CN102358732B - Preparation method for tetraglycidyl-diamine compound - Google Patents
Preparation method for tetraglycidyl-diamine compound Download PDFInfo
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- 0 CCc(cc(Cc(c(*)c1CC)cc(*)c1N)c(*)c1*)c1N Chemical compound CCc(cc(Cc(c(*)c1CC)cc(*)c1N)c(*)c1*)c1N 0.000 description 1
Abstract
The invention provides a preparation method for a tetraglycidyl-diamine compound which has a structure formula I as described in the specification. In the structural formula, R1=H, CH3 or C2H5, and R2=H or Cl. The tetraglycidyl-diamine compound with the chemical structural general formula I is prepared through the following steps that: amide with a chemical structural general formula II reacts with epichlorohydrin at a temperature of 35 to 50 DEG C for 9 to 13 hours in the presence of the catalyst of zinc perchlorate or lanthanum nitrate, wherein, the mol ratio of amide to epichlorohydrin is 1:4-10; then acetone and 18 to 50 wt % of an aqueous solution of sodium hydroxide are added, and an obtained mixture is subjected to reaction at a temperature of 61 to 65 DEG C for 3 to 6 hours; toluene is added for extraction of the product of the tetraglycidyl-diamine compound with the chemical structural general formula I. The performance index of the product varies with the chemical structure of a diamine compound.
Description
One, technical field
The present invention relates to a kind of preparation method of four Racemic glycidol diamine compounds, relate to or rather a kind of preparation method of the four Racemic glycidol diamine compounds with chemical structure of general formula I.
Structure I
R in structural formula I
1=H, CH
3, C
2h
5; R
2=H, Cl
Two, background technology
Epoxy resin is widely used in tackiness agent, coating, casting material, insulating material and reinforced composite technique.N-glycidyl compound has applicable high-performance, and this epoxy resin being coupled together by glycidyl and aromatic group, is often favored by aerospace industry.
About N, N, N ', N '-four glycidyl group-3,3 '-diethyl-4, the preparation method of 4 '-diaminodiphenyl-methane reports existing a lot.There is USP.5 with the maximally related patent of the present invention, 280,069, Jan.18,1994, U.S.P.5,362,849, Nov.8,1994 and CN200910054702.7,2009,07,13.Front two sections of United States Patent (USP)s application 3,3 '-diethyl-4,4 '-diaminodiphenyl-methane, toluene and lanthanum nitrate catalyzer are heated to 60 DEG C under 120mmHg pressure, then with 1 hours, epoxy chloropropane are added therebetween, then add residual catalyst, in 80 DEG C of reactions 19 hours, then be cooled to 60 DEG C, then add benzyl tri-chlorination aqueous ammonium, aqueous sodium hydroxide solution, feeding study on period 3 hours, carry out vacuum hydro-extraction, then add water stratification, add the neutralization of biphosphate sodium water solution.Use again methylbenzene extraction product, boil off toluene and obtain product.CN200910054702.7 discloses etherification reaction and uses saltpetre or halogen acetate to make catalyzer, answers the mixture of spent glycol and water as solvent.Etherification temperature 50～70 DEG C/4～7 hours.Cyclisation temperature 50～60 DEG C/3～5 hours, cyclisation is used sodium hydroxide and salt of wormwood mixed alkali liquor.Above-mentioned United States Patent (USP) technology is all used vacuum hydro-extraction in etherificate and cyclisation stage.Operate comparatively numerous and diverse, and contrast response temperature drift.Its feature temperature of reaction of above-mentioned Chinese patent technology is low, must improved place be the etherificate stage can not make spent glycol, must not use mixed alkaline solution when cyclisation.In order to improve the defect of above-mentioned patented technology, the present inventors propose suitable technical scheme through concentrating on studies.
Three, summary of the invention
The present inventors have done a large amount of research work, prior art is analyzed relatively, more desirable technical scheme is proposed, the feature of this technical scheme is can be by 3, 3 '-diethyl-4, 4 '-diaminodiphenyl-methane and epichlorohydrin reaction synthesize four glycidyl group-3, 3 '-diethyl-4, 4 '-diaminodiphenyl-methane, also can synthesize the four glycidyl group diamine compound that aminate structure is more complicated, for example, N, N, N ', N '-four glycidyl group-3, 3 ', 5, 5 ' tetraethyl--2, 6 '-bis-chloro-4, 4 '-bis-amido ditans, N, N, N ', N '-four glycidyl group-3, 3 '-5, 5 '-tetraethyl--4, 4 '-diaminodiphenyl-methane and N, N, N ', N '-four glycidyl group-3, 3 ' diethyl-5, 5 '-dimethyl-4, 4 '-diaminodiphenyl-methane.
The present invention is a kind of preparation method of the four Racemic glycidol diamine compounds with chemical structure of general formula I.
Structure I
R in structural formula I
1=H, CH
3, C
2h
5; R
2=H, Cl
This four Racemic glycidols diamine compound is to be prepared by aminate and the epichlorohydrin reaction with chemical structure of general formula II.
Structure I I
R in formula II
1=H, CH
3, C
2h
5; R
2=H, Cl
Chemical structure of general formula II aminate and epoxy chloropropane 1: 4 in molar ratio～10, under zinc perchlorate or the existence of lanthanum nitrate catalyzer, here catalyst levels is 1.5～3 % by weight of chemical general formula II aminate weight, in 35～50 DEG C of reaction 9-13 hour, then add acetone solvent and 28～30 % by weight aqueous sodium hydroxide solutions in 61～65 DEG C of reactions 3～6 hours, add the four Racemic glycidol diamine compounds of methylbenzene extraction chemical structure of general formula I, boil off the four Racemic glycidol diamine compound products that toluene must have chemical structure of general formula I, the viscosity of product, oxirane value is different with the chemical structure of diamine compound.
In the present invention, the weight ratio of acetone solvent consumption and epoxy chloropropane consumption is 1: 1.
In the present invention, toluene consumption is two times of epoxy chloropropane weight.The consumption of 28-50 % by weight aqueous sodium hydroxide solution is that the diamine compound of chemical structure of general formula II and the mol ratio of sodium hydroxide are 1: 4～8.
Four its performance index of Racemic glycidol diamine compound I of preparing according to the invention process are different and different with raw material chemical structure.Existing list is shown it:
Four, embodiment
Illustrate it in order to implement better spy of the present invention, but embodiment not limitation of the present invention.
Embodiment 1
In 500ml there-necked flask, add 100g (1.08mol) epoxy chloropropane, 0.5g zinc perchlorate catalyzer, be heated to 50 DEG C, add 56.7g (0.15mol) 3 in batches, 3 ', 5, 5 '-tetraethyl--2, 6 '-bis-chloro-4, 4 '-bis-amido ditans, after stirring reaction 10 hours, add 100g acetone to continue reaction 3 hours, be added dropwise to 30 % by weight aqueous sodium hydroxide solution 200g, carry out ring-closure reaction 4 hours in 63 DEG C, add 200g toluene, separate toluene phase, boil off toluene and obtain N, N, N ', N '-four glycidyl group 3, 3 ', 5, 5 '-tetraethyl--2, 6 '-bis-chloro-4, 4 '-bis-amido ditans, its oxirane value is 0.416 equivalent/100g, viscosity 310000mPa.S.
Embodiment 2
Except using 39.2g (0.15mol) 3,3 '-diethyl-4,4 '-diaminodiphenyl-methane replaces 3,3 ', 5,5 ' tetraethyl--2,6 '-bis-chloro-4,4 '-bis-amido ditans, 0.8g lanthanum nitrate replaces outside zinc perchlorate, other formulas are the same with embodiment 1 with operation steps, product four glycidyl group-3,3 '-diethyl-4,4 '-diaminodiphenyl-methane, 25 DEG C of its viscosity, 5200mPa.S, oxirane value 0.76 equivalent/100g.
Embodiment 3
Except using 72g (0.25mol) 3,3 '-diethyl-5,5 '-dimethyl-4, outside 4 '-diaminodiphenyl-methane and 2.16g lanthanum nitrate catalyzer, other formula is the same with embodiment 1 with operation steps, and product four shrinks 3,3 '-diethyl-5,5 '-dimethyl-4,25 DEG C of 59000mPa.S of 4 '-diaminodiphenyl-methane viscosity, oxirane value 0.572 equivalent/100g.
Claims (1)
1. a preparation method for four Racemic glycidol diamine compounds, is characterized in that:
R in structural formula I
1=C
2h
5, R
2=Cl;
R in formula II
1=C
2h
5, R
2=Cl;
In 500ml there-necked flask, add 100g epoxy chloropropane, 0.5g zinc perchlorate catalyzer, be heated to 50 DEG C, add 56.7g to meet the compound 3 of formula II in batches, 3 ', 5, 5 '-tetraethyl--2, 6'-bis-chloro-4, 4 '-bis-amido ditans, after stirring reaction 10 hours, add 100g acetone to continue reaction 3 hours, be added dropwise to 30 % by weight aqueous sodium hydroxide solution 200g, carry out ring-closure reaction 4 hours in 63 DEG C, add 200g toluene, separate toluene phase, boil off the compound N that toluene obtains meeting structural formula I, N, N ', N '-four glycidyl group 3, 3 ', 5, 5 '-tetraethyl--2, 6'-bis-chloro-4, 4'-bis-amido ditans, its oxirane value is 0.416 equivalent/100g, viscosity 310000mPa.S.
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| CN103242265B (en) * | 2013-05-15 | 2015-07-08 | 东华大学 | Preparation method of N,N,N',N'-tetraglycidyl-2,2-bi[4-(4-amino phenoxyl)]propane |
| EP3411362B1 (en) * | 2016-02-04 | 2023-06-07 | Grasim Industries Limited | A process for preparation of an aromatic n-glycidylamine |
| CN109516965A (en) * | 2018-11-22 | 2019-03-26 | 西安元创化工科技股份有限公司 | A kind of synthetic method of TGDDM epoxy resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5280069A (en) * | 1990-05-05 | 1994-01-18 | Ciba-Geigy Corporation | N-glycidyl compound |
| CN101157672A (en) * | 2007-11-08 | 2008-04-09 | 上海市合成树脂研究所 | Method for preparing bis[3-chlorin-4-di(2,3- epoxy propyl) aminophenyl] methane |
| CN101665475A (en) * | 2009-07-13 | 2010-03-10 | 上海市合成树脂研究所 | Preparation method of tetraglycidyl-3,3'-diethyl-4,4'-diaminodiphenyl-methane |
-
2011
- 2011-08-30 CN CN201110253285.6A patent/CN102358732B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5280069A (en) * | 1990-05-05 | 1994-01-18 | Ciba-Geigy Corporation | N-glycidyl compound |
| CN101157672A (en) * | 2007-11-08 | 2008-04-09 | 上海市合成树脂研究所 | Method for preparing bis[3-chlorin-4-di(2,3- epoxy propyl) aminophenyl] methane |
| CN101665475A (en) * | 2009-07-13 | 2010-03-10 | 上海市合成树脂研究所 | Preparation method of tetraglycidyl-3,3'-diethyl-4,4'-diaminodiphenyl-methane |
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Effective date of registration: 20210129 Address after: No. 1251, Zhulu West Road, Xujing Town, Qingpu District, Shanghai, 201702 Patentee after: SHANGHAI PLASTICS RESEARCH INSTITUTE Co.,Ltd. Address before: 200235 No. 36, Shanghai, Caobao Road Patentee before: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS Co.,Ltd. |