CN101139327A - Method for preparing aminophenol triglycidyl group compound - Google Patents
Method for preparing aminophenol triglycidyl group compound Download PDFInfo
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- CN101139327A CN101139327A CNA2007100466340A CN200710046634A CN101139327A CN 101139327 A CN101139327 A CN 101139327A CN A2007100466340 A CNA2007100466340 A CN A2007100466340A CN 200710046634 A CN200710046634 A CN 200710046634A CN 101139327 A CN101139327 A CN 101139327A
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- aminophenol
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- epoxy chloropropane
- triglycidyl group
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Abstract
A preparation method of the aminophenol tri-glycidyl compound comprises: the molar ratio between the aminophenol and the epichlorohydrin is 1 to between 9 and 15; at the temperature between 25 and 55 DEG C, the aminophenol is added into the mixture of the epichlorohydrin and alcohol solvent in patches; the material feeding time is 2 to 3 hours; the temperature between 45 and 55 DEG C is maintained for 3 to 5 hours; then the aqueous solution of sodium hydroxide of 50 percent of the weight ratio is added; the molar ratio between the added sodium hydroxide and the aminophenol is 4 to 1; and the aqueous solution of sodium hydroxide is added in three times; the reaction is done for 3 hours at the temperature between 50 and 60 DEG C; the excessive epichlorohydrin and alcohol solvent are vaporized; the solution is statically laid to be separated; the distilled solution of the epichlorohydrin is recycled to be used as the raw material of the reaction. The residue in the reactor is extracted with toluene and is washed with water for 3 times; the left toluene product is vaporized; the color of the product is yellow brown; the collection rate is between 95 and 98 percent; the epoxy value is between 0.85 and 1.00; the viscosity is less than or equal to 2500mPa.S; the hue of the added sodium is between 5 and 7.
Description
One, technical field
The present invention relates to trifunctional epoxy resin's preparation method, relate to the preparation method of aminophenol triglycidyl group compound or rather.
Two, background technology
The chemical structure of aminophenol triglycidyl group compound of the present invention is:
With regard to its presoma amino-phenol, amino can be in phenolic hydroxyl group to one, one, an adjacent position.
Because the second-order transition temperature of low, the fine properties of aminophenol triglycidyl group compound viscosity, curing moulded piece is up to 230 ℃, workability and excellent heat resistance in addition, this product is widely used as electrically insulating material, laminated product, tackiness agent and structured material etc.For example: JP.03-21631,1991-01-30 discloses with aminophenol triglycidyl group compound system carbon-fibre composite.US Pat.No6,468,659.oct.22,2002 disclose 0, N, N-triglycidyl group-4-amino-phenol and N, N, N, ' N, '-four glycidyl group-4.4 '-diaminodiphenyl-methane and with preparing adhesive etc.
Preparation method about aminophenol triglycidyl group compound reports a lot.From the information of Patent publish, shorten the reaction times, as if having only and seek good catalyzer, otherwise the reaction times will reach more than 20 hours.For example: JP02-025474,26,01.1990 disclosures are made catalyzer with sodium bisulfite or Sodium Pyrosulfite.JP04-139230,13,05.1992 disclosures are made catalyzer with tetramethyl ammonium chloride.The prior art statement can be shortened the reaction times with selected catalyzer, can reduce or eliminate gel again and divide by product.From present situation, it is advantage really that applications catalyst shortens the reaction times, still must keep punching as for eliminating by product, from the explained hereafter angle, uses catalyzer correspondingly also to increase cost.So seek a kind of ideal technical scheme under the prerequisite of not using catalyzer, can shorten the reaction times again, do not produce by product gel branch again.This just becomes purpose of the present invention.
Three, summary of the invention
Present inventors are through studying for a long period of time, and the experience accumulation of Sheng Chaning for many years changes the distillation that reaches superfluous epoxy chloropropane by feed way and reclaims, and promptly distillates the epoxy chloropropane standing demix, remove to contain pure water layer, organic layer-epoxy chloropropane recycled.Obtain easy and simple to handlely, do not need the technical scheme that the catalyst reaction time just can shorten, quality product is stable again.
The present invention adds epoxy chloropropane, alcoholic solvent in the reactor earlier, then in the ratio of mol ratio=1: 9～15 of amino-phenol and epoxy chloropropane, add amino-phenol in the reactive system in 25～55 ℃ in batches, the reinforced time is 2～3 hours, and the back of having fed in raw material was in 45～55 ℃ of insulations 3～5 hours.Follow the Dropwise 50 weight %NaOH aqueous solution, the mol ratio of addition amount of sodium hydroxide and amino-phenol is 4: 1, divide and add for three times in the reactive system, in 50～60 ℃ of reactions 3 hours, underpressure distillation, recovery epoxy chloropropane, distillate standing demix are collected the epoxy chloropropane distillate and are made reaction raw materials usefulness, and the underpressure distillation operating parameters is 60～65 ℃/500～700mmHg here, steam to almost not having till the distillate, contain pure water and be removed.
The resistates that steams behind the superfluous epoxy chloropropane is the aminophenol triglycidyl group compound methylbenzene extraction; the extracting solution water is given a baby a bath on the third day after its birth inferior repeatedly; under 120 ℃/700mmHg, steam toluene; cooling obtains the yellowish brown product; yield 95～98%; oxirane value 0.85～1.00, viscosity≤2500mPa.S, Jia Dena form and aspect 5～7.
Solvent for use of the present invention is to choose any one kind of them from methyl alcohol, ethanol, Virahol, butanols, ethylene glycol.
According to the addition reaction of the invention process amino-phenol and epoxy chloropropane, reinforced 2～3 hours time, be incubated 3～5 hours, the reaction times significantly shortens.
According to the present invention superfluous epoxy chloropropane is distilled, reclaims the distillate standing demix, organic phase directly circulation is made reaction raw materials usefulness, and this method of disposal does not have patent to mention so far.
Its yield of the aminophenol triglycidyl group compound that the present invention makes is 95～98%, color and luster yellowish brown, viscosity≤2500mPa.S, Jia Dena form and aspect 5～7.
Four, specific embodiments
Especially exemplified by example it is described in order to implement the present invention better, but is not limitation of the present invention.
Embodiment 1
With containing 1203g (13 moles) epoxy chloropropane and 552g ethylene glycol in the 5 liter four-hole boiling flasks of the condensing separator that is equipped with agitator, thermometer, nitrogen ingress pipe, dropping funnel and epoxy chloropropane and water azeotropic mixture, logical nitrogen, stir in 40 ℃ and add 109g (1 mole) para-aminophenol in batches, be controlled in 2.5 hours and add, when temperature is raised to 50 ℃ of insulations 4 hours.Then be added dropwise to 50 weight % aqueous sodium hydroxide solution 320g (4 moles of NaOH), divide to be added dropwise in the reactive system for three times, dropwise the back in 55 ℃ of reactions 3 hours.The underpressure distillation that continues, recovery epoxy chloropropane, in 60 ℃/600mmHg distillation down, being distilled to does not almost have till the distillate.Distillate standing over night, layering, reaction raw materials usefulness is made in the epoxy chloropropane circulation, and the mixture of water and ethylene glycol is got rid of, and handles in addition.Behind the underpressure distillation epoxy chloropropane, with 1200ml methylbenzene extraction resistates, extracting solution washes with water 3 times, in 120 ℃, steams toluene under the 700mmHg, obtain yellowish brown para-aminophenol triglycidyl group compound, must measure 271g, yield 98%, its oxirane value is 0.90, viscosity 2500mPa.S, Jia Dena form and aspect 6.
Embodiment 2
Remove and replace para-aminophenol with m-aminophenol, replace outside the ethylene glycol with ethanol, epoxy chloropropane add-on 1388g (15 moles), 25 ℃ of charge temperatures, the reinforced 3 hours time was in 55 ℃ of insulations 5 hours, add alkali and finish the back in 60 ℃ of reactions 3 hours, distillate 65 ℃ of epoxy chloropropane temperature, outside the pressure 500mmHg, other prescription and operation steps and embodiment 1 are just the same.The result obtains yellowish brown m-aminophenol triglycidyl group compound, and it must measure 263g, and yield is 95%, oxirane value 0.85, viscosity 2490mPa.S, Jia Dena form and aspect 5.
Embodiment 3
Remove with adjacent amino-phenol replacement para-aminophenol, replace outside the ethylene glycol epoxy chloropropane add-on 833g (9 moles) with Virahol, 55 ℃ of charge temperatures, the reinforced 2 hours time, and in 45 ℃ of insulations 3 hours, other prescription and operation steps and embodiment 1 were just the same, the result obtains the adjacent aminophenol triglycidyl group compound of yellowish brown, it must be measured and be that 269g, yield 97%, oxirane value are 1.00, viscosity 2485mPa.S, the Jia Dena form and aspect are 7.
Claims (3)
1. the preparation method of aminophenol triglycidyl group compound is characterised in that the mol ratio of amino-phenol and epoxy chloropropane is 1: 9～15, and amino-phenol adds in the reactive system in 25～55 ℃ in batches in alcoholic solvent, and the reinforced time is 2～3 hours; The material add finish after, in 45～55 ℃ of insulations 3-5 hour, follow Dropwise 50 weight % aqueous sodium hydroxide solution, the mol ratio of addition amount of sodium hydroxide and amino-phenol is 4: 1, divide to add for three times in the reactive system, in 50～60 ℃ of reactions 3 hours, underpressure distillation epoxy chloropropane, the distillate standing demix is collected the epoxy chloropropane distillate and is made reaction raw materials usefulness; Use the methylbenzene extraction aminophenol triglycidyl group compound, washing steams toluene under 120 ℃/700mmHg, and cooling obtains yellowish brown product, yield 95～98%, oxirane value 0.85～1.00, viscosity≤2500mPa.S, Jia Dena form and aspect 5～7.
2. according to the preparation method of the aminophenol triglycidyl group compound of claim 1, be characterised in that it is in 60～65 ℃/500～700mmHg distillation down that the step of epoxy chloropropane is reclaimed in described underpressure distillation, till almost not having distillate and coming out, the distillate standing stay-over demixion, collect subnatant, circulation is made reaction raw materials and is used.
3. according to the preparation method of the aminophenol triglycidyl group compound of claim 1, be characterised in that described alcoholic solvent is to choose any one kind of them from methyl alcohol, ethanol, Virahol, butanols, ethylene glycol.
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| CN2007100466340A CN101139327B (en) | 2007-09-29 | 2007-09-29 | Method for preparing aminophenol triglycidyl group compound |
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| CN2007100466340A CN101139327B (en) | 2007-09-29 | 2007-09-29 | Method for preparing aminophenol triglycidyl group compound |
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| CN101139327B CN101139327B (en) | 2010-07-28 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145570A (en) * | 2013-03-14 | 2013-06-12 | 浙江大学 | Synthetic method of m-ethoxy-N,N-diethylaniline |
| CN104478831A (en) * | 2014-11-24 | 2015-04-01 | 上海华谊树脂有限公司 | Preparation method of triglycidyl-meta-aminophenol epoxy resin |
| CN104558519A (en) * | 2014-12-19 | 2015-04-29 | 常州市尚科特种高分子材料有限公司 | Method for preparing tetraglycidyl 4,4'-diamidodicyclohexylmethane epoxy resin |
| JP2017043573A (en) * | 2015-08-28 | 2017-03-02 | 東レ・ファインケミカル株式会社 | 2-glycidyl-oxy-n,n-diglycidyl aniline production process |
| US10023548B2 (en) | 2014-05-15 | 2018-07-17 | Aditya Birla Chemicals (Thailand) Ltd. | Energy efficient manufacturing process for preparing N,O-triglycidyl aminophenols |
-
2007
- 2007-09-29 CN CN2007100466340A patent/CN101139327B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145570A (en) * | 2013-03-14 | 2013-06-12 | 浙江大学 | Synthetic method of m-ethoxy-N,N-diethylaniline |
| CN103145570B (en) * | 2013-03-14 | 2014-12-24 | 浙江大学 | Synthetic method of m-ethoxy-N,N-diethylaniline |
| US10023548B2 (en) | 2014-05-15 | 2018-07-17 | Aditya Birla Chemicals (Thailand) Ltd. | Energy efficient manufacturing process for preparing N,O-triglycidyl aminophenols |
| CN104478831A (en) * | 2014-11-24 | 2015-04-01 | 上海华谊树脂有限公司 | Preparation method of triglycidyl-meta-aminophenol epoxy resin |
| CN104558519A (en) * | 2014-12-19 | 2015-04-29 | 常州市尚科特种高分子材料有限公司 | Method for preparing tetraglycidyl 4,4'-diamidodicyclohexylmethane epoxy resin |
| JP2017043573A (en) * | 2015-08-28 | 2017-03-02 | 東レ・ファインケミカル株式会社 | 2-glycidyl-oxy-n,n-diglycidyl aniline production process |
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| CN101139327B (en) | 2010-07-28 |
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Address after: 200235 No. 36, Shanghai, Caobao Road Patentee after: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS CO., LTD. Address before: 200235 Xuhui District, Caobao Road, No. 36, Patentee before: Shanghai Inst. of Synthetic Resin |
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