CN105585454B - Preparation method of hindered bisphenol antioxidant - Google Patents
Preparation method of hindered bisphenol antioxidant Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 30
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 30
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 29
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001953 recrystallisation Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 59
- 239000002253 acid Substances 0.000 claims description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 19
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 238000001291 vacuum drying Methods 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 9
- 238000000967 suction filtration Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000008098 formaldehyde solution Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 28
- 239000006227 byproduct Substances 0.000 description 12
- -1 2, 6- DI-tert-butylphenol compounds Chemical class 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 239000002530 phenolic antioxidant Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 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 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a hindered bisphenol antioxidant, which comprises the following process steps of adding 2, 6-di-tert-butylphenol and a catalyst into a reaction vessel, adding 3-8m L catalyst into 1mol of 2, 6-di-tert-butylphenol, stirring to be molten at the temperature of 40-60 ℃, adding a formaldehyde solution, wherein the molar ratio of formaldehyde to 2, 6-di-tert-butylphenol is 1: 2.0-2.2, heating to 60-80 ℃ after the addition is finished, reacting for 2-5 hours, carrying out suction filtration, washing for 3-5 times by using hot water at 40-50 ℃, carrying out vacuum drying on a filter cake, recrystallizing a crude product, adding 0.5-5m L recrystallization solvent into each 1g of the crude product, and carrying out vacuum drying to obtain a yellow needle crystal.
Description
Technical field
The present invention relates to a kind of preparation method of antioxidant for lubricant oil, more particularly to a kind of system of hindered bisphenol type antioxidant
Preparation Method.
Background technology
Antioxidant can significantly improve oil ageing stability, prevent oil product putrid and deteriorated.In different types of antioxygen
It is a kind of very effective chain terminating agent to shield phenolic antioxidant of the phenol as representative in agent.Hindered bisphenol antioxidant refers to using
Alkylidene or sulfide linkage are directly connected to the phenolic antioxidant of two phenol units that are obstructed.Compared with single phenol type, the volatilization of bisphenol type and
Extraction loss is small, and thermal stability is high, and anti-aging effect is good.Currently, it is related by resistance type bis-phenolic antioxidants, 4,4'- di-2-ethylhexylphosphine oxides (2,
6- DI-tert-butylphenol compounds) preparation process report it is less, domestic existing preparation process by-product is more, the product differentiation of every batch of
Greatly.
Application No. is 200810072071.7 patents of invention to disclose a kind of high 4,4' content dihydroxy of one-step synthesis method
The method of base diphenyl methane refers to a kind of preparation process of high 4, the 4' content bis-phenol of synthesis, which is first
Phenol is added to the container, heating water bath, after phenol melting, phosphoric acid is added and is stirred obtained mixed liquor, then to mixed liquor
Middle addition formalin, isolates acid after reaction, oil phase is neutralized with sodium bicarbonate, and vacuum distillation removes phenol and water, through cold
But it, crystallizes, obtain product after filtering, but in the preparation process reaction process, since the ortho position of raw material phenol does not have substituent group,
Even if adjusting the generation of unavoidable several isomers if catalyst and process conditions, so the yield of target product is only
60% can be reached.
Application No. is 200610097976.0 patents of invention to disclose a kind of bisphenol compound antioxidant product for preparing
The method of process for cleanly preparing, which, which mainly uses, contains anion surfactant, acidic catalyst
Water is reaction dissolvent, using free-of-liquid fat aldehyde and dialkyl group phenol as raw material, through condensation reaction, generates bisphenol compound antioxidant production
Product.Although dicyandiamide solution of the reaction process based on water can reuse, number of repetition is limited, therefore in production process
A certain amount of waste water containing organic matter and acid impurities is still will produce, is unfavorable for the protection of environment, and filter the filter of gained
Cake also needs to recrystallize, and to increase power consumption, increases reaction cost.
Application No. is 201110463103.8 patents of invention to disclose a kind of clean manufacturing side preparing bis-phenolic antioxidants
Method, it mainly carries out reacting under the action of catalyst preparing bis-phenol kind antioxidant by alkyl phenol with aldehyde material, the preparation
Method is to put into alkyl substituted phenol, lower alcohols solvent, catalyst in reaction kettle successively, and stirring heating is slowly added dropwise
Formalin maintains the reflux for reacting, and generates mass crystallization, and the reaction was continued a period of time, cools down after being neutralized with organic acid, mistake
Filter, obtains solid powdery product.For the preparation method process using highly basic NaOH, KOH solid as catalyst, industrial alcohols are solvent
It prepares by resistance type bisphenol compound, i.e., 4,4 '-di-2-ethylhexylphosphine oxides (2,6- DI-tert-butylphenol compounds), needs consumption big in preparation process
Amount solvent, usage amount 2,5-10 times (molar ratio) of 6- DI-tert-butylphenol compounds, meanwhile, the usage amount of solvent excessively will increase
The cost recovery of solvent.
Invention content
The object of the present invention is to provide a kind of preparation methods of hindered bisphenol type antioxidant, and this method is simple for process, reaction
Condition is relatively soft, and yield is high, and purity is high, at low cost.
To achieve the above object, the present invention provides a kind of preparation method of hindered bisphenol type antioxidant, including following technique
Step：2,6- DI-tert-butylphenol compounds and catalyst are added into reactor, 3-8mL is added in 2, the 6- DI-tert-butylphenol compounds per 1mol
Catalyst is stirred under 40-60 DEG C of temperature condition to molten, addition formalin, formaldehyde and 2,6- DI-tert-butylphenol compounds
Molar ratio is 1：2.0-2.2 is warming up to 60-80 DEG C after the completion of addition, react 2-5 hours, filtered, with 40-50 DEG C of hot water
Washing 3-5 times, filter cake vacuum drying, recrystallizes crude product, 0.5-5mL recrystallization solvents is added per 1g crude products, through vacuum
It is dry, obtain yellow needle-like crystals；
Wherein specific reaction equation is as follows：
Raw material 2,6- DI-tert-butylphenol compounds are heated to fusing point or more, can not only be used at the reaction temperatures in the preparation method
Raw material avoids the use of organic solvent but also as solvent, can be conducive to the protection of environment while reducing cost again.
The preparation method of hindered bisphenol type antioxidant of the present invention, wherein the preferred mixed acid solution of the catalyst,
The volume ratio of strong acid during mixed acid solution at this time includes at least one weak acid and is at least one, the weak acid and middle strong acid is preferred
1:1。
Using the mixed acid solution of weak acid and middle strong acid as catalyst, it is strong to avoid the strong acid such as sulfuric acid, hydrochloric acid, sodium hydroxide
The direct use of alkali, slows down the severe degree of reaction while ensure that catalytic effect, reduce the generation of by-product.Waste water passes through
After adjusting PH to neutrality, it can be recycled.
The preparation method of hindered bisphenol type antioxidant of the present invention, wherein the preferred acetic acid of the weak acid, carbonic acid or two
Person combines, the preferred phosphoric acid of the middle strong acid, formic acid or both combination.
The preparation method of hindered bisphenol type antioxidant of the present invention, wherein the preferred purity >=99wt% of the acetic acid,
Preferred purity >=the 85wt% of phosphoric acid, the preferred purity >=99wt% of formic acid, the saturated aqueous solution of carbonic acid preferably carbon dioxide.
The preparation method of hindered bisphenol type antioxidant of the present invention, wherein the preferred toluene of the recrystallization solvent and different
The volume ratio preferably 1 of the mixed solution of octane, the toluene and isooctane:1.
It is recrystallization solvent to select toluene and isooctane, and recrystallization solvent dosage is few, is easily recycled uses, product color with
Crystal form is more preferably.
The preparation method of hindered bisphenol type antioxidant of the present invention, wherein the preferred 37- of formalin concentration
40wt%.
The preparation method of hindered bisphenol type antioxidant of the present invention, wherein the addition manner of the formalin is preferred
It is added at one time or is added dropwise addition.
The preparation method of hindered bisphenol type antioxidant of the present invention, wherein reaction vessel before formalin addition
Preferred 45-55 DEG C of interior temperature.
In above-mentioned temperature range, it can both ensure that 2,6- DI-tert-butylphenol compounds were liquid, and can prevent that formaldehyde is added
Shi Fanying excessively acutely generates by-product.
The preparation method of hindered bisphenol type antioxidant of the present invention, wherein the formaldehyde and 2,6- DI-tert-butylphenol compounds
Molar ratio preferably 1：2.05-2.10.
The present invention is prepared using solventless method by resistance type bis-phenolic antioxidants, is by 2,6- DI-tert-butylphenol compounds raw material and catalysis
Agent is heated to molten condition, and formalin is then added, and can be obtained target after reacting a period of time under the conditions of certain temperature
Crude product.Crude product is recrystallized again, just obtain high-purity by resistance type bis-phenolic antioxidants.
In preparation process, by being heated to fusing point or more to 2,6- DI-tert-butylphenol compounds, make 2,6- DI-tert-butylphenol compounds
While as reactant, solvent action is also played, therefore is not required to the addition organic solvents such as methanol or ethyl alcohol, it is molten to abandon alcohols polarity
The use of agent, not only saves raw material, reduces cost, moreover it is possible to reduce discharge, environmental protection.
Since the phenolic hydroxyl group ortho position of 2,6- DI-tert-butylphenol compounds is occupied by tertiary butyl, only phenolic hydroxyl group contraposition is prone to hydroxyl
Aldehyde condensation reaction, by-product is few, relatively low to the Active pharmaceutical of catalyst, and diluted acid can be used as the catalyst of reaction.With weak
Acid is that catalyst slows down the severe degree of reaction while ensureing catalytic effect, reduces the generation of by-product.Wash work
After the adjusted PH to neutrality of filtrate in skill, it can be recycled.Using toluene and isooctane as recrystallization solvent, dosage is few, decompression
Distillation recovery is easier, and more preferably, purity is high for product color and crystal form.
It is characteristic of the invention that：The present invention is not required to addition alcohol organic solvent, and simple production process is at low cost, prepares work
By-product in skill is few, and antioxidant purity and yield are high, and are conducive to the protection of environment, compared with single phenol antioxidant, bisphenol type
Antioxidant molecular weight increases, and reduces volatility and toxicity, improves antioxygen efficiency, more suitable for making at relatively high temperatures
With can be used for industrial lubricant and I. C. engine oil.
Description of the drawings
Fig. 1 is infrared (FTIR) spectrogram of 4,4' methylene bis (2,6 di t butyl phenol) prepared by the present invention.
Fig. 2 be the present invention prepare 4,4' methylene bis (2,6 di t butyl phenol) nuclear-magnetism (1H-NMR) spectrogram.
Fig. 3 be the present invention prepare 4,4' methylene bis (2,6 di t butyl phenol) nuclear-magnetism (13C-NMR) spectrogram.
Fig. 4 is the differential scanning calorimetry instrument (DSC) of 4,4' methylene bis (2,6 di t butyl phenol) prepared by the present invention
Spectrogram.
Fig. 5 is the chemical equation that the present invention prepares 4,4' methylene bis (2,6 di t butyl phenol).
Specific implementation mode
The present invention is described in further detail with reference to specific embodiment, but the present invention is not by following embodiments
Limitation.The change of any design and scope without departing from the present invention, is within the scope of the present invention.
Catalyst charge：
In the present invention, the addition of catalyst is not particularly limited, usually relative to 2,6-, bis- uncles of every 1mol
Catalyst 3-8mL is added in butylphenol.If the catalyst that the 2,6 di t butyl phenol relative to every 1mol is added is less than 3mL
When, then there are catalytic effect unobvious, the possibility that reaction is slow, reaction is incomplete, reaction can not carry out.And if relative to every
When the catalyst that 2, the 6- DI-tert-butylphenol compounds of 1mol are added is more than 8mL, then other than increasing cost, by-product is more,
Better catalytic effect can not be obtained.
Catalyst type：
In the present invention, the type of catalyst is not particularly limited, usually selects mixed acid solution, for example, comprising extremely
A kind of few mixed acid solution of weak acid and at least one middle strong acid.
The weak acid can for example be enumerated：Acetic acid, carbonic acid or combination thereof.The middle strong acid can for example be enumerated：Phosphorus
Acid, formic acid or combination thereof.Using the mixed acid solution of weak acid and middle strong acid as catalyst, sulfuric acid, hydrochloric acid, hydrogen-oxygen are avoided
The direct use for changing the strong acid and strong bases such as sodium slows down the severe degree of reaction while ensure that catalytic effect, reduce by-product
Generation.After the adjusted PH to neutrality of waste water, it can be recycled.
The acetic acid can for example select the acetic acid of purity >=99wt%, the phosphoric acid can for example select purity >=
The phosphoric acid of 85wt%, the formic acid can for example select the formic acid of purity >=99wt%, the carbonic acid that can for example select dioxy
Change the saturated aqueous solution of carbon.
The volume ratio of the weak acid and middle strong acid preferably 1:1.If the dosage of weak acid is less than middle strong acid, there is reaction
Not exclusively, the relatively low possibility of yield.And if when the dosage of weak acid is more than middle strong acid, there is reaction acutely, by-product is more
Possibility.
The ratio of formaldehyde and 2,6 di t butyl phenol：
In the present invention, the ratio of PARA FORMALDEHYDE PRILLS(91,95) and 2,6- DI-tert-butylphenol compounds is not particularly limited, usually molar ratio 1：
2.0-2.2 preferably 1：2.05-2.10.If the molar ratio of formaldehyde and 2,6 di t butyl phenol is less than 1：When 2.2,2,6-
The dosage that DI-tert-butylphenol compounds are used as solvent is excessive, other than increasing cost, has no other beneficial effects.And if formaldehyde
It is more than 1 with the molar ratio of 2,6 di t butyl phenol：When 2.0, formaldehyde is excessive in reaction process, may influence the pure of product
Degree.
The addition of recrystallization solvent：
In the present invention, the addition of recrystallization solvent is not particularly limited, is usually added relative to every 1g crude products
Enter 0.5-5mL recrystallization solvents.If be less than 0.5mL relative to the recrystallization solvent that every 1g crude products are added, exist and divide
It is poor from the effect of purifying, the not high possibility of products obtained therefrom purity.And if the recrystallization relative to the addition of every 1g crude products is molten
When agent is more than 5mL, then recrystallization solvent dosage is excessive, low yield, increases cost recovery.
The type of recrystallization solvent：
In the present invention, the type of recrystallization solvent is not particularly limited, such as toluene and isooctane can be selected
Mixed solution.
The volume ratio of the toluene and isooctane preferably 1:1.If the dosage of toluene is less than isooctane, exists and tie again
The possibility of brilliant low yield.And if when the dosage of toluene is more than isooctane, there is the possibility for increasing cost.
It stirs to the temperature condition of molten：
In the present invention, the temperature condition stirred to molten is not particularly limited, usually 40-60 DEG C.If stirred
When mixing to the temperature of molten less than 40 DEG C, then 2,6- DI-tert-butylphenol compounds fusing points are not reached, are not homogeneous solutions.And if stirred
It mixes when being more than 60 DEG C to the temperature of molten, then it is excessively high to there is temperature, and it is violent to be added dropwise formaldehyde reaction, the more possibility of by-product.
Add heat up after the completion of formalin temperature condition extremely：
In the present invention, to heat up after the completion of addition formalin temperature extremelyConditionIt is not particularly limited, usually
60-80℃.If the institute's temperature extremely that heats up after the completion of adding formalin is less than 60 DEG C, there is the incomplete of reaction, produce
The lower possibility of rate.And if when the institute's temperature extremely that heats up after the completion of addition formalin is more than 80 DEG C, it is more to there is generation
By-product possibility.
The concentration of formalin：
In the present invention, the concentration of PARA FORMALDEHYDE PRILLS(91,95) solution is not particularly limited, usually 37-40wt%.Formaldehyde is molten at room temperature
The saturated concentration of liquid is 37-40wt%.
The addition manner of formalin：
In the present invention, the addition manner of PARA FORMALDEHYDE PRILLS(91,95) solution is not particularly limited, for example, can select be added at one time or
The addition manner being added is added dropwise in person.
Prepare the reaction time of catalyst：
In the present invention, the reaction time for preparing catalyst is not particularly limited, usually 2-5 hours.If reaction
When time is less than 2 hours, then there is the incomplete possibility of reactant reaction.And if when the reaction time is more than 5 hours, exist
Increase energy consumption, the possibility that by-product increases.
The temperature condition of water used in suction filtration：
In the present invention, the temperature condition of water used in suction filtration is not particularly limited, usually 40-50 DEG C.If institute
When being less than 40 DEG C with the temperature of water, then it is not up to fusing point in the presence of 2,6- DI-tert-butylphenol compounds, the possibility that can not be filtered out.And if institute
When being more than 50 DEG C with the temperature of water, then other than increasing cost, other beneficial effects are had no.
Washing times in suction filtration：
In the present invention, the washing times in suction filtration are not particularly limited, usually 3-5 times.If washing times are small
When 3 times, then in the presence of washing be not thorough, in product residual impurity possibility.And if washing times be more than 5 times when, in addition to
It increases except cost, has no other beneficial effects.
Embodiment 1：
The 2,6- of 422g (2.05mol) is added in the 1L reaction kettles equipped with mechanical agitation, thermometer and reflux condensing tube
The mixed acid solution (5mL acetic acid and 5mL phosphoric acid) of DI-tert-butylphenol compounds, 10mL, 60 DEG C of heating water baths wait for 2,6- di-tert-butyls
Phenol fully melts, and 99.48mL formalins (37wt%) (1mol) are added dropwise, and after being added dropwise, 70 DEG C of water bath with thermostatic control stirrings 3 are small
When.It is washed 4 times with 50 DEG C of deionized waters, each deionized water dosage 400mL, until washing lotion is neutrality, after decompression filters, vacuum is dried
It is 24 hours dry.It is recrystallized with 800mL toluene and isooctane mixed solvent, toluene and each 400mL of isooctane, through filtering, vacuum is dried
Yellow needle-like crystals 360g is obtained after dry, yield is 85% after testing, purity 99.7%.
And products obtained therefrom is characterized, characterization result is shown in shown in Fig. 1, Fig. 2, Fig. 3, Fig. 4：
As shown in Figure 1,3636cm-1Neighbouring absorption peak corresponds to phenolic hydroxyl group；2949-2952cm-1Neighbouring absorption peak,
Corresponding to the asymmetric stretching vibration of methyl and methylene；2870-2876cm-1Neighbouring absorption peak corresponds to methyl and methylene
Symmetrical stretching vibration；1385-1398cm-1Neighbouring absorption peak is the symmetrical deformation vibration of methyl；1250cm-1Neighbouring suction
It receives peak and corresponds to carbon-to-carbon symmetrical deformation vibration；770cm-1Neighbouring absorption peak is the absorption peak of four substituted benzene rings.
As shown in Figure 2, the chemical shift of each hydrogen and peak area integral (1H-NMR 600MHz, CDCl3) be respectively：δ
Ha=3.86ppm, (2.00H)；δ Hb=1.44ppm, (36.98)；δ Hc=7.02ppm, (3.96H)；δ Hd=5.05ppm,
(2.03H)。
From the figure 3, it may be seen that the chemical peak position of each carbon and area are consistent with theoretical value.
As shown in Figure 4, the fusing point of product is 156.8 DEG C, and melting range is narrow, and purity is high.
Embodiment 2：
It is added 226.6g's (1.1mol) in the 500mL there-necked flasks equipped with mechanical agitation, thermometer and reflux condensing tube
The mixed acid solution (4.4mL acetic acid and 4.4mL formic acid) of 2,6- DI-tert-butylphenol compounds, 8.8mL, 40 DEG C of stirring in water bath wait for 2,6-
DI-tert-butylphenol compounds fully melt, and 46mL formalins (40wt%) (0.5mol), after being added dropwise, 80 DEG C of waters bath with thermostatic control is added dropwise
Stirring 4 hours.It is washed 5 times with 40 DEG C of deionized waters, each deionized water dosage 200mL, until washing lotion is neutrality, decompression filters
Afterwards, vacuum drying 24 hours.It is recrystallized with 300mL toluene and isooctane mixed solvent, toluene and each 150mL of isooctane, through taking out
It filters, yellow needle-like crystals 191g is obtained after vacuum drying, yield is 90% after testing, purity 99.6%.
Embodiment 3：
The 2,6- of 422g (2.05mol) is added in the 1L reaction kettles equipped with mechanical agitation, thermometer and reflux condensing tube
DI-tert-butylphenol compounds, 6.15mL mixed acid solutions (3.075mL carbonic acid and 3.075mL formic acid), 50 DEG C of stirring in water bath wait for 2,6- bis-
Tert-butyl phenol fully melts, and 97.11mL formalins (37wt%) (0.976mol), after being added dropwise, 60 DEG C of constant temperature is added dropwise
Stirring in water bath 3 hours.It is washed 3 times with 45 DEG C of deionized waters, each deionized water dosage 400mL, after decompression filters, filter cake vacuum
Drying 24 hours.It is recrystallized with 600mL toluene and isooctane mixed solvent, toluene and each 300mL of isooctane, through filtering, vacuum
Yellow needle-like crystals 368g is obtained after drying.Yield is 87% after testing, purity 99.8%.
Embodiment 4：
It is added 211g's (1.025mol) in the 500mL there-necked flasks equipped with mechanical agitation, thermometer and reflux condensing tube
2,6- tert-butyl phenols, 6mL mixed acid solutions (3mL carbonic acid and 3mL phosphoric acid), 50 DEG C of stirring in water bath wait for 2,6- di-tert-butyls
Phenol fully melts, and is added at one time 51mL formalins (37wt%) (0.5125mol), after being added dropwise, 70 DEG C of waters bath with thermostatic control
Stirring 2 hours.It is washed 4 times with 50 DEG C of deionized waters, each deionized water dosage 300mL, after decompression filters, filter cake vacuum drying
24 hours.It is recrystallized with 100mL toluene and isooctane mixed solvent, toluene and each 50mL of isooctane, through filtering, after vacuum drying
Obtain yellow needle-like crystals 192g.Yield is 81% after testing, purity 99.7%.
Embodiment 5：
It is added 211g's (1.025mol) in the 500mL there-necked flasks equipped with mechanical agitation, thermometer and reflux condensing tube
2,6- tert-butyl phenols, 8mL mixed acid solutions (4mL carbonic acid and 4mL phosphoric acid), 50 DEG C of stirring in water bath wait for 2,6- di-tert-butyls
Phenol fully melts, and 36.5mL formalins (37wt%) (0.4875mol) are added dropwise, after being added dropwise, 70 DEG C of water bath with thermostatic control stirrings 5
Hour.It is washed 4 times with 50 DEG C of deionized waters, each deionized water dosage 300mL, after decompression filters, filter cake vacuum drying 24 is small
When.It is recrystallized with 960mL toluene and isooctane mixed solvent, toluene and each 480mL of isooctane, through filtering, after vacuum drying
Yellow needle-like crystals 204g.Yield is 86% after testing, purity 99.2%.
Claims (7)
1. a kind of preparation method of hindered bisphenol type antioxidant, comprises the following steps that：Bis- uncles of 2,6- are added into reactor
Butylphenol and catalyst, 3-8mL catalyst is added in 2, the 6- DI-tert-butylphenol compounds per 1mol, under 40-60 DEG C of temperature condition
To molten formalin is added, the molar ratio of formaldehyde and 2,6- DI-tert-butylphenol compounds is 1 in stirring：2.0-2.2 addition is completed
After be warming up to 60-80 DEG C, react 2-5 hour, filtered, washed 3-5 times with 40-50 DEG C of hot water, filter cake is dried in vacuo, to thick
Product recrystallizes, and 0.5-5mL recrystallization solvents are added per 1g crude products, vacuum dried, obtains yellow needle-like crystals；
The catalyst is mixed acid solution, including strong acid, the weak acid and middle strong acid at least one weak acid and at least one
Volume ratio be 1:1；The weak acid is acetic acid, carbonic acid or both combination, and the middle strong acid is phosphoric acid, formic acid or both combination；
Wherein specific reaction equation is as follows：
2. the preparation method of hindered bisphenol type antioxidant according to claim 1, wherein acetic acid purity >=99wt%,
Phosphoric acid purity >=85wt%, formic acid purity >=99wt%, carbonic acid are the saturated aqueous solution of carbon dioxide.
3. the preparation method of hindered bisphenol type antioxidant according to claim 1, wherein the recrystallization solvent is toluene
With the mixed solution of isooctane, the volume ratio of the toluene and isooctane is 1:1.
4. according to the preparation method of claims 1 to 3 any one of them hindered bisphenol type antioxidant, wherein the formalin
A concentration of 37-40wt%.
5. according to the preparation method of claims 1 to 3 any one of them hindered bisphenol type antioxidant, wherein the formalin
Addition manner be added at one time or be added dropwise addition.
6. the preparation method of hindered bisphenol type antioxidant according to claim 4, wherein the addition side of the formalin
Formula is to be added at one time or be added dropwise addition.
7. according to the preparation method of claims 1 to 3 any one of them hindered bisphenol type antioxidant, wherein the formaldehyde and 2,
The molar ratio of 6- DI-tert-butylphenol compounds is 1：2.05-2.10.
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| CN110627622A (en) * | 2019-09-12 | 2019-12-31 | 广东省石油与精细化工研究院 | Preparation method of high-purity tetramethyl bisphenol A |
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| CN102516035A (en) * | 2011-12-19 | 2012-06-27 | 胶州市精细化工有限公司 | Preparation method of bisphenol F |
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| JP2006036685A (en) * | 2004-07-27 | 2006-02-09 | Sumitomo Chemical Co Ltd | Method for producing bisphenols |
| CN102603491A (en) * | 2011-12-13 | 2012-07-25 | 山东省临沂市三丰化工有限公司 | Clean production method for preparing bisphenol antioxidant |
| CN102516035A (en) * | 2011-12-19 | 2012-06-27 | 胶州市精细化工有限公司 | Preparation method of bisphenol F |
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