CN105646232A - Method for preparing 4,4'-bis(phenyl isopropyl)diphenylamine - Google Patents
Method for preparing 4,4'-bis(phenyl isopropyl)diphenylamine Download PDFInfo
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- CN105646232A CN105646232A CN201610058786.1A CN201610058786A CN105646232A CN 105646232 A CN105646232 A CN 105646232A CN 201610058786 A CN201610058786 A CN 201610058786A CN 105646232 A CN105646232 A CN 105646232A
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- diphenylamines
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- phenyl base
- propyloxy phenyl
- atlapulgite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing 4,4'-bis(phenyl isopropyl)diphenylamine. Under the action of catalyst activated clay, diphenylamine and alpha-methyl styrene react at the temperature of 105 DEG C-165 DEG C to generate a crude product 4,4'-bis(phenyl isopropyl)diphenylamine, 4,4'-bis(phenyl isopropyl)diphenylamine is filtered, then recrystallized with solvent, and then subjected to centrifugal baking smashing or pelleting to obtain high-purity 4,4'-bis(phenyl isopropyl)diphenylamine, the activated clay and diphenylamine are prepared into jelly mixed liquor, and alpha-methyl styrene is uniformly added into the mixed liquor of the activated clay and diphenylamine in a fractionated mode. Compared with the prior art, reaction speed is high, efficiency is high, three wastes are not generated, and 4,4'-bis(phenyl isopropyl)diphenylamine is high in purity and good in color.
Description
Technical field
The present invention relates to antioxidant chemosynthesis technical field, relate in particular to one and prepare 4,4 '-bis-(phenylIsopropyl) method of diphenylamines.
Background technology
4,4 '-bis-(propyloxy phenyl base) diphenylamines can be used for protecting natural rubber and butylbenzene, isoamyl, neoprene, fourthThe synthetic rubber such as base because of heat, light, ozone cause aging. There is good cooperative effect with sulfur-bearing antioxidant. SuitableFor light color and gorgeous look rubber. Also can be used as polyurethane foam plastics, polyolefin, carbon black-filled polyolefinAnd the antioxidant of rubber and plastic electric wire, packaging material for food and adhesive etc., especially at the colored cable of neopreneHeat aging property in sheath is better. Conventionally by diphenylamines and AMS at activated bauxite catalystThere is lower reaction and make. At present, have for the antioxidant of plastics and rubber technical field a variety of,Relatively be typically amine and phenolic antioxidant.
4,4 '-bis-(propyloxy phenyl base) diphenylamines, trade name antioxidant KY-405, conventionally by diphenylamines and α-Methyl styrene is synthetic, and diphenylamines is a kind of important meticulous Organic Chemicals, of many uses, is mainly used inThe industries such as rubber chemicals, explosive stabilizing agent, medicine, dyestuff are the main synthesis materials of many amine antioxidants.
For example Chinese patent CN1195661A discloses one and has prepared age resistor by diphenylamines and 2 methyl styrenes4,4 ' one 2 cumenyl 1 " method of a cumenyl diphenylamines. The method adopts in course of reactionA large amount of solvents, and carry out acidifying with hydrochloric acid in post processing, then use in alkali and after washing, labour intensity large andSerious to equipment corrosion, and the color of product is poor.
For example Chinese patent CN101538207B discloses one and has prepared 4 again, 4 '-bis-(α, alpha-alpha-dimethyl benzylsBase) method of diphenylamines, relate to the chemosynthesis technical field of a kind of diphenylamines synthetized oxidation preventive agent KY-405.Under the effect of catalyst activity carclazyte, under 105～175 DEG C of temperature conditions, by diphenylamines and Alpha-Methyl benzeneEthene reacts, and generates thick product 4,4 '-bis-(alpha, alpha-dimethylbenzyl) diphenylamines, after filteringBy solvent recrystallization, obtain highly purified 4,4 '-bis-(α, α-bis-again after centrifugal oven dry pulverizing or granulationMethyl-benzyl) diphenylamines. Atlapulgite and reactant in the method belong to heterocatalysis, and catalyst directly addsIn diphenylamines and AMS, carry out stirring reaction, the poor reaction speed of catalytic effect is slow. And knotPoor other impurity of easy generation of direct cooling down crystallization effect when brilliant.
Summary of the invention
Urge for overcoming catalyst in 4,4 '-bis-(propyloxy phenyl base) the diphenylamines preparation process existing in prior artThe problem of changing weak effect, the invention provides one and prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines.
One prepares 4, and the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, in the effect of catalyst activity carclazyteUnder, under 105～165 DEG C of temperature conditions, diphenylamines and AMS are reacted, generate slightly produceProduct 4,4'-bis-(propyloxy phenyl base) diphenylamines, after filtering by solvent recrystallization, again pulverize through centrifugal oven dry orAfter granulation, obtain highly purified 4,4'-bis-(propyloxy phenyl base) diphenylamines, described atlapulgite and diphenylamines are first joinedAgglutination mixing material, AMS gradation evenly joins the mixing material of atlapulgite and diphenylaminesIn.
Further, AMS divides the mixed liquor that evenly joins atlapulgite and diphenylamines for 3-5 timeIn body.
Further, AMS divides the mixing material that evenly joins atlapulgite and diphenylamines for 4 timesIn.
Further, AMS evenly joined atlapulgite and diphenylamines in 5 to 10 minutesIn mixing material.
Further, when described re-crystallization step starts, use Insulation to surface to form epitaxial.
Further, the molar ratio of diphenylamines and AMS is 1:2.0～2.6.
Further, the percentage by weight of described atlapulgite and diphenylamines is 12～20%.
Further, the percentage by weight of described atlapulgite and diphenylamines is 14%.
Further, the filtration temperature in described filtration step is 98 DEG C-165 DEG C.
Further, the solvent of described recrystallization is the benzinum that boiling range is greater than 100 DEG C.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention is first made into gluey mixing material by atlapulgite and diphenylamines before reaction starts, due toAtlapulgite belongs to out-phase reaction diphenylamines and reacting of AMS, therefore that atlapulgite is directBe added in diphenylamines and AMS and can make catalytic effect poor, the reaction time is long, and first will liveProperty carclazyte and diphenylamines are made into gluey mixing material and are beneficial to the dispersion of atlapulgite, thereby Reaction time shorten is carriedThe utilization rate of high catalyst.
(2) AMS gradation evenly joins in the mixing material of atlapulgite and diphenylamines, due toThe AMS easy polymerization reaction take place that is heated, therefore the amount of AMS is unsuitable excessive too many,Carry out adding for even time and can guarantee that in course of reaction, thereby AMS can excessively not ensure all the time too muchThe stationarity of reaction.
(3) the present invention uses Insulation to surface to form epitaxial in the time that re-crystallization step starts, and like this canMake crystallization process more steady, thereby reduce the content of impurity, improve the purity of product.
(4) adopt method for crystallising to remove low boiling impurity unreacted or that generate, only need filter, dryDo and just can obtain high-quality product, process is simple, and preparation efficiency is high.
(5) under the condition that does not add organic solvent, react, can remove low boiling by solvent recrystallizationComponent, the mother liquor of centrifugal filtration gained carries out distillating recovering solvent benzinum, and can recycled.
(6) adopt atlapulgite as catalyst, can from reaction medium, separate by filtering, by dryingPurification can continue to apply mechanically, and is easy to separate and economize on resources, and does not produce pollutant. And atlapulgite priceLow, reduce synthetic cost, the consumption of atlapulgite can change and be unlikely to reaction to be produced in a big wayRaw harmful effect, and its course of reaction one-step synthesis, after the complexity such as acidified, alkali neutralization, washingProcessing procedure, do not have the three wastes to produce, and the purity of product is high, and color is good.
Brief description of the drawings
Fig. 1 is the method flow schematic diagram of preparing 4,4 '-bis-(propyloxy phenyl base) diphenylamines in the present invention;
Fig. 2 is the cutaway view of the rotary granulator in the present invention;
Fig. 3 is the cutaway view of the rotary granulator granulation rotating disk in the present invention.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further elaborated. Should be appreciated that this placeThe specific embodiment of describing, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
With reference to flow chart 1, this detailed description of the invention has disclosed one and has prepared 4,4 '-bis-(propyloxy phenyl base) hexicholThe method of amine, specifically a kind of laboratory prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines.
In the present embodiment, the percentage by weight of atlapulgite and diphenylamines is 12%, diphenylamines and Alpha-Methyl benzeneThe mol ratio of ethene is 1:2.0.
Raw material and prepare the selection of equipment, comprises that diphenylamines (purity >=99.5%), α monomethyl styrene are (pureDegree >=99%), benzinum (analyzing pure), atlapulgite, thermostatic type magnetic stirring apparatus, vavuum pump, returned coldCondenser, feeding device, nitrogen protection device, 1L round bottom three neck reaction flasks, thermometer, iron stand, trueEmpty glass stopper, electric heating cover, Buchner funnel and other glass apparatus.
Measure 16.9g diphenylamines and join in 1L round bottom three neck reaction flasks, take 2g atlapulgite and joinIn diphenylamines, add while stirring, in whipping process, slowly heat up, and optionally add in whipping processSurfactant, until diphenylamines and atlapulgite form colloidal liquid, now rises to heating-up temperature120-135 DEG C, and open condensed water, adopt running water as preferred condensed water. Now by load weighted23.6g AMS is divided into 4 parts, and every part of 5.9g fills the AMS having divided by reinforcedPut and point add in reaction flask for four times, the interpolation time is controlled in 5-10 minute and completes at every turn, adds for the first timeThe time interval that adds AMS and add for the second time AMS is in 10 minutes, secondInferior interpolation AMS and the time interval of adding for the third time AMS are 10-20 minute,The time interval of adding AMS and the 4th interpolation AMS for three times is 20-30 minute,Whole reaction needs 3.0h from adding for the first time AMS to completing, control temperature 120～145 DEG C, be then cooled to below 120 DEG C. In addition in course of reaction, visual response situation is accelerated mixing speed. DoFor preferably, atlapulgite needs before use through 80-100 DEG C of heating, drying processed, to prevent reactionIn process, there is bumping.
In the time that mixture still remains on reaction temperature, carry out heat preservation hot filtration, concrete will be pre-in 120 DEG C of baking ovensThe Buchner funnel that heat is crossed is fixed on conical flask, and on pad, double-deck filter paper soaks and guarantees that edge does not have with reaction solutionThere is crack, reacted solution is poured in Buchner funnel, open vavuum pump. Be placed in as preferred conical flaskTemperature is the interior insulation of the heating jacket of 120 DEG C, treats after filtrate is drained, rubber tube to be pulled up, and closes vavuum pump to keep awayExempt from suck-back. Now the mother liquor in conical flask is the thick solution of product, and filter point is catalyst.
Mother liquor is poured in the four neck flasks that thermometer, agitating device and condenser pipe are housed, by prepreparedBenzinum joins in four neck flasks, stirs and maintains the temperature at more than 100 DEG C with electric heating cover, treats benzinumMix completely with mother liquor after, close stirring, now the temperature of electric heating cover is adjusted to 98 DEG C of insulations, untilLiquid surface forms epitaxial, removes electric heating cover. Be down to while approaching room temperature until temperature, adopt the vacuum filtration will be thickProduct solution filters. Filtration is completed to later filter part dries is 4,4 '-bis-(propyloxy phenyl bases)Diphenylamines crude product. Can obtain 4,4 '-bis-(propyloxy phenyl base) diphenylamines final products through pulverizing. WhereinThe weight of crude product is 38g, and yield is 81%, and the time of whole reaction is 3.0-3.5 hour, with prior artIn conventional method compare and shortened the reaction time, improved efficiency.
As preferably, the atlapulgite filtering down for the first time can be through drying, pulverization process recycle,And the mother liquor filtering for the second time can be recycled by distillation, because the Main Ingredients and Appearance in mother liquor is benzinumAnd the impurity of remaining excessive α monomethyl styrene and reaction in reaction, and the boiling point of benzinum is 100 DEG C-120 DEG C, the cinnamic boiling point of α monomethyl is 165 DEG C, and impurity is that polymer boiling point is higher, therefore adoptsDistill and benzinum can be separated as the first fraction by the temperature of 120 DEG C-165 DEG C, adopt higher thanThe temperature of 165 DEG C is distilled and α monomethyl styrene can be separated. Preferably, in the present embodimentAdopt and first with 140 DEG C, benzinum is separated as the first fraction, then temperature is risen to 170 DEG C by α monomethyl benzeneEthene is separated as the second fraction, and last remaining mother liquor is polymeric impurities, can adopt general uselessMethod for treating water is processed, thereby reaches environment friendly and pollution-free object.
Embodiment 2
With reference to flow chart 1, this detailed description of the invention has disclosed one and has prepared 4,4 '-bis-(propyloxy phenyl base) hexicholThe method of amine, specifically a kind of laboratory prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines.
Be with the difference of embodiment 1, the atlapulgite in the present embodiment and the percentage by weight of diphenylamines are14%, the mol ratio of diphenylamines and AMS is 1:2.4.
Prepare 4 by the present embodiment, 4 '-bis-(propyloxy phenyl base) diphenlyamine reaction times prepared than embodiment 14,4 '-bis-(propyloxy phenyl base) diphenlyamine reaction time shorten 0.3 hour.
Embodiment 3
With reference to flow chart 1, this detailed description of the invention has disclosed one and has prepared 4,4 '-bis-(propyloxy phenyl base) hexicholThe method of amine, specifically a kind of laboratory prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines.
Be with the difference of embodiment 1, the atlapulgite in the present embodiment and the percentage by weight of diphenylamines are20%, the mol ratio of diphenylamines and AMS is 1:2.6.
Prepare 4 by the present embodiment, 4 '-bis-(propyloxy phenyl base) diphenlyamine reaction times prepared than embodiment 14,4 '-bis-(propyloxy phenyl base) diphenlyamine reaction is suitable.
Embodiment 4
With reference to flow chart 1, this detailed description of the invention has disclosed one and has prepared 4,4 '-bis-(propyloxy phenyl base) hexicholThe method of amine, specifically a kind of laboratory prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines.
Be with the difference of embodiment 1, in the present embodiment, select most preferably scheme, atlapulgite and diphenylaminesPercentage by weight is 14%, and the mol ratio of diphenylamines and AMS is 1:2.6.
Prepare 4 by the present embodiment, 4 '-bis-(propyloxy phenyl base) diphenlyamine reaction times prepared than embodiment 14,4 '-bis-(propyloxy phenyl base) diphenlyamine reaction time shorten 0.5h.
Embodiment 5
With reference to flow chart 1, this detailed description of the invention has disclosed one and has prepared 4,4 '-bis-(propyloxy phenyl base) hexicholThe method of amine, specifically a kind of method of industry preparation 4,4 '-bis-(propyloxy phenyl base) diphenylamines.
Atlapulgite in the present embodiment and the percentage by weight of diphenylamines are 14%, diphenylamines and Alpha-Methyl benzene secondThe mol ratio of alkene is 1:2.6.
The selection of raw material and equipment, comprises diphenylamines, α monomethyl styrene, benzinum, atlapulgite, bandThe reactor of cooling and reflux device, solid-liquid blender, stirred tank, press filtration pot, charging device, crystallizing pond, essenceHeat up in a steamer tower, blast drier and pulverizing prilling granulator.
Concrete, 1.69 tons of diphenylamines and 0.236 ton of atlapulgite are mixed and stirred in solid-liquid blenderMix, in whipping process, adopt Steam Heating, in solid-liquid blender, be also provided with temperature measuring equipment in addition, work as diphenylaminesWhile forming colloidal liquid with atlapulgite, stop stirring. By charging device by the mixing of diphenylamines and atlapulgiteLiquid joins in reactor, simultaneously open stir, and by temperature increase to 120-135 DEG C. Treat temperature stabilizationAfter, point by feeding device, 4.94 tons of AMSs are added in reactor for 4 times, when each reinforcedBetween be controlled at 5-10 minute, prevent that the reinforced too fast accessory substance that causes from increasing. Because AMS is subject to thermal capacitanceEasily polymerization reaction take place, the even interpolation of gradation can guarantee that in course of reaction, AMS all the time can mistakeAmount is too many, thereby reduces the generation of accessory substance. As preferably, in course of reaction, pass into nitrogen as protectionGas covers, thereby prevents raw material oxidation. After reaction time reaches 2.5 hours, do not have sampling in 10 minutes to survey twoAniline content, when the content of diphenylamines is less than 0.1% expression sufficient reacting, is now delivered to press filtration by reactantIn crossing, carry out heat preservation hot filtration, the solid filtering down is transported to and in blast drier, carries out dried recovered. Incited somebody to actionMother liquor after filter is delivered to the benzinum that stirred tank adds boiling range to be greater than 100 DEG C by charging device, whipping processThe temperature of stirred tank is remained on to 100 DEG C, to be mixedly liquid is put into crystallizing pond after completely, simultaneously in crystallizationSteam insulation is opened in the top in pond, after surface produces epitaxial, stops delivering vapor, carries out decrease temperature crystalline, treats temperatureDegree is transported to centrifuge by material while being down to room temperature and carries out centrifugation. The solid that centrifugation obtains isThe product of 4,4 '-bis-(propyloxy phenyl base) diphenylamines. The crude product obtaining is carried out to air blast oven dry, re-use pulverizingPrilling granulator carries out granulation, thereby obtains satisfactory product. Preferably, after pulverizing, the order number of product is less than60 orders, the product after granulation is hemispherical, particle diameter 3～6mm.
As preferably, the granulation process in this detailed description of the invention adopts rotary granulator. Concrete, ginsengAccording to Fig. 2 and Fig. 3, the rotary granulator in this detailed description of the invention comprises rotary granulator shell 1 and makesGrain part 2, granulation part 2 is positioned at an inside of machine shell 1, granulation part 2 and rotary granulator shell1 is fixedly connected with by flange.
Wherein, the upper end of rotary granulator shell 1 is provided with air blast 11, air blast 11 and rotary granulationMachine shell 1 is fixedly connected with by screw, is positioned at rotary granulation as the motor position of preferred air blast 11The outer end of machine shell 1, the lower end of rotary granulator shell 1 offers the discharge gate 12 for discharge. RevolveThe inner position except granulation part 2 of rotatable comminutor shell 1 is hollow form. As preferably, discharge gate12 lower end is arc port, and its opening part is positioned at side, can conveniently feed like this.
In addition, granulation part 2 comprises woven hose 21, granulation rotating disk 22 and rotating shaft 23, woven hose 21, granulationRotating disk 22 and rotating shaft 23 are one-body molded, and woven hose 21 is flexibly connected with rotary granulator shell 1, connectPlace can horizontally rotate, and granulation rotating disk 22 can rotate under the drive of rotating shaft 23. As preferably, infuseThe periphery of pipe 21 is coated with steam and carries cavity 211, can by the interior delivering vapor of past steam conveying cavity 211To reach the object of heating and thermal insulation. The inside of granulation rotating disk 22 is provided with capillary liquid outlet 221, capillary liquid outlet221 communicate with woven hose 21, and the stoste of granulation can utilize centrifugal force to throw away by capillary liquid outlet 221.Capillary liquid outlet 221 is long micropipe shape, is 60 μ m as the diameter of preferred capillary liquid outlet 221, longDegree is suitable with the radius of granulation rotating disk 22. The lower end of rotating shaft 23 is provided with drive motors 231, drive motors 231Be fixedly connected with by screw with rotating shaft 23. As preferably, all parts of granulation part 2 is heat insulation potteryPorcelain is made, and heat-proof quality is good, and heat is difficult for scattering and disappearing.
The operation principle of the rotary granulator in this specific embodiment: by 4 in the present invention, 4 '-bis-(phenylIsopropyl) diphenylamines fusing fluid adds from woven hose 21, and open drive motors 231 and make granulation rotating disk 22Rotation, opens air blast 11, and now due to 4,4 '-bis-(propyloxy phenyl base) diphenylamines fusing fluid is centrifugalUnder the effect of power, will throw away from capillary liquid outlet 221, because temperature reduces rapidly, the drop being thrown out of is solidifying rapidlyDischarge from discharge gate 12 under the effect of air blast 11 admittedly granulate. Not discontinuous operation of this rotary granulator,Granulation efficiency is high.
As preferably, the mother liquor that centrifugation obtains is delivered to rectifying column, reclaims 120 DEG C of cuts by rectifyingBenzinum and 165 DEG C of cut AMSs circulate, and under mother liquor normal temperature for solid can be with common solidUseless burning disposal together. Because main component in mother liquor is C, N and O element, thereby can carry out burning disposalAnd can not cause environmental pollution. Benzinum and AMS can be recycled and reused for production by processing, and saveResource, reduced cost, avoided unnecessary environmental pollution simultaneously.
The product that the present invention makes has the advantages such as nontoxic, tasteless, look shallow, in polyethers and foamed plastics thereof, doesFast light anti-aging antioxidant, can be used as lubricating oil antioxidant, also can be used as polyurethane foam plastics andThe antioxidant of India-rubber wire, cable, packaging material for food, adhesive, especially at the colored cable cover(ing) of neopreneIn it is heat-resisting, fast light, ageing resistace is remarkable. The present invention be in amine antioxidants few in number several nontoxic,One of tasteless, look shallow antioxidant kind, can be widely used in various elastomers, is applied to polyethylene, poly-The plastic color master such as propylene and polyvinyl chloride grain.
Above-mentioned explanation illustrates and has described the preferred embodiments of the present invention, as previously mentioned, is to be understood that the present invention alsoNon-ly be confined to disclosed herein form, should do not regard the eliminating to other embodiment as, and can be used for various itsHis combination, amendment and environment, and can be in invention contemplated scope described herein, by above-mentioned instruction or relevantTechnology or the knowledge in field are changed. And the change that those skilled in the art carry out and variation do not depart from of the present inventionSpirit and scope, all should be in the protection domain of claims of the present invention.
Claims (10)
1. prepare the method for 4,4 '-bis-(propyloxy phenyl base) diphenylamines for one kind, under the effect of catalyst activity carclazyte,Under 105～165 DEG C of temperature conditions, diphenylamines and AMS are reacted, generate thick product4,4'-bis-(propyloxy phenyl base) diphenylamines, after filtering by solvent recrystallization, pulverize or make through centrifugal oven dry againAfter grain, obtain highly purifiedly 4,4'-bis-(propyloxy phenyl base) diphenylamines, is characterized in that: described atlapulgite andDiphenylamines is first made into gluey mixing material, and AMS gradation evenly joins atlapulgite and diphenylaminesMixing material in.
2. one according to claim 1 prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, its spyLevy and be: AMS divides in the mixing material that evenly joins atlapulgite and diphenylamines for 3-5 time.
3. one according to claim 2 prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, its spyLevy and be: AMS divides in the mixing material that evenly joins atlapulgite and diphenylamines for 4 times.
4. prepare 4 according to the one described in claim 1,2 or 3, the side of 4 '-bis-(propyloxy phenyl base) diphenylaminesMethod, is characterized in that: AMS evenly joined atlapulgite and diphenylamines in 5 to 10 minutesMixing material in.
5. one according to claim 1 prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, its spyLevy and be: described re-crystallization step is used Insulation to surface to form epitaxial while beginning.
6. one according to claim 1 prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, its spyLevy and be: the molar ratio of diphenylamines and AMS is 1:2.0～2.6.
7. one according to claim 1 prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, its spyLevy and be: the percentage by weight of described atlapulgite and diphenylamines is 12～20%.
8. one according to claim 7 prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, its spyLevy and be: the percentage by weight of described atlapulgite and diphenylamines is 14%.
9. one according to claim 1 prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, its spyLevy and be: the filtration temperature in described filtration step is 98 DEG C-165 DEG C.
10. one according to claim 1 prepares 4, the method for 4 '-bis-(propyloxy phenyl base) diphenylamines, itsBe characterised in that: the solvent of described recrystallization is the benzinum that boiling range is greater than 100 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369418A (en) * | 2018-10-10 | 2019-02-22 | 河南师范大学 | A kind of continuous synthesis technology and synthesizer of energy saving and environment friendly alkyl benzene amine class I liquid I antioxidant |
| CN111517962A (en) * | 2020-06-11 | 2020-08-11 | 新乡市瑞丰新材料股份有限公司 | Preparation method of amine anti-aging agent |
| CN113773205A (en) * | 2021-09-24 | 2021-12-10 | 天津利安隆新材料股份有限公司 | Preparation method of 4,4' -di (phenylisopropyl) diphenylamine |
| CN113912500A (en) * | 2020-07-10 | 2022-01-11 | 华东理工大学 | Method for preparing amine compound by using microchannel reactor |
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| CN101538207A (en) * | 2009-04-23 | 2009-09-23 | 江苏飞亚化学工业有限责任公司 | Method for preparing 4,4-bis (alpha, alpha-dimethylbenzyl) diphenylamine |
| CN101538208A (en) * | 2009-04-23 | 2009-09-23 | 江苏飞亚化学工业有限责任公司 | Method for preparing mixture of 4-(alpha, alpha-dimethylbenzyl) diphenylamine and 4,4-bis (alpha, alpha-dimethylbenzyl) diphenylamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538207A (en) * | 2009-04-23 | 2009-09-23 | 江苏飞亚化学工业有限责任公司 | Method for preparing 4,4-bis (alpha, alpha-dimethylbenzyl) diphenylamine |
| CN101538208A (en) * | 2009-04-23 | 2009-09-23 | 江苏飞亚化学工业有限责任公司 | Method for preparing mixture of 4-(alpha, alpha-dimethylbenzyl) diphenylamine and 4,4-bis (alpha, alpha-dimethylbenzyl) diphenylamine |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369418A (en) * | 2018-10-10 | 2019-02-22 | 河南师范大学 | A kind of continuous synthesis technology and synthesizer of energy saving and environment friendly alkyl benzene amine class I liquid I antioxidant |
| CN111517962A (en) * | 2020-06-11 | 2020-08-11 | 新乡市瑞丰新材料股份有限公司 | Preparation method of amine anti-aging agent |
| CN111517962B (en) * | 2020-06-11 | 2023-08-15 | 新乡市瑞丰新材料股份有限公司 | Preparation method of amine anti-aging agent |
| CN113912500A (en) * | 2020-07-10 | 2022-01-11 | 华东理工大学 | Method for preparing amine compound by using microchannel reactor |
| CN113773205A (en) * | 2021-09-24 | 2021-12-10 | 天津利安隆新材料股份有限公司 | Preparation method of 4,4' -di (phenylisopropyl) diphenylamine |
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