CN105985224A - Synthetic method of semi-hindered bisphenol antioxidant - Google Patents
Synthetic method of semi-hindered bisphenol antioxidant Download PDFInfo
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 30
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title claims abstract description 24
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 23
- 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 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 43
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 238000004448 titration Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000003208 petroleum Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001953 recrystallisation Methods 0.000 claims description 12
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 11
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 11
- 230000006837 decompression Effects 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 11
- -1 after titration Chemical compound 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 239000008098 formaldehyde solution Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 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 2
- 241001597008 Nomeidae Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000013632 homeostatic process Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A synthetic method of a semi-hindered bisphenol antioxidant is disclosed, wherein the antioxidant has the following structural formula:wherein: r1And R2At least one of them is tert-butyl when R is1When it is tert-butyl, R2Is C1-C8 alkyl; when R is2When it is tert-butyl, R1Is C1-C8 alkyl. The synthesis method comprises the following steps: adding half-hindered monophenol, an alkali solution catalyst and 95-98% ethanol into a reaction container provided with a mechanical stirrer, a dropping funnel and a reflux condenser, heating until the ethanol flows back, dropping a formaldehyde solution, carrying out a phenolic condensation reaction for 3-8 hours after titration, carrying out reduced pressure distillation to remove the ethanol, washing the product with distilled water until the washing solution is neutral, carrying out suction filtration, carrying out vacuum drying on a filter cake, recrystallizing the filter cake, and carrying out vacuum drying to obtain a yellow powdery product.
Description
Technical field
The present invention relates to the synthesis technique of a kind of antioxidant for lubricant oil, be specifically related to a kind of half resistance bisphenol type and resist
The synthetic method of oxygen agent.
Background technology
Conventional antioxidant is aromatic amine or the sulfur-bearing of Hinered phenols and organic phosphorus compound.Hinered phenols
Antioxidant includes single phenols, bisphenols and Polyphenols etc..The molecule of single phenolic hindered phenol antioxygen only has one
Individual hindered phenol unit, can suppress or delay the oxidative degradation of lubricating oil, fuel oil, prevent on the acid number of oil product
Rise, but relative molecular mass is little, volatility is relatively big, is therefore suitable only for and makes under the working condition relatively relaxed
With.
Chinese patent CN 102757313 A discloses a kind of asymmetric hindered phenol antioxygen and synthetic method,
It is that 2.4-dimethyl, styrene are being added ferric chloride or zinc chloride makees catalyst, under condition of no solvent
At 40-80 DEG C of single step reaction, after having reacted, add solvent dilution, through washing, be dehydrated, filtering, desolventizing
Obtain product.
Chinese patent CN 102050760 A discloses the catalysis of a kind of Hinered phenols derivant antioxidant to be prepared
Method, uses catalytic dehydration technique to prepare Hinered phenols derivant antioxidant, and reaction raw materials is the most acidified instead
Should obtain two kinds of intermediate with single hydrazidesization reaction, then solvent and two kinds of intermediate add reactor, are urging
Under the effect of agent, it is heated to reflux, dehydration occurs, then passes through fraction water device water-dividing.Although first
Step acidification reaction process use alkali be catalyst, methanol or ethanol as solvent, but reaction principle is with this specially
The phenol formaldehyde condensation of profit is entirely different, and target product is different.
Summary of the invention
It is an object of the invention to provide a kind of half synthetic method hindering bisphenol type antioxidant, the letter of the method technique
Single, productivity is high, and purity is high, and solvent is recyclable.
The present invention provides a kind of half synthetic method hindering bisphenol type antioxidant, and this antioxidant has following structure
Formula:
Wherein: R1With R2In at least one be the tert-butyl group, work as R1During for the tert-butyl group, R2For C1-C8
Alkyl；Work as R2During for the tert-butyl group, R1Alkyl for C1-C8.
Synthetic method comprises the steps: in the reaction equipped with mechanical agitation, Dropping funnel and reflux condensing tube
Adding the half single phenol of resistance, aqueous slkali catalyst and concentration in container is 95-98% ethanol, is heated to alcohol reflux,
Dropping formalin, after titration, phenol formaldehyde condensation reacts 3-8 hour, and decompression is distilled off ethanol, so
It is neutral for washing product to water lotion with distilled water afterwards, sucking filtration, and filter cake is vacuum dried, heavily ties filter cake
Crystalline substance, vacuum drying obtains product as yellow powder.
Of the present invention half synthetic method hindering bisphenol type antioxidant, wherein, the alkyl of C1-C8 is preferably
Methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl.
Of the present invention half synthetic method hindering bisphenol type antioxidant, wherein, the half single phenol of resistance rubs with formaldehyde
That ratio preferably 2～2.1:1.
Of the present invention half synthetic method hindering bisphenol type antioxidant, wherein, the consumption of aqueous slkali catalyst
It is preferably 1mol formaldehyde and uses 60-100g aqueous slkali.
Of the present invention half synthetic method hindering bisphenol type antioxidant, wherein, the consumption of ethanol is 1mol
The half single phenol of resistance is preferably used 0.8-1.2L ethanol.
Of the present invention half synthetic method hindering bisphenol type antioxidant, wherein, aqueous slkali catalyst preferably by
Lithium hydrate and barium hydroxide are configured to, for 1:1, the aqueous slkali that mass fraction is 10% in mass ratio.Catalysis
Agent is necessary for mixed base, if using single alkali as catalyst, by-product is on the high side, affects product purity,
After the two is compounding, catalytic effect is moderate, and productivity is higher.
Of the present invention half synthetic method hindering bisphenol type antioxidant, wherein, the solvent of recrystallization is preferred
For petroleum ether, every 1g crude product preferably uses 1-5mL petroleum ether, the product purity after recrystallization reach 98% with
On.
The synthetic method of the half resistance bisphenol type antioxidant that the present invention provides, is reaction dissolvent by using ethanol,
And it is heated to alcohol reflux, it is ensured that the homeostasis of reaction temperature, and ethanol reclaim be more prone to.Urge
Agent uses mixing dilute alkaline solution, reduces the generation of by-product while ensureing catalytic effect.Wash with water
Product, after the adjusted PH of filtrate to neutrality, can be recycled.Use petroleum ether as recrystallization solvent,
Consumption is few, and decompression distillation is recyclable.
The invention have the characteristics that with aqueous slkali as catalyst, ethanol is that solvent production is asymmetric partly hinders bisphenol type
Antioxidant, technique is simple, and productivity is high, and purity is high, and ethanol and petroleum ether solvent are easily recycled use, reduces
Polluting, reaction condition is gentle, and waste water can be recycled, recrystallization solvent consumption is few, and product antioxidation is imitated
The best, its greasy filth growing amount is few, is more suitable for industrial lubricant and I. C. engine oil.
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is premised on technical solution of the present invention
Under implement, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
The alkyl of C1-C8:
In the present invention, being not particularly limited the alkyl of C1-C8, the alkyl of usual described C1-C8 can
It is enumerated as methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl n-hexyl, n-heptyl or n-octyl.
The half single phenol of resistance and the mol ratio of formaldehyde:
In the present invention, half-and-half the single phenol of resistance is not particularly limited with the mol ratio of formaldehyde, the generally half single phenol of resistance and
The mol ratio of formaldehyde is 2～2.1:1, if the mol ratio of the half single phenol of resistance and formaldehyde is less than 2:1, due to half
The single phenol consumption of resistance is very few, causes target product purity low, and partly hinders single phenol mol ratio with formaldehyde more than 2.1:
1, owing to the half single phenol consumption of resistance is too much, cause waste, cost increases, and post processing bothers, and there is no other has
Benefit effect.
The consumption of aqueous slkali catalyst:
In the present invention, the consumption of aqueous slkali catalyst is not particularly limited, usual aqueous slkali catalyst
Consumption is that 1mol formaldehyde uses 60-100g aqueous slkali, if aqueous slkali consumption uses less than 1mol formaldehyde
60g aqueous slkali, owing to the consumption of aqueous slkali catalyst is very few, causes catalytic effect inconspicuous, catalytic efficiency
Reducing, reaction is not exclusively；And if aqueous slkali consumption uses 100g aqueous slkali more than 1mol formaldehyde, due to
The consumption of aqueous slkali catalyst is too much, causes waste, and by-product is more, there is no other beneficial effects.
The consumption of ethanol:
In the present invention, being not particularly limited ethanol consumption, the consumption of usually ethanol is that 1mol partly hinders list
Phenol uses 0.8-1.2L ethanol, if the consumption of ethanol uses 0.8L ethanol less than the 1mol half single phenol of resistance, by
Very few in ethanol consumption, cause material concentration higher, during dropping, local response is violent, and ethanol
Consumption uses 1.2L ethanol more than the 1mol half single phenol of resistance, owing to ethanol consumption is too much, causes waste, increases
Cost recovery, there is no other beneficial effects.
Aqueous slkali catalyst forms:
In the present invention, being not particularly limited aqueous slkali catalyst composition, usual aqueous slkali catalyst is by hydrogen
Lithium oxide and barium hydroxide are configured to, for 1:1, the aqueous slkali that mass fraction is 10% in mass ratio, if hydrogen
Lithium oxide and barium hydroxide are in mass ratio less than 1:1, then very few due to Lithium hydrate consumption, cause by-product
More；And Lithium hydrate and barium hydroxide are in mass ratio more than 1:1, owing to Lithium hydrate consumption is too much, make
Become waste, and reactivity is on the low side, there is no other beneficial effects.
Lithium hydrate and barium hydroxide are configured to the mass fraction aqueous slkali less than 10% for 1:1 in mass ratio,
Owing to concentration is too low, cause catalytic effect the best, and Lithium hydrate and barium hydroxide are 1:1 in mass ratio
Being configured to the mass fraction aqueous slkali more than 10%, due to excessive concentration, cause reaction acutely, by-product is inclined
Many, there is no other beneficial effects.
Recrystallization:
In the present invention, being not particularly limited recrystallization, the solvent of recrystallization is petroleum ether, every 1g
Crude product 1-5mL petroleum ether, if used by every 1g crude product, petroleum ether is less than 1mL, due to petroleum ether
Consumption is very few, causes recrystallization effect undesirable, still with the presence of impurity, and if used by every 1g crude product
Petroleum ether is more than 5mL, owing to petroleum ether consumption is too much, causes waste, and increases cost recovery, there is no it
His beneficial effect.
Embodiment 1
329.64g is added in equipped with the 3L there-necked flask of mechanical agitation, constant pressure funnel and reflux condensing tube
(2.01mol) 2-methyl-6-DI-tert-butylphenol compounds, 1.6L mass fraction is the ethanol of 95%, 100g mass
Mark is the mixed ammonium/alkali solutions (5g Lithium hydrate and 5g barium hydroxide) of 10%, is heated to alcohol reflux,
Dropping 75mL formalin (37wt%), 4-5 per second drips, and after dropping, keeps alcohol reflux to continue
Continuous stirring 4 hours.Decompression is distilled off ethanol, is washed with distilled water to washing liquid for neutrality, each distilled water
Consumption 300mL, after decompression sucking filtration, filter cake vacuum drying 24 hours.With 300mL petroleum ether recrystallization,
Sucking filtration, obtains yellow powdery solid 310g after vacuum drying.Productivity is 87% after testing, and purity is 98%.
This product joins in HVIH P6 base oil with quality 0.5%, and rotary oxygen bomb is 100 minutes, its antioxygen
Effect is better than single phenol antioxidant.
Embodiment 2
Add in equipped with the 1L there-necked flask of mechanical agitation, constant pressure funnel and reflux condensing tube
2-ethyl-6-the DI-tert-butylphenol compounds of 181.56g (1.02mol), 2L mass fraction is the ethanol of 95%, 50g
Mass fraction is the mixed ammonium/alkali solutions (2.5g Lithium hydrate and 2.5g barium hydroxide) of 10%, is heated to second
Alcohol reflux, dropping 37.5mL formalin (37wt%), 4-5 per second drips, and after dropping, keeps
Alcohol reflux continues stirring 6 hours.Decompression is distilled off ethanol, and being washed with distilled water to washing liquid is neutrality,
Distilled water consumption 200mL every time, after decompression sucking filtration, filter cake vacuum drying 24 hours.Use 200mL oil
Ether recrystallization, sucking filtration, obtain yellow powdery solid 171g after vacuum drying.Productivity is 89% after testing,
Purity is 98.3%.
Embodiment 3
Add in equipped with the 1L there-necked flask of mechanical agitation, constant pressure funnel and reflux condensing tube
2-butyl-6-the DI-tert-butylphenol compounds of 206g (1mol), 1.2L mass fraction is the ethanol of 95%, 50g mass
Mark is the mixed ammonium/alkali solutions (2.5g Lithium hydrate and 2.5g barium hydroxide) of 10%, is heated to ethanol and returns
Stream, dropping 38mL formalin (37wt%), 4-5 per second drips, and after dropping, keeps ethanol to return
Stream continues stirring 3 hours.Decompression is distilled off ethanol, and being washed with distilled water to washing liquid is neutrality, steams every time
Distilled water consumption 150mL, after decompression sucking filtration, filter cake vacuum drying 24 hours.Heavily tie with 150mL petroleum ether
Crystalline substance, sucking filtration, obtain yellow powdery solid 183g after vacuum drying.Productivity is 83% after testing, and purity is
98.6%.
Embodiment 4
491.4g is added in equipped with the 3L there-necked flask of mechanical agitation, constant pressure funnel and reflux condensing tube
(2.1mol) 2-hexyl-6-DI-tert-butylphenol compounds, 1.62L mass fraction is the ethanol of 98%, 100g mass
Mark is the mixed ammonium/alkali solutions (2.5g Lithium hydrate and 2.5g barium hydroxide) of 10%, is heated to ethanol and returns
Stream, dropping 73mL formalin (37wt%), 4-5 per second drips, and after dropping, keeps ethanol to return
Stream continues stirring 8 hours.Decompression is distilled off ethanol, and being washed with distilled water to washing liquid is neutrality, steams every time
Distilled water consumption 300mL, after decompression sucking filtration, filter cake vacuum drying 24 hours.Heavily tie with 400mL petroleum ether
Crystalline substance, sucking filtration, obtain yellow powdery solid 446.4g after vacuum drying.Productivity is 90% after testing, and purity is
98%.
Claims (8)
1. a synthetic method for half resistance bisphenol type antioxidant, this antioxidant has a following structural formula:
Wherein: R1With R2In at least one be the tert-butyl group, work as R1During for the tert-butyl group, R2For C1-C8
Alkyl；Work as R2During for the tert-butyl group, R1Alkyl for C1-C8.
Synthetic method comprises the steps: in the reaction equipped with mechanical agitation, Dropping funnel and reflux condensing tube
Adding the half single phenol of resistance, aqueous slkali catalyst and concentration in container is 95-98% ethanol, is heated to alcohol reflux,
Dropping formalin, after titration, phenol formaldehyde condensation reacts 3-8 hour, and decompression is distilled off ethanol, so
It is neutral for washing product to water lotion with distilled water afterwards, sucking filtration, and filter cake is vacuum dried, heavily ties filter cake
Crystalline substance, vacuum drying obtains product as yellow powder.
2. the synthetic method of half resistance bisphenol type antioxidant as claimed in claim 1, it is characterised in that: institute
The alkyl stating C1-C8 is methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl
Or n-octyl.
3. the synthetic method of half resistance bisphenol type antioxidant as claimed in claim 2, it is characterised in that: half
The single phenol of resistance is 2～2.1:1 with the mol ratio of formaldehyde.
4. the synthetic method of half resistance bisphenol type antioxidant as claimed in claim 3, it is characterised in that: alkali
The consumption of solution catalyst is that 1mol formaldehyde uses 60-100g aqueous slkali.
5. the synthetic method of half resistance bisphenol type antioxidant as claimed in claim 4, it is characterised in that: second
The consumption of alcohol is that the 1mol half single phenol of resistance uses 0.8-1.2L ethanol.
6. half as described in any one of Claims 1 to 5 hinders the synthetic method of bisphenol type antioxidant, its feature
It is: aqueous slkali catalyst is configured to mass fraction for 1:1 by Lithium hydrate in mass ratio with barium hydroxide and is
The aqueous slkali of 10%.
7. half as described in any one of Claims 1 to 5 hinders the synthetic method of bisphenol type antioxidant, its feature
It is: the solvent of described recrystallization is petroleum ether, every 1g crude product 1-5mL petroleum ether.
8. the synthetic method of half resistance bisphenol type antioxidant as claimed in claim 6, it is characterised in that: institute
The solvent stating recrystallization is petroleum ether, every 1g crude product 1-5mL petroleum ether.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111088100A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Diesel engine oil composition and preparation method thereof |
| CN111088095A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Air compressor oil composition and preparation method thereof |
| CN111088098A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | High-temperature chain oil composition and preparation method thereof |
| CN111088094A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Automatic transmission fluid and preparation method thereof |
| CN116082129A (en) * | 2022-09-14 | 2023-05-09 | 大连理工大学 | Method for preparing Galvanic oxygen radical by oxidizing hydrogen peroxide |
Citations (2)
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| RO104972B1 (en) * | 1989-08-09 | 1994-12-19 | Combinatul Petrochimic Teleaje | Antioxidizing admixture and producing process thereof |
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| CN111088100A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Diesel engine oil composition and preparation method thereof |
| CN111088095A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Air compressor oil composition and preparation method thereof |
| CN111088098A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | High-temperature chain oil composition and preparation method thereof |
| CN111088094A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Automatic transmission fluid and preparation method thereof |
| CN111088095B (en) * | 2018-10-23 | 2022-10-21 | 中国石油化工股份有限公司 | Air compressor oil composition and preparation method thereof |
| CN111088094B (en) * | 2018-10-23 | 2022-10-21 | 中国石油化工股份有限公司 | Automatic transmission fluid and preparation method thereof |
| CN111088098B (en) * | 2018-10-23 | 2022-10-21 | 中国石油化工股份有限公司 | High-temperature chain oil composition and preparation method thereof |
| CN111088100B (en) * | 2018-10-23 | 2022-10-21 | 中国石油化工股份有限公司 | Diesel engine oil composition and preparation method thereof |
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