide powder and water, colliding at a high speed at 80 ℃, drying the obtained material, and heating to 180 ℃ to obtain activated carbon-based-alumina, wherein the molar ratio of the aluminum chloride powder to the sodium hydroxide powder is 1: 3.6;
C. dissolving potassium fluoride in water, uniformly mixing, adding activated carbon-alumina, soaking for 3h, and drying at 120 ℃ for 6h to obtain the fluorination auxiliary agent.
Wherein the molar ratio of tartaric acid to potassium fluoride is 0.5: 1, the mass ratio of the activated carbon to the potassium fluoride is 1: 0.6.
comparative example 1
This comparative example differs from example 5 in that the ceramic balls are porous ceramics.
Comparative example 2
This comparative example differs from example 5 in that the ceramic balls were added in an amount of 8% by mass of o-xylene.
Comparative example 3
This comparative example differs from example 5 in that the ceramic balls were added in an amount of 22% by mass of o-xylene.
Comparative example 4
This comparative example is different from example 5 in that the preparation method of the ceramic ball does not include the porous ceramic pretreatment of step S1, and the specific steps at this time are: uniformly mixing the modified TPU, the nano silicon powder and the N, N-dimethylformamide, then adding polyethylene glycol to prepare a coating liquid, spraying the coating liquid on the surface of the porous ceramic, immediately immersing the porous ceramic in deionized water for 2 days after spraying, and finally taking out and drying to obtain a finished ceramic ball.
Comparative example 5
The comparative example is different from example 5 in that the preparation method of the ceramic ball comprises the following steps of S2: uniformly mixing the modified TPU and the N, N-dimethylformamide, adding polyethylene glycol to prepare a coating solution, spraying the coating solution on the surface of the pretreated porous ceramic, immediately immersing the porous ceramic in deionized water for 2 days after spraying, and finally taking out and drying to obtain a finished ceramic ball.
Comparative example 6
This comparative example is different from example 5 in that the apparent porosity of the porous ceramic in the raw material for preparing the ceramic balls was 55%.
Comparative example 7
This comparative example is different from example 5 in that the porous ceramics in the raw materials for preparing the ceramic balls all have a volume weight of 0.98g/cm3。
Comparative example 8
Book pairThe ratio was different from example 5 in that this comparative example was different from example 5 in that the porous ceramics were all 1.1 g/cm in volume weight in the raw materials for preparing the ceramic balls3。
Comparative example 9
This comparative example is different from example 5 in that the porous ceramics in the raw materials for preparing the ceramic balls all have a volume weight of 1.25g/cm3。
Comparative example 10
This comparative example is different from example 5 in that the porous ceramics in the raw materials for preparing the ceramic balls all have a volume weight of 1.4g/cm3。
Comparative example 11
This comparative example is different from example 5 in that the porous ceramics in the raw materials for preparing the ceramic balls all have a volume weight of 1.48g/cm3。
Comparative example 12
The comparative example is different from example 5 in that the porous ceramic is prepared from the following raw materials in volume weight distribution: 1.1 g/cm315% of the total amount of the components is 1.25g/cm3Accounting for 40 percent, 1.4g/cm315% of the total amount of the components is 1.48g/cm3The balance is occupied.
Comparative example 13
The comparative example is different from example 5 in that the porous ceramic is prepared from the following raw materials in volume weight distribution: 0.98g/cm3Accounting for 5 percent, 1.25g/cm3Accounting for 40 percent, 1.4g/cm315% of the total amount of the components is 1.48g/cm3The balance is occupied.
Comparative example 14
The comparative example is different from example 5 in that the porous ceramic is prepared from the following raw materials in volume weight distribution: 0.98g/cm35% of the total amount of the components, 1.1 g/cm315% of the total amount of the components, 1.4g/cm315% of the total amount of the components is 1.48g/cm3The balance is occupied.
Comparative example 15
The comparative example is different from example 5 in that the porous ceramic is prepared from the following raw materials in volume weight distribution: 0.98g/cm35% of the total amount of the components, 1.1 g/cm315% of the total amount of the components is 1.25g/cm3Accounting for 40 percent, 1.48g/cm3The balance is occupied.
Comparative example 16
The comparative example is different from example 5 in that the porous ceramic is prepared from the following raw materials in volume weight distribution: 0.98g/cm35% of the total amount of the components, 1.1 g/cm315% of the total amount of the components is 1.25g/cm3Accounting for 40 percent, 1.4g/cm3The balance is occupied.
Comparative example 17
This comparative example differs from example 6 in that the modified TPU material is a common polyester type TPU, i.e., a polyester type thermoplastic polyurethane elastomer rubber.
Comparative example 18
The comparative example differs from example 6 in that the modified TPU material was prepared by the process of: according to the mass ratio of 100: 7.5: 1.5 uniformly mixing polyethylene, maleic anhydride and dicyclohexyl peroxydicarbonate, introducing the mixture into a double-screw extruder, carrying out reactive extrusion at 150 ℃ to obtain polyethylene grafted maleic anhydride, and then carrying out reaction according to a mass ratio of 0.2: 1, uniformly mixing polyethylene grafted maleic anhydride and polyester TPU granules, introducing the mixture into a double-screw extruder, and extruding at 160 ℃ to obtain a modified TPU finished product.
Comparative example 19
This comparative example differs from example 6 in that the process for preparing the modified TPU material does not include step a, when step b is: according to the mass ratio of 100: 7.5: 1.5 evenly mixing polyethylene, maleic anhydride and dicyclohexyl peroxydicarbonate, introducing into a double-screw extruder, extruding at 150 ℃, and granulating to obtain granules I.
Comparative example 20
This comparative example differs from example 6 in that the maleic anhydride was replaced by the maleic anhydride in step a of the process for the preparation of the modified TPU material.
Comparative example 21
This comparative example differs from example 6 in that the process for preparing the modified TPU material does not include step c, where step d is: according to the mass ratio of 0.2: 1, uniformly mixing the granules I and polyester type TPU granules, introducing the mixture into a double-screw extruder, and extruding at 160 ℃ to obtain a finished product.
Comparative example 22
This comparative example differs from example 7 in that the fluorination aid was replaced by potassium fluoride.
Comparative example 23
The comparative example is different from example 7 in that the mass ratio of the fluorination auxiliary agent to the chlorination solution is 0.4: 1.
comparative example 24
The comparative example is different from example 7 in that the mass ratio of the fluorination auxiliary agent to the chlorination solution is 0.8: 1.
comparative example 25
The comparative example differs from example 7 in that the fluorination aid was prepared by the following method: dissolving potassium fluoride in water, uniformly mixing, adding activated carbon, soaking for 3h, and drying at 120 ℃ for 6h to obtain the fluorination auxiliary agent.
Comparative example 26
This comparative example differs from example 7 in that the fluorination aid was prepared by a method that did not include step a, i.e., that did not pretreat the activated carbon.
Comparative example 27
This comparative example differs from example 7 in that the fluorination aid was prepared by a method that does not include step B, when step C is: dissolving potassium fluoride in water, uniformly mixing, adding pretreated activated carbon, soaking for 3h, and drying at 120 ℃ for 6h to obtain the fluorination auxiliary agent.
Comparative example 28
The present comparative example differs from example 7 in that the preparation method of the fluorination aid, step B, is: and (3) placing the pretreated activated carbon in a 1200r/min jet mill, then simultaneously spraying alumina powder, colliding at a high speed at 80 ℃, and drying the obtained material to obtain the activated carbon-based-alumina.
Comparative example 29
This comparative example differs from example 7 in that the process for the preparation of the fluorination aid, step B, is: uniformly mixing aluminum chloride powder, sodium hydroxide powder and water, filtering to obtain a precipitate, placing the precipitate and pretreated activated carbon in a 1200r/min jet mill, colliding at a high speed at 80 ℃, drying the obtained material, and heating to 180 ℃ to obtain the activated carbon-based-alumina.
First, the invention synthesizes the total yield of the reaction of o-trifluoromethyl benzoyl chloride
O-trifluoromethylbenzoyl chloride was synthesized according to the methods of examples 1 to 7 of the present invention and comparative examples 1 to 29, and the results are shown in Table 1, wherein the total yield of the reaction was calculated after the reaction was completed.
TABLE 1
As is clear from the results in Table 1, the total reaction yields of the o-trifluoromethylbenzoyl chloride synthesized according to the methods of examples 1 to 7 of the present invention were all 75% or more; especially, the total yield of the examples 5, 6 and 7 reaches 94-95%, and the reaction efficiency is higher.
Compared with the embodiment 1, the embodiment 2 has the advantages that the ceramic balls are prepared and added into the chlorination kettle, the chlorination reaction is promoted, and the total yield is obviously improved; on the basis of example 2, example 3 carries out non-polar modification on the TPU material for preparing the ceramic balls, and consequently the total yield is also improved. Compared with the example 1, the example 4 also prepares the fluorination auxiliary agent to be added into the fluorination kettle, so that the fluorination reaction is promoted, and the total yield is improved. As the initial raw material level o-xylene has more byproducts of the chlorination reaction and the fluorination reaction which are sequentially carried out, the invention respectively improves the utilization rate of chlorine and the utilization rate of hydrogen fluoride by designing the ceramic ball and the fluorination auxiliary agent, thereby improving the generation of target products.
Comparative examples 1-16 changed the preparation method of the ceramic balls compared to example 5; comparative examples 17-21 alter the method of making the modified TPU material compared to example 6; comparative examples 22-29 changed the preparation method of the fluorination assistant compared to example 7; as a result, the overall reaction yields of comparative examples 1 to 29 were all reduced to different degrees, indicating that the overall yield of o-trifluoromethylbenzoyl chloride could be increased only by the process according to the invention.
The invention has the beneficial effects that: the synthesis method of o-trifluoromethyl benzoyl chloride provided by the invention takes o-xylene as a starting material, has high reaction safety and is green and environment-friendly, and the utilization rate of chlorine and hydrogen fluoride is improved, byproducts are reduced, and the yield of a target product, i.e. o-trifluoromethyl benzoyl chloride, is comprehensively improved by preparing and adding the ceramic ball, the modified TPU material and the fluorinated assistant.
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 o-trifluoromethyl benzoyl chloride is characterized in that: the method specifically comprises the following steps:
(1) chlorination of
Adding o-xylene and a chlorination catalyst into a chlorination kettle, heating a jacket to 90-100 ℃, introducing dry chlorine into the chlorination kettle, stirring for reaction for 24 hours, sampling, and stopping the reaction when the content of 1- (dichloromethyl) -2- (trichloromethyl) benzene in a chlorination solution reaches 54-60% through gas chromatography analysis;
(2) fluorination of
Pumping the chlorination liquid into a fluorination kettle, adding a fluorination auxiliary agent, introducing hydrogen fluoride, introducing steam into a jacket, heating to 80 ℃ for reaction for 6 hours, cooling coil pipe chilled water to 50 ℃ after the reaction is finished, and putting liquid in the kettle into a distillation kettle for reduced pressure distillation to obtain a 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product;
(3) hydrolysis
Pumping the 1- (dichloromethyl) -2- (trifluoromethyl) benzene crude product into a hydrolysis kettle, adding water and a catalyst FeCl3Carrying out hydrolysis reaction at normal pressure, wherein the reaction temperature is 120 ℃, sampling after 5h of reaction, stopping the reaction after detecting that no 1- (dichloromethyl) -2- (trifluoromethyl) benzene exists in the hydrolysate, and then carrying out reduced pressure distillation on the hydrolysate to obtain a crude product of o-trifluoromethylbenzaldehyde;
(4) acyl chloride
Pumping the crude product of o-trifluoromethylbenzaldehyde into a reaction kettle, preserving heat by jacket steam, introducing dry chlorine gas at 80 ℃ for acyl chlorination reaction, sampling after 8h of reaction, transferring into a distillation kettle for reduced pressure distillation when no o-trifluoromethylbenzaldehyde is detected, and obtaining the crude product of o-trifluoromethylformyl chloride;
(5) rectification
And transferring the crude o-trifluoromethyl formyl chloride into a rectifying tower, introducing steam into a rectifying kettle jacket, and obtaining the finished o-trifluoromethyl benzoyl chloride after the rectification is finished.
2. The method for synthesizing o-trifluoromethylbenzoyl chloride as claimed in claim 1, characterized in that:
in the step (1), the mass ratio of the o-xylene to the chlorination catalyst is 1: (0.02-0.03), the introduction amount of chlorine is 0.22-0.26mol/h, and the chlorination catalyst is N, N-dimethylformamide or azobisisobutyronitrile;
the distillation conditions in the step (2) are-0.09 MPa and 100 ℃, and the introduction amount of the hydrogen fluoride is 0.5-0.7 mol/h;
the distillation conditions in the steps (3) and (4) are 100-: (2-4), catalyst FeCl3The dosage of the composition is 0.1-0.3%;
the introduction amount of the chlorine in the step (4) is 0.13-0.18 mol/h;
the distillation conditions in the step (5) are-0.09 MPa and 100-120 ℃.
3. A ceramic ball used in the method for synthesizing o-trifluoromethylbenzoyl chloride as recited in claim 1, wherein: when the reaction in the step (1) is started, adding the ceramic balls into a chlorination kettle, wherein the adding amount of the ceramic balls is 10-20% of the mass of o-xylene, and the ceramic balls are made of porous ceramic and modified TPU waterproof breathable films wrapped on the surfaces of the porous ceramic and the modified TPU waterproof breathable films.
4. A ceramic ball according to claim 3, wherein: the preparation method of the ceramic ball comprises the following steps:
s1, drying the porous ceramic, soaking the porous ceramic in silicone oil for 20-30min, filtering, and drying the obtained material in a centrifugal machine for 30-40min to obtain the pretreated porous ceramic;
s2, uniformly mixing the modified TPU, the nano silicon powder and the N, N-dimethylformamide, adding polyethylene glycol to prepare a coating liquid, spraying the coating liquid on the surface of the pretreated porous ceramic, immediately immersing the porous ceramic in deionized water for 2-3 days after spraying, and finally taking out and drying to obtain the finished ceramic ball.
5. Ceramic balls according to claim 4, characterized in that: in the step S2, the mass ratio of the modified TPU, the nano silicon powder, the N, N-dimethylformamide and the polyethylene glycol is 1: (0.04-0.1): (3-5): (0.02-0.06).
6. Ceramic balls according to claim 4, characterized in that: the pore diameter of the porous ceramic is 10-50 μm, the particle diameter is 1-3mm, and the apparent porosity is>60 percent; the volume weight distribution of the porous ceramic is as follows: 0.98-1.05 g/cm35-10% of the total weight of the composition, 1.1-1.2 g/cm315-25% of the total weight of the composition, 1.25-1.35g/cm320-40% of the total weight of the composition, 1.4-1.45g/cm38-15% of the total weight of the composition, 1.48-1.55g/cm3The balance is occupied.
7. A modified TPU material for the preparation of ceramic balls according to any of claims 3 to 6, characterized in that: the preparation method of the modified TPU material comprises the following steps:
a. uniformly mixing vinylamine and an initiator, then dropwise adding the tiglic anhydride, and stirring and reacting for 3-5h at the temperature of 80-100 ℃ to obtain a copolymerization product;
b. uniformly mixing polyethylene, the copolymerization product obtained in the step a and dicyclohexyl peroxydicarbonate, introducing the mixture into a double-screw extruder, extruding at the temperature of 140-;
c. uniformly mixing polyester type TPU granules and aromatic ester, and then introducing the mixture into a grinder with the temperature of 100-;
d. and uniformly mixing the granules I and the granules II, introducing the mixture into a double-screw extruder, and extruding at the temperature of 150-.
8. The modified TPU material of claim 7, wherein: in the step a, the mass ratio of vinylamine to tiglic anhydride is 1: (1.1-1.3), the initiator is azobisisobutyronitrile or azobisisoheptonitrile, and the amount of the initiator is 1-3% of the reaction raw material; in the step b, the mass ratio of the polyethylene to the copolymerization product to the dicyclohexyl peroxydicarbonate is 100: (5-10): (1-2); in the step c, the mass ratio of the polyester TPU granules to the aromatic ester is 1: (0.02-0.06); in the step d, the mass ratio of the first granules to the second granules is (0.1-0.3): 1.
9. a fluorination aid for use in the process for the synthesis of ortho-trifluoromethylbenzoyl chloride according to claim 1, characterized in that: the mass ratio of the fluorination auxiliary agent to the chlorination liquid is (0.5-0.7): the preparation method of the fluorination auxiliary agent comprises the following steps:
A. uniformly mixing tartaric acid and water, adding activated carbon, dispersing for 1-2h in a dispersion machine with the speed of 400-500r/min, and drying to obtain pretreated activated carbon;
B. placing the pretreated activated carbon in a 1000-1200r/min airflow crusher, then simultaneously spraying aluminum chloride powder, sodium hydroxide powder and water, colliding at a high speed at 60-80 ℃, drying the obtained material, and heating to 160-180 ℃ to obtain activated carbon-based-alumina;
C. dissolving potassium fluoride in water, uniformly mixing, adding activated carbon-based-alumina, soaking for 1-3h, and drying at 110-120 ℃ for 5-6h to obtain the fluorination auxiliary agent.
10. The fluorination aid of claim 9, wherein: the molar ratio of tartaric acid to potassium fluoride is (0.3-0.5): 1, the mass ratio of the activated carbon to the potassium fluoride is 1: (0.4-0.6); in the step B, the molar ratio of the aluminum chloride powder to the sodium hydroxide powder is 1: (3-3.6).
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