CN108484367A - A method of recycling 2,4- DI-tert-butylphenol compounds from 168 mother liquor of antioxidant - Google Patents
A method of recycling 2,4- DI-tert-butylphenol compounds from 168 mother liquor of antioxidant Download PDFInfo
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- CN108484367A CN108484367A CN201810207792.8A CN201810207792A CN108484367A CN 108484367 A CN108484367 A CN 108484367A CN 201810207792 A CN201810207792 A CN 201810207792A CN 108484367 A CN108484367 A CN 108484367A
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- antioxidant
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- mother liquor
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 36
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 34
- 239000012452 mother liquor Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 45
- 239000012044 organic layer Substances 0.000 claims description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- 235000006708 antioxidants Nutrition 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 18
- KIDXYAWWICJAFK-UHFFFAOYSA-N O.[Na].OC Chemical compound O.[Na].OC KIDXYAWWICJAFK-UHFFFAOYSA-N 0.000 claims description 17
- 230000006837 decompression Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 14
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 9
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229940043279 diisopropylamine Drugs 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000012259 ether extract Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 8
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical class CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical group CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- DWBZUUKLOFQIGX-UHFFFAOYSA-N azane;methylsulfinylmethane Chemical compound N.CS(C)=O DWBZUUKLOFQIGX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- CMFNMSMUKZHDEY-UHFFFAOYSA-N peroxynitrous acid Chemical compound OON=O CMFNMSMUKZHDEY-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
The invention belongs to chemical fields, and in particular to the method that one kind recycling 2,4 DI-tert-butylphenol compounds from 168 mother liquor of antioxidant.This method isolates and purifies in mother liquor 2,4 DI-tert-butylphenol compounds using the method for liquid-phase extraction, 2,4 high DI-tert-butylphenol compounds of purity is obtained finally by recrystallization by carrying out vacuum rotary steam processing to 168 mother liquor of specific antioxidant.This method process conditions are mild, easily-controllable, and the rate of recovery is high, has largely saved cost.
Description
Technical field
The invention belongs to chemical fields, and in particular to one kind recycling 2,4- di-tert-butyls from 168 mother liquor of antioxidant
The method of phenol.
Background technology
Antioxidant refer to those can alleviate high molecular material Auto-oxidation reaction speed, prevent material high temperature extrusion,
A kind of substance of oxidative degradation occurs when molding.Antioxidant 168 (phosphorous acid three (2,4- di-tert-butyls) ester) is one
Auxiliary antioxidant of the kind with splendid antioxidant effect, LD50 are more than or equal to 10000mg/kg, belong to practical nontoxicity grade
Not；It is a kind of hydrolysis low volatility phosphite ester, has the function of peroxynitrite decomposition compound, and hindered phenol anti-oxidants and is obstructed
Amine light stabilizer and with there is good synergistic effect, is widely used in the high scores such as polyethylene, polypropylene, makrolon, ABS resin
In sub- material.And 2,4-DTBP be produce plastic antioxidants important source material, be fine chemical product it is important in
Mesosome, is widely used in plastics, rubber, fuel oil etc., also can be used as Hinered phenols antioxidant, light stabilizer, insecticide, phenolic aldehyde tree
The raw material of fat, coating, adhesive etc..The country produces irgasfos 168, ultra-violet absorber by raw material of 2,4- DI-tert-butylphenol compounds
UV-327,980 type phenolic resin have formed large-scale production, and especially antioxidant 168 is as the novel of high molecular material
Antioxidant, consumption at home are very big.
Currently, the production technology of China's antioxidant 168 is mainly existed using 2,4-DTBP and phosphorus trichloride
It is synthesized under basic catalyst.(money Jian Hua, Liu Lin, the synthesis of Liu Chunsheng phosphorous acid three (2,4- di-tert-butyls) ester such as money Jian Hua
[J] Speciality Petrochemicals, 2001, (6):It 37-38.) has studied and is with 2,4 DI-tert-butylphenol compounds (2,4 diphenol), phosphorus trichloride
Primary raw material, FS1 (basic species) are catalyst, have synthesized antioxidant phosphorous acid three (2,4 di-tert-butyl-phenyl) ester under normal pressure,
The influence of raw material proportioning, catalyst amount, reaction temperature, reaction time to products collection efficiency, determining optimised process item are investigated
Part is：130 DEG C of reaction temperature, 2,4 diphenol: PCl3(the amount ratio of substance)=1: 0.34, reaction time 60min, catalyst amount
(to the mass ratio of 2,4 diphenol) 0.35%, average yield is 88.5% after recrystallization.Yang Yue equalitys (Yang Yueping, Hu Changying, clock
Huaining, Wang Zhiyuan, the degradation of Zeng Guangfeng antioxidants 168 and its measurement [J] the modern food science and technology of catabolite, 2016,
32(6):304-309.) research finds irgasfos 168 standard items and is added in polypropylene film, by ultraviolet or microwave
Processing can degrade, and generate catabolite.Using n-hexane as Extraction solvent, irgasfos 168 in polypropylene film is established
And its gas chromatography-mass spectrum of catabolite 2,4- DI-tert-butylphenol compounds and three (2,4- di-t-butyls phenyl) phosphates detection
Method；The result shows that：Irgasfos 168 is added in polypropylene through ultraviolet, microwave treatment, degradation rate is respectively 31.88%,
11.79%, 3 catabolites are generated, determine that two of which is 2,4-DTBP and three (2,4- bis--tertiary fourths by mark product
Base phenyl) phosphate, thus it is speculated that another loses the product of a ditertiary butylphenol for irgasfos 168；Irgasfos 168 standard items
Through ultraviolet or microwave treatment, degradation rate is below 5%.
Although however, more for researchs such as the preparation process of irgasfos 168, degradation characteristic, crystalline structures at present,
It is very few for the research of the recycling for the 2,4- DI-tert-butylphenol compounds for not having to react completely in irgasfos 168 mother liquor.For anti-
The large-scale production of oxidant 168, if can effectively recycle and be recycled for antioxygen by the 2,4-DTBP in mother liquor
The preparation of agent will save prodigious cost.
Invention content
It is returned from 168 mother liquor of antioxidant the technical problem to be solved by the present invention is in view of the foregoing drawbacks, provide one kind
The method for receiving 2,4- DI-tert-butylphenol compounds.This method process conditions are mild, easily-controllable, and the rate of recovery is high.
To achieve the goals above, the present invention adopts the following technical scheme that：
(1) acquisition of 168 mother liquor of antioxidant：With 2,4 DI-tert-butylphenol compounds, phosphorus trichloride for primary raw material, diisopropyl
Amine is catalyst, and after being reacted in solvent I, decompression steams solvent I, and solvent II is added and purifies 2-4 times, is recrystallized to give after purification
Product be antioxidant 168, remaining solution is 168 mother liquor of antioxidant；
(2) mother liquor pre-processes：Mother liquor pre-processes：After mother liquor decompression is steamed solvent II, with petroleum ether dissolution, solution is obtained
III；
(3) liquid-phase extraction：Solution III is washed with saturated nacl aqueous solution, is then extracted with sodium hydrate methanol solution
Organic layer 3 times, the water layers for merging 3 extractions are simultaneously acidified with hydrochloric acid, then with petroleum ether extraction 3 times, obtain organic layer I；Organic layer is used
Then pure water extracts organic layer 3 times with sodium hydrate methanol solution, the water layers for merging 3 extractions are simultaneously acidified with hydrochloric acid, then
With petroleum ether extraction 3 times, organic layer II is obtained；
(4) it recrystallizes：Organic layer II pure waters, then dried with magnesium sulfate, up to 2,4 two after cooling, filtering, drying
Tert-butyl phenol.
Further, in above-mentioned steps (1), solvent I is selected from one or both of dimethylbenzene, toluene.
Further, in above-mentioned steps (1), solvent II is selected from one or both of isopropanol, hexamethylene.
Further, in above-mentioned steps (1), the molar ratio of 2,4 DI-tert-butylphenol compounds and phosphorus trichloride is (3.0-3.1):1,
The dosage of catalyst is the 0.5-1.0% of 2,4 DI-tert-butylphenol compounds quality.
Further, the volume ratio of phosphorus trichloride and solvent I are 1:30.
Further, the step (1) is：2,4 DI-tert-butylphenol compounds and diisopropylamine are mixed with solvent I, by temperature
It rises to 42-45 DEG C and keeps, phosphorus trichloride is added dropwise, after reacting 70-90min, decompression steams solvent I, and solvent II is added and carries
2-4 times pure, the product being recrystallized to give after purification is antioxidant 168, and remaining solution is 168 mother liquor of antioxidant.
In 168 producing process of antioxidant, experiments have shown that using diisopropylamine as catalyst, relative to liquefied ammonia, bromination tetrem
The catalyst such as ammonium are capable of the hydrochloric acid of better absorbing reaction generation, improve the conversion ratio of product, have better catalytic activity.
Further, in above-mentioned steps (3), saturated sodium-chloride is 1 with solution III volume ratio:2, sodium hydrate methanol solution
It is 1 with solution III volume ratio:(3-4).
Further, a concentration of 1.0-2.5mol/L of sodium hydrate methanol solution.
Further, in step (3), pure water is 1 with solution III volume ratio:2.
Further, in step (3), for the first time and pH value of solution is all adjusted to 6-7 by second of hydrochloric acid acidification.
Further, in step (4), pure water is 1 with organic layer II volume ratios：(3-4), magnesium sulfate drying time are 8-10h.
The technical solution of the application has following advantage：
2,4 DI-tert-butylphenol compounds are separated and recovered relative to resin adsorption and the very big journey of rectifying from mother liquor using liquid-phase extraction
Reduce cost recovery on degree, and liquid-phase extraction is without high-temperature high-voltage reaction, it is easy to operate, easily-controllable, and the rate of recovery is high, quality
It is good, it is at low cost；It solves waste water handling problem, and has recycled 2,4 DI-tert-butylphenol compounds in mother liquor, recycled to reach
Purpose, economize on resources, realize the unification of environmental benefit and economic benefit.
In above-mentioned technical proposal, reaction raw materials selection, the selection of catalyst, the selection of extractant, reagent dosage, reaction when
Between, reaction temperature, be all to be obtained by long-term complicated experiment, be that the synergistic effect of above-mentioned many factors supports jointly
Advantageous effect of the invention.
Specific implementation mode
The present invention is further elaborated with reference to embodiments.These embodiments be only for illustrative purposes,
And do not limit the scope of the invention and essence.For those of ordinary skill in the art to which the present invention belongs, it is not departing from
Under the premise of inventive concept, a number of simple deductions or replacements can also be made, is regarded as belonging to the scope of protection of the present invention.
Embodiment 1
7.004g (0.034moL) 2 is added in the reaction bulb equipped with mechanical agitator, thermometer and reflux condensing tube,
4 DI-tert-butylphenol compounds, 0.07g diisopropylamines and the mixing of 30mL dimethylbenzene, rise to 45 DEG C by temperature and keep, trichlorine is added dropwise
Change phosphorus 1mL (0.011moL), after reacting 80min, decompression steams dimethylbenzene, and isopropanol is added and purifies 3 times, is recrystallized after purification
To product be antioxidant 168, remaining solution is 168 mother liquor of antioxidant.
After the decompression of 168 mother liquor of antioxidant steams isopropanol, with petroleum ether dissolution and it is settled to 50mL, chlorine is saturated with 25mL
Change sodium solution washing, the sodium hydrate methanol solution of 12.5mL2.0mol/L is then used to extract organic layer 3 times, merges 3 extractions
Water layer and hydrochloric acid is added to be acidified to pH is 7, then with 30mL petroleum ether extractions 3 times, obtain organic layer I；Organic layer 25mL pure water
Washing, then uses 12.5mL2.0mol/L sodium hydrate methanol solutions extraction organic layer 3 times, and the water layer for merging 3 extractions is used in combination
It is 7 that hydrochloric acid, which is acidified to pH, then with 30mL petroleum ether extractions 3 times, obtains organic layer II；
Organic layer II twice, then with magnesium sulfate dries 10h with 30mL pure waters, cooling, filtering, it is dry after white knot
Brilliant 2,4 DI-tert-butylphenol compounds.It is 90.8% to test obtained 168 yield of antioxidant, 2,4 two uncle of white crystal recycled
Butylphenol, it is 97.0% that liquid chromatogram, which measures purity, the rate of recovery 94.7%, 54.5-55.5 DEG C of fusing point.
Embodiment 2
6.798g (0.033moL) 2 is added in the reaction bulb equipped with mechanical agitator, thermometer and reflux condensing tube,
4 DI-tert-butylphenol compounds, 0.07g diisopropylamines and the mixing of 30mL toluene, rise to 42 DEG C by temperature and keep, tri-chlorination is added dropwise
Phosphorus 1mL (0.011moL), after reacting 90min, decompression steams toluene, and hexamethylene is added and purifies 3 times, is recrystallized to give after purification
Product is antioxidant 168, and remaining solution is 168 mother liquor of antioxidant.
After the decompression of 168 mother liquor of antioxidant steams hexamethylene, with petroleum ether dissolution and it is settled to 50mL, chlorine is saturated with 25mL
Change sodium solution washing, the sodium hydrate methanol solution of 15mL2.5mol/L is then used to extract organic layer 3 times, merges 3 extractions
Water layer and hydrochloric acid is added to be acidified to pH is 6.8, then with 30mL petroleum ether extractions 3 times, obtain organic layer I；Organic layer 25mL pure water
Washing, then uses 12.5mL2.0mol/L sodium hydrate methanol solutions extraction organic layer 3 times, and the water layer for merging 3 extractions is used in combination
It is 7 that hydrochloric acid, which is acidified to pH, then with 30mL petroleum ether extractions 3 times, obtains organic layer II；
Organic layer II twice, then with magnesium sulfate dries 10h with 30mL pure waters, cooling, filtering, it is dry after white knot
Brilliant 2,4 DI-tert-butylphenol compounds.It is 89.3% to test obtained 168 yield of antioxidant, 2,4 two uncle of white crystal recycled
Butylphenol, it is 96.1% that liquid chromatogram, which measures purity, the rate of recovery 93.5%, 54.0-55.5 DEG C of fusing point.
Embodiment 3
7.004g (0.034moL) 2 is added in the reaction bulb equipped with mechanical agitator, thermometer and reflux condensing tube,
4 DI-tert-butylphenol compounds, 0.07g catalyst and the mixing of 30mL dimethylbenzene, rise to 45 DEG C by temperature and keep, tri-chlorination is added dropwise
Phosphorus 1mL (0.011moL), after reacting 80min, decompression steams dimethylbenzene, and isopropanol is added and purifies 3 times, is recrystallized to give after purification
Product be antioxidant 168, remaining solution is 168 mother liquor of antioxidant.
After the decompression of 168 mother liquor of antioxidant steams isopropanol, with petroleum ether dissolution and it is settled to 50mL, chlorine is saturated with 25mL
Change sodium solution washing, the sodium hydrate methanol solution of 12.5mL2.0mol/L is then used to extract organic layer 3 times, merges 3 extractions
Water layer and hydrochloric acid is added to be acidified to pH is 7, then with 30mL petroleum ether extractions 3 times, obtain organic layer I；Organic layer 25mL pure water
Washing, then uses 12.5mL2.0mol/L sodium hydrate methanol solutions extraction organic layer 3 times, and the water layer for merging 3 extractions is used in combination
It is 7 that hydrochloric acid, which is acidified to pH, then with 30mL petroleum ether extractions 3 times, obtains organic layer II；
Organic layer II twice, then with magnesium sulfate dries 10h with 30mL pure waters, cooling, filtering, it is dry after white knot
Brilliant 2,4 DI-tert-butylphenol compounds.Table 1 is that catalyst is processed to product yield and subsequent recovery in 168 preparation process of antioxidant
The influence of journey.
Influence of 1 catalyst of table to product yield and recovering effect
| Catalyst | Diisopropylamine | Liquefied ammonia | Dimethyl sulfoxide | Teabrom |
| 168 yield % of antioxidant | 90.8 | 80.2 | 82.3 | 83.6 |
| 2,4 DI-tert-butylphenol compounds recycle purity % | 97.0 | 90.1 | 88.4 | 87.9 |
| 2,4 DI-tert-butylphenol compounds rate of recovery % | 94.7 | 87.6 | 80.6 | 83.8 |
Embodiment 4
7.004g (0.034moL) 2 is added in the reaction bulb equipped with mechanical agitator, thermometer and reflux condensing tube,
4 DI-tert-butylphenol compounds, 0.07g diisopropylamines and the mixing of 30mL dimethylbenzene, rise to 45 DEG C by temperature and keep, trichlorine is added dropwise
Change phosphorus 1mL (0.011moL), after reacting 80min, decompression steams dimethylbenzene, and isopropanol is added and purifies 3 times, is recrystallized after purification
To product be antioxidant 168, remaining solution is 168 mother liquor of antioxidant.
After the decompression of 168 mother liquor of antioxidant steams isopropanol, with petroleum ether dissolution and it is settled to 50mL, chlorine is saturated with 25mL
Change sodium solution washing, the liquid-phase extraction liquor of 12.5mL2.0mol/L is then used to extract organic layer 3 times, merges 3 extractions
Water layer and hydrochloric acid is added to be acidified to pH is 7, then with 30mL petroleum ether extractions 3 times, obtain organic layer I；Organic layer is washed with 25mL pure water
It washs, then uses 12.5mL2.0mol/L sodium hydrate methanol solutions extraction organic layer 3 times, merge the water layer of 3 extractions and use salt
It is 7 that acid, which is acidified to pH, then with 30mL petroleum ether extractions 3 times, obtains organic layer II；
Organic layer II twice, then with magnesium sulfate dries 10h with 30mL pure waters, cooling, filtering, it is dry after white knot
Brilliant 2,4 DI-tert-butylphenol compounds.Table 2 is influence of the selection for recovering effect of liquid-phase extraction liquid.
Influence of the 2 liquid-phase extraction liquid of table to recovering effect
Embodiment 5
7.004g (0.034moL) 2 is added in the reaction bulb equipped with mechanical agitator, thermometer and reflux condensing tube,
4 DI-tert-butylphenol compounds, 0.07g diisopropylamines and the mixing of 30mL dimethylbenzene, rise to 45 DEG C by temperature and keep, trichlorine is added dropwise
Change phosphorus 1mL (0.011moL), after reacting 80min, decompression steams dimethylbenzene, and isopropanol is added and purifies 3 times, is recrystallized after purification
To product be antioxidant 168, remaining solution is 168 mother liquor of antioxidant.
After the decompression of 168 mother liquor of antioxidant steams isopropanol, with petroleum ether dissolution and it is settled to 50mL, chlorine is saturated with 25mL
Change sodium solution washing, the sodium hydrate methanol solution of 2.0mol/L is then used to extract organic layer 3 times, merges the water layer of 3 extractions
And it is 7 that hydrochloric acid, which is added, to be acidified to pH, then with 30mL petroleum ether extractions 3 times, obtain organic layer I；Organic layer 25mL pure waters, so
12.5mL2.0mol/L sodium hydrate methanol solutions extraction organic layer is used afterwards 3 times, merge the water layer of 3 extractions and be acidified with hydrochloric acid
It is 7 to pH, then with 30mL petroleum ether extractions 3 times, obtains organic layer II；
Organic layer II twice, then with magnesium sulfate dries 10h with 30mL pure waters, cooling, filtering, it is dry after white knot
Brilliant 2,4 DI-tert-butylphenol compounds.Table 2 is influence of the selection for recovering effect for also wanting to extract liquor.Table 2 is the choosing of liquid-phase extraction liquid
Select the influence for recovering effect.
Influence of the 3 liquid-phase extraction liquid dosage of table to recovering effect
The technical solution of the application, links linking is close, and collocation is reasonable, indispensable, this specific combination structure
At preparation method, produce apparent synergistic function.
The foregoing is merely the preferred embodiments of the application, are not intended to limit the scope of the claims of the application, every utilization
Equivalent structure or equivalent flow shift made by present specification is applied directly or indirectly in other relevant technology necks
Domain includes similarly in the scope of patent protection of the application.
Claims (10)
1. a kind of method for recycling 2,4-DTBP in 168 mother liquor from antioxidant, which is characterized in that including following step
Suddenly：
(1) acquisition of 168 mother liquor of antioxidant：With 2,4 DI-tert-butylphenol compounds, phosphorus trichloride for primary raw material, diisopropylamine is
Catalyst, after being reacted in solvent I, decompression steams solvent I, and solvent II is added and purifies 2-4 times, the production being recrystallized to give after purification
Product are antioxidant 168, and remaining solution is 168 mother liquor of antioxidant；
(2) mother liquor pre-processes：After mother liquor decompression is steamed solvent II, with petroleum ether dissolution, solution III is obtained；
(3) liquid-phase extraction：Solution III is washed with saturated nacl aqueous solution, is then extracted with sodium hydrate methanol solution organic
Layer 3 times, the water layers for merging 3 extractions are simultaneously acidified with hydrochloric acid, then with petroleum ether extraction 3 times, obtain organic layer I；Organic layer pure water
Then washing extracts organic layer 3 times with sodium hydrate methanol solution, the water layers for merging 3 extractions are simultaneously acidified with hydrochloric acid, then use stone
Oily ether extracts 3 times, obtains organic layer II；
(4) it recrystallizes：Organic layer II twice, then with magnesium sulfate is dried with pure water, up to 2,4 two after cooling, filtering, drying
Tert-butyl phenol.
2. according to the method described in claim 1, it is characterized in that, in the step (1), solvent I is in dimethylbenzene, toluene
One or two.
3. according to the method described in claim 1, it is characterized in that, in the step (1), solvent II is selected from isopropanol, hexamethylene
One or both of alkane.
4. according to the method described in claim 1, it is characterized in that, in the step (1), 2,4 DI-tert-butylphenol compounds and trichlorine
The molar ratio for changing phosphorus is (3.0-3.1)：1, the dosage of catalyst is the 0.5-1.0% of 2,4 DI-tert-butylphenol compounds quality.
5. according to claim 1-4 any one of them methods, which is characterized in that the step (1) is：By 2,4 di-t-butyls
Phenol (2,4 diphenol) and diisopropylamine are mixed with solvent I, and temperature is risen to 42-45 DEG C and is kept, phosphorus trichloride is added dropwise,
After reacting 70-90min, decompression steams solvent I, and solvent II is added and purifies 2-4 times, and the product being recrystallized to give after purification is anti-
Oxidant 168, remaining solution are 168 mother liquor of antioxidant.
6. according to the method described in claim 1, it is characterized in that, in the step (3), saturated sodium-chloride and solution III body
Product is than being 1:2, sodium hydrate methanol solution is 1 with solution III volume ratio：(3-4).
7. according to the method described in claim 6, it is characterized in that, a concentration of 1.0- of the sodium hydrate methanol solution
2.5mol/L。
8. according to the method described in claim 1, it is characterized in that, in the step (3), pure water is with solution III volume ratio
1:2。
9. according to the method described in claim 1, it is characterized in that, in the step (3), it is acidified for the first time with second of hydrochloric acid
PH value of solution is all adjusted to 6-7.
10. according to the method described in claim 1, it is characterized in that, in the step (4), pure water and organic layer II volume ratios
It is 1：(3-4), magnesium sulfate drying time are 8-10h.
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| CN114057548A (en) * | 2021-12-03 | 2022-02-18 | 陕西艾科莱特新材料有限公司 | Method for recovering 2, 4-di-tert-butylphenol from antioxidant 168 concentrated mother liquor |
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| CN114057548A (en) * | 2021-12-03 | 2022-02-18 | 陕西艾科莱特新材料有限公司 | Method for recovering 2, 4-di-tert-butylphenol from antioxidant 168 concentrated mother liquor |
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