CN105017127A - Preparation method for N,N'-4,4'-diphenylmethyene bismaleimide - Google Patents
Preparation method for N,N'-4,4'-diphenylmethyene bismaleimide Download PDFInfo
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- CN105017127A CN105017127A CN201510394566.1A CN201510394566A CN105017127A CN 105017127 A CN105017127 A CN 105017127A CN 201510394566 A CN201510394566 A CN 201510394566A CN 105017127 A CN105017127 A CN 105017127A
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- diaminodiphenyl
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- maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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Abstract
The preparation method comprises a preparation method for a rubber vulcanizer N,N'-4,4'-diphenylmethyene bismaleimide in the presence of an ionic liquid. The preparation method synthesizes N,N'-4,4'-diphenylmethyene bismaleimide by taking 4,4'-diaminodiphenyl-methane and maleic anhydride as raw materials. The preparation method is simple in reaction process and does not need catalysts such as anhydrides and the like, and the obtained product is high in purity.
Description
Technical field
The present invention relates to a kind of vulcanizer
n, the preparation method of N '-4,4 '-diphenyl methane dimaleimide, it belongs to chemical assistant technical field.
Background technology
, N '-4,4 '-diphenyl methane dimaleimide, is called for short BMI, is the organic compound containing two phenyl ring and double imide group.BMI both can be used as vulcanizer in actual applications, can be used as again the rubber cocuring agent in peroxide systems, of many uses.In addition, BMI is again the monomer of bismaleimide polymer, and its polymkeric substance has good radiation resistance, high thermal resistance, wet fastness etc., is widely used in the field such as aerospace, electronics.Production about BMI receives the extensive concern of scientists.
The synthetic method of BMI mainly contains two kinds at present: the first is acetic anhydride evaporation, because this method needs to consume a large amount of irretrievable acetic anhydride and solvent, and solvent and byproduct acetic acid cause a large amount of waste water to be difficult to process, thus higher (the Yuan Jun of cost of the BMI of this method production, Zeng Ying, Ai Jun, East China University of Science's journal: natural science edition, 2006,217-220); The second is azeotropic distn, and hot closed loop dehydration under an acidic catalyst effect, water is steamed reactor by the azeotrope simultaneously utilizing water and solvent to be formed.Thus accelerating hot ring-closure reaction, this method needs to add an acidic catalyst, and an acidic catalyst cannot be recycled, and causes cost to raise (Cao Na, Yuan Haitao, Fu Yuhua, He Junhui, Beijing University of Chemical Technology's journal, 2007,594-598).
We adopt ionic liquid to make solvent, with MALEIC ANHYDRIDE with
n, N '-4,4 '-diphenyl methane dimaleimide is raw material, catalyst-free, without diacetyl oxide condition under synthesize
n, N '-4,4 '-diphenyl methane dimaleimide, reaction solvent recoverable, reduces production cost, easily controls, and is easier to suitability for industrialized production.
Summary of the invention
The object of this invention is to provide one
n, the preparation method of N '-4,4 '-diphenyl methane dimaleimide.The method adopts with 4,4 '-diaminodiphenyl-methane, maleic anhydride for raw material, at ionic liquid [Bmim] [PF
6] in synthesized
n, N '-4,4 '-diphenyl methane dimaleimide, this reaction process is simple, and the purity obtaining product is high.
The object of the invention is to be achieved through the following technical solutions:
A kind of rubber ingredients
n, N '-4,4 '-diphenyl methane dimaleimide, structural formula is as follows:
The invention provides aforementioned rubber auxiliary agent
n, the preparation method of N '-4,4 '-diphenyl methane dimaleimide is according to MALEIC ANHYDRIDE, 4, and the sequencing of 4 '-diaminodiphenyl-methane, ionic liquid, adds raw material in reactor, after completion of the reaction, filters, washing, dry product.
One of feature of the present invention is the selection of proportioning raw materials: be raw material with MALEIC ANHYDRIDE, utilize itself and 4,4 '-diaminodiphenyl-methane carries out substitution reaction.If adopt 4,4 '-diaminodiphenyl-methane is excessive, and the aftertreatment of product brings a lot of difficulty.Through repetition test, be that 1.0-1.1:2.1-2.3 is advisable with the mol ratio of 4,4 '-diaminodiphenyl-methane, MALEIC ANHYDRIDE.In preferred scheme, described mol ratio is that 1.0 ~ 1.1:2.1 ~ 2.2(is more preferably, and described mol ratio is 1.0:2.1).
Two of feature of the present invention is selections of reaction conditions: adopt first adding 4,4 '-diaminodiphenyl-methane, MALEIC ANHYDRIDE join in reactor (round-bottomed flask), then ionic liquid is added, temperature of reaction rises to 120-150 DEG C (preferred 125-135 DEG C, more preferably 130 DEG C).
Foregoing preparation method, preferred scheme is, the reaction times is that 4 ~ 6h(is more preferably 4.5-5.5h).
Products obtained therefrom of the present invention can be weighed from fusing point, nuclear magnetic resonance spectrum index.Its preparation method is that 4,4 '-diaminodiphenyl-methane, MALEIC ANHYDRIDE, ionic liquid are placed in round-bottomed flask, starts to stir, and is warming up to 120-140 DEG C, reacting by heating time 4 ~ 6h; After completion of the reaction, filter, washing, dry product.The method speed of response is fast, reaction process simple, and the product purity obtained is high.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection domain is not by this restriction.In embodiment, each raw material or equipment all can obtain from market.
embodiment 1:5.0mmol 4 is added, 4 '-diaminodiphenyl-methane, 10.5 mmol MALEIC ANHYDRIDE, 3ml ionic liquid [Bmim] [PF in reaction flask
6], 130 DEG C of reacting by heating 5h, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 93%.Gained N, N '-4,4 '-diphenyl methane dimaleimide, outward appearance is yellow powder, and fusing point is 152-154 DEG C.Structural formula is as follows:
。
The nuclear magnetic data of products obtained therefrom is as follows:
1H NMR (400MHz, DMSO
，ppm), δ = 7.41-7.32(8H, m, ArH), 7.21 (4H, m, -CH=CH-),4.02（2H, s, -CH2）.
As can be seen from nuclear magnetic resonance data: this compound structure is symmetrical, phenyl ring just in time has 8 hydrogen, vinyl has 4 hydrogen, benzyl has 2 hydrogen, have 14 hydrogen, just in time meet product structure.
As seen from the above analysis: product, after Modern spectroscopy characterizes, is desired target product.
embodiment 2:5.0mmol 4 is added, 4 '-diaminodiphenyl-methane, 10.0 mmol MALEIC ANHYDRIDE, 3ml ionic liquid, 130 DEG C of reacting by heating 5h in reaction flask, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 88%.
embodiment 3:5.0mmol 4 is added, 4 '-diaminodiphenyl-methane, 11.0 mmol MALEIC ANHYDRIDE, 3ml ionic liquid [Bmim] [PF in reaction flask
6], 130 DEG C of reacting by heating 5h, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 95%.
embodiment 4:5.0mmol 4 is added, 4 '-diaminodiphenyl-methane, 10.5 mmol MALEIC ANHYDRIDE, 3ml ionic liquid [Bmim] [PF in reaction flask
6], 120 DEG C of reacting by heating 5h, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 81%.
embodiment 5:5.0mmol 4 is added, 4 '-diaminodiphenyl-methane, 10.5mmol MALEIC ANHYDRIDE, 3ml ionic liquid [Bmim] [PF in reaction flask
6], 130 DEG C of reacting by heating 4h, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 84%.
embodiment 6:5.0mmol 4 is added, 4 '-diaminodiphenyl-methane, 11.5mmol MALEIC ANHYDRIDE, 3ml ionic liquid [Bmim] [PF in reaction flask
6], 130 DEG C of reacting by heating 6h, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 94%.
embodiment 7:5.2mmol 4 is added, 4 '-diaminodiphenyl-methane, 11.0mmol MALEIC ANHYDRIDE, 3ml ionic liquid [Bmim] [PF in reaction flask
6], 130 DEG C of reacting by heating 4h, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 87%.
embodiment 8:5.2mmol 4 is added, 4 '-diaminodiphenyl-methane, 11.0mmol MALEIC ANHYDRIDE, 3ml ionic liquid [Bmim] Br, 130 DEG C of reacting by heating 4h in reaction flask, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 80%.
After above-described embodiment 1-8 reaction terminates, find 4, the mol ratio of 4 '-diaminodiphenyl-methane, MALEIC ANHYDRIDE is that 1-1.1:2.1-2.3 is advisable in scope, and ionic liquid is [Bmim] [PF
6], temperature of reaction 120-140 DEG C, reaction times 4-6h, yield is higher, reaches re-set target.Gained
n, the performance assessment criteria of N '-4,4 '-diphenyl methane dimaleimide product is as follows: outward appearance: yellow powder; Fusing point (DEG C) 152-154, productive rate is up to 95%.
Claims (6)
1. the preparation method of a vulcanizer N, N '-4,4 '-diphenyl methane dimaleimide, is characterized in that, according to 4,4 '-diaminodiphenyl-methane, MALEIC ANHYDRIDE, ionic liquid [Bmim] [PF
6] sequencing, raw material is added in reactor, after completion of the reaction, suction filtration, washing, drying obtains product.
2. preparation method according to claim 1, is characterized in that, described 4, and the mol ratio of 4 '-diaminodiphenyl-methane, MALEIC ANHYDRIDE is that 1.0-1.1:2.1-2.3 is advisable (preferred, described mol ratio is 1.0:2.1).
3. preparation method according to claim 1, is characterized in that, reaction solvent is ionic liquid [Bmim] [PF
6].
4. preparation method according to claim 1, is characterized in that, the temperature of reaction of reactor is 130 ~ 150 DEG C (preferred 125-135 DEG C, more preferably 130 DEG C).
5. preparation method according to claim 1, is characterized in that, the reaction times is that 4 ~ 6h(is more preferably 4.5-5.5h).
6. a vulcanizer N, the preparation method of N '-4,4 '-diphenyl methane dimaleimide, is characterized in that, 5.0mmol 4 is added, 4 '-diaminodiphenyl-methane, 10.5 mmol MALEIC ANHYDRIDE, 3ml ionic liquid [Bmim] [PF in reaction flask
6], 130 DEG C of reacting by heating 5h, after reacting complete cooling, add in 5mL ethanol, have yellow solid to generate, suction filtration, dry, productive rate 93%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562964A (en) * | 2004-03-22 | 2005-01-12 | 浙江大学宁波理工学院 | Synthetic method of imine ramification |
| CN102363607A (en) * | 2011-11-28 | 2012-02-29 | 中国科学院上海有机化学研究所 | Method for synthesizing maleimide by using strongly acidic room-temperature ionic liquid as medium |
-
2015
- 2015-07-08 CN CN201510394566.1A patent/CN105017127A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562964A (en) * | 2004-03-22 | 2005-01-12 | 浙江大学宁波理工学院 | Synthetic method of imine ramification |
| CN102363607A (en) * | 2011-11-28 | 2012-02-29 | 中国科学院上海有机化学研究所 | Method for synthesizing maleimide by using strongly acidic room-temperature ionic liquid as medium |
Non-Patent Citations (1)
| Title |
|---|
| 曹娜等: "N,N’-4,4’-二苯甲烷双马来酰亚胺的催化合成", 《北京化工大学学报(自然科学版)》 * |
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