CN101870693B - Bismaleimide containing 1,3,4-oxadiazole structure and preparation method thereof - Google Patents
Bismaleimide containing 1,3,4-oxadiazole structure and preparation method thereof Download PDFInfo
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- CN101870693B CN101870693B CN2010102114390A CN201010211439A CN101870693B CN 101870693 B CN101870693 B CN 101870693B CN 2010102114390 A CN2010102114390 A CN 2010102114390A CN 201010211439 A CN201010211439 A CN 201010211439A CN 101870693 B CN101870693 B CN 101870693B
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- oxadiazole structure
- bismaleimides
- oxadiazole
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Abstract
The invention relates to a bismaleimide containing a 1,3,4-oxadiazole structure and a preparation method thereof. In the structural formula of bismaleimide, substituents of R1 to R4 can be hydrogen atom, halogen atom, or same or different fat alkane of C1 to C20 and derivatives thereof, or same of different aromatic of C6 to C12 and derivatives thereof. The bismaleimide with a 1,3,4-oxadiazole structure is prepared by reacting diamine with a 1,3,4-oxadiazole structure with maleic anhydride to produce bismaleamic and performing imide cyclization reaction under the action of catalyst and dehydrating agent. The bismaleimide containing the1,3,4-oxadiazole structure has an asymmetric structure; and two reactive groups have different reaction activities in different chemical environments and can successively react at different curing temperatures. In addition, the cured product of the bismaleimide with a 1,3,4-oxadiazole structure has excellent heat resistance and is suitable for being used as a high-performance polymer composite matrix.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to contain 1,3,4-oxadiazole structure bismaleimides and preparation method thereof.
Background technology
Bismaleimides is a kind of important Thermocurable polyimide, has the good characteristic of polyimide, for example: good thermostability, electrical insulation capability, excellent chemicals-resistant burn into radiation hardness, moisture-proof heat and mechanical property etc.Bismaleimides is small molecules thereby the workability that has the loop-like epoxy resins again ability simultaneously, and moulding process is flexible.Two keys at its molecule two ends owing to the strong electrophilic effect that receives two carbonyls have strong Electron Affinities can with diamines, nucleophilic group generation nucleophilic additions such as diphenol also can have power supply property unsaturated double-bond generation copolyreaction with allylic cpd etc.Bismaleimides carries out modification owing to but its molecular structure design mode can react with multiple monomer again by force, can prepare the thermosetting material that satisfies the various uses needs, is widely used in fields such as aerospace, mechano-electronic, communications and transportation.
By 2,5-two (4-aminophenyl)-1,3,4-oxadiazole synthetic 2,5-two (4-dimaleoyl imino phenyl)-1,3,4-oxadiazole (seeing structural formula A) have excellent thermotolerance, high carbon residue rate, high limiting oxygen index(LOI) (LOI) and good flame-retardance.But this monomer molecule structure all is made up of inflexible virtue heterocycle, has the symmetry and the rigidity of height, makes it when having above-mentioned plurality of advantages considerable shortcoming arranged also, for example: very high fusing point, its fusing point is near 300 ℃; Very poor solvability is insoluble in most of organic solvents.HMP makes fusion solidify at once, and curing reaction temperature is high, and exothermic heat of reaction is concentrated, and causes the melt-processed difficulty.Poorly solublely also make it not process with solution method.Therefore this monomer is difficult to use in glue paste and matrix material.
A.2,5-two (4-dimaleoyl imino phenyl)-1,3,4-oxadiazole structural formula
Document (polymer, 2007,48) has reported that two kinds contain two 1,3, and the monomeric compound method of chain-prolonged type bismaleimides of 4-oxadiazole ring has been studied solvability and curing reaction characteristic.Its solvability has obtained tangible improvement can be dissolved in chloroform, methylene dichloride, N, but dinethylformamide equal solvent fusing point still very high (266 ℃, 263 ℃), and processing characteristics is also very poor.And both having contained high heatproof oxidation performance 1,3,4-oxadiazole heterocycle contains bismaleimides of rotatable fat ether connecting key and preparation method thereof again and does not see as yet that up to now disclosed patent or bibliographical information are arranged.
Summary of the invention
One of the object of the invention is to provide a kind of favorable solubility, and fusing point is low, and curing exotherm is steady, and the cured article fine heat-resisting performance contain 1,3,4-oxadiazole structure bismaleimides.It is above-mentioned novel 1,3 that two of the object of the invention is to provide, the preparation method of 4-oxadiazole structure bismaleimides.
The present invention solves the technical scheme that its technical problem takes: one type contains 1,3, and 4-oxadiazole structure bismaleimides has following structural formula:
Substituent R in the formula
1To R
4Be Wasserstoffatoms, halogen atom, or C
1To C
20Identical or different fat alkane and verivate thereof, or C
6To C
12Identical or different aromatic hydrocarbon and verivate thereof.
What the present invention relates to contains 1,3, and 4-oxadiazole structure bismaleimides synthetic route is following:
Substituent R in the formula
1To R
4Be Wasserstoffatoms, halogen atom, or C
1To C
20Identical or different fat alkane and verivate thereof, or C
6To C
12Identical or different aromatic hydrocarbon and verivate thereof.
Its preparation method may further comprise the steps:
(1) contain 1,3,4-oxadiazole structure span comes the synthetic of amido acid
To contain 1,3, the diamine of 4-oxadiazole structure and maleic anhydride are dissolved in respectively in the aprotic polar solvent, and containing 1,3, the drips of solution of the diamine of 4-oxadiazole structure is added in the maleic anhydride solution then, stir 2～10 hours.After reaction finishes, if be then direct filtration of reaction solvent, with fresh reaction solvent washing leaching cake, vacuum drying with a kind of in acetone, THF, the ETHYLE ACETATE; If with N, a kind of in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone is reaction solvent; In reaction system, drip precipitation agent water; Static, suction filtration are with low boiling point solvent methyl alcohol, acetone or THF flush cake, vacuum drying.
(2) contain 1,3,4-oxadiazole structure bismaleimides synthetic
Span is come amido acid to be dissolved in or is suspended in the aprotic polar solvent, add acetate, be heated to 20～90 ℃, drip triethylamine and diacetyl oxide.Reaction finishes the back and slowly splashes into reaction solution in the water, with the sedimentation and filtration that generates, vacuum-drying.
Step (1) is described to contain 1,3, and the mole proportioning of 4-oxadiazole structure aromatic diamine and maleic anhydride is 1: 2～1: 2.5, and temperature of reaction is 0～60 ℃, and the reaction times is 2～10 hours.
The described non-protonic solvent of step (1) is acetone, THF, ETHYLE ACETATE, N, a kind of in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone.The solvent of recommending is a kind of in acetone, THF, the ETHYLE ACETATE.
The described dewatering agent of step (2) is a diacetyl oxide, and temperature of reaction is 20～90 ℃, and the reaction times is 2～10 hours.
The described aprotic polar solvent of step (2) is an acetone, N, dinethylformamide, DMAC N,N, the mixed solvent of one or more in the N-Methyl pyrrolidone.
The described acetate of step (2) is one or more mixtures of sodium-acetate, magnesium acetate, nickel acetate and Cobaltous diacetate.
The consumption of the said dewatering agent diacetyl oxide of step (2) is 2～4 times that span comes amido acid, and the consumption of said catalyst of triethylamine is 0.1～2.5 times that span comes amido acid, and the consumption of acetate is that every mole of span of 0.1～3g comes amido acid.
The invention has the beneficial effects as follows that designing and synthesizing one type contains 1,3,4-oxadiazole structure bismaleimides, its primary structure are that fragrant heterocycle structure can keep good thermotolerance; Introducing 1; 3, the synthetic characteristics according to it in the time of 4-oxadiazole structure are introduced flexible fat ehter bond at an end of ring, and the spinability of ehter bond has improved the flexibility of molecular structure; Also destroyed simultaneously the regularity of molecular structure, its solvability increase, fusing point are reduced; And the reactive group at two ends is in different chemical environments, and its reactive behavior is different, can make two key consecutive reactions guarantee that curing reaction heat emits gently.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is done further explanation.
Fig. 1 be 2-of the present invention to dimaleoyl imino phenyl-5-to dimaleoyl imino Phenoxymethyl-1,3,4-oxadiazole (curve A) and presoma span thereof come the ir spectra of amido acid (curve B).
Fig. 2 be 2-of the present invention to dimaleoyl imino phenyl-5-to dimaleoyl imino Phenoxymethyl-1,3, the nucleus magnetic hydrogen spectrum of 4-oxadiazole.
Embodiment
Below in conjunction with specific embodiment, further explain the present invention.Its purpose is to understand better the present invention, and unrestricted protection scope of the present invention.
Embodiment 1
2-to dimaleoyl imino phenyl-5-to dimaleoyl imino Phenoxymethyl-1,3,4-oxadiazole synthetic:
(1) 0.11mol maleic anhydride and 50ml acetone are added in the reaction kettle stirring and dissolving.0.05mol is contained 1,3, and 4-oxadiazole structure aromatic diamine is dissolved in the 200ml acetone, slowly is added drop-wise in the reaction kettle then.At room temperature stir 6h.After reaction finishes, the crystal that generates is filtered, use 150ml washing with acetone filter cake again, vacuum-drying obtains yellow span and comes amido acid, productive rate 93%.FT-IR (KBr, cm
-1): [seeing Fig. 1 (B)] 3289,1543 (NH), 1708,1633 (C=O).
(2) come amido acid to be suspended in the 150ml acetone 0.04mol span, add the 0.15g Cobaltous diacetate, be heated to 60 ℃, drip 6ml triethylamine and 12ml diacetyl oxide, question response liquid becomes constant temperature timing 5h behind the homogeneous phase.Reaction finishes the back and slowly splashes into reaction solution in the water of stirring, the crystal that generates is filtered vacuum-drying.Obtain yellow bismaleimides crystal, productive rate 84%.FT-IR (KBr, cm
-1): [seeing Fig. 1 (A)] 3099,691 (=C-H), 1720 (C=O), 1392,1150 (C-N-C).
1H NMR (400MHz, DMSO-d
6): (see figure 2) δ 8.15 (2H, ArH), 7.63 (2H, ArH), 7.30 (2H, ArH), 7.25 (2H ,-C=CH), 7.23 (2H, J=9.1Hz, ArH), 7.17 (2H ,-C=CH) 5.56 (2H ,-CH
2-).
Embodiment 2
2-to dimaleoyl imino phenyl-5-(3-methyl-4-dimaleoyl imino Phenoxymethyl-1,3,4-oxadiazole synthetic:
(1) 0.11mol maleic anhydride and 30ml acetone are added in the reaction kettle stirring and dissolving.0.05mol is contained methyl and 1,3, and 4-oxadiazole structure aromatic diamine is dissolved in the 120ml acetone, slowly is added drop-wise in the reaction kettle then.At room temperature stir 10h.After reaction finishes, the crystal that generates is filtered, use 100ml washing with acetone filter cake again, vacuum-drying obtains yellow span and comes amido acid, productive rate 95%.FT-IR(KBr，cm
-1)：3289，1543(-NH)，2963，2926(-CH
3)1708，1633(C＝O)。
(2) come amido acid to be suspended in the 150ml acetone 0.04mol span, add the 0.15g Cobaltous diacetate, be heated to 50 ℃, drip the 7ml triethylamine, question response liquid drips the 10ml diacetyl oxide, constant temperature 7h after becoming homogeneous phase.Reaction finishes the back and slowly splashes into reaction solution in the water of stirring, the crystal that generates is filtered vacuum-drying.Obtain yellow bismaleimides crystal, productive rate 87%.FT-IR(KBr，cm
-1)：3097，692(＝C-H)，2961，2929(-CH
3)，1718(C＝O)，1396，1149(C-N-C)。
Claims (8)
1. one kind contains 3, and 4-oxadiazole structure bismaleimides is characterized in that it has following structural formula:
Substituent R in the formula
1To R
4Be Wasserstoffatoms, C
1To C
20The fat alkane base, and above-mentioned four substituting groups are identical or different each other.
2. prepare and as claimed in claim 1ly contain 1,3, the method for 4-oxadiazole structure bismaleimides; It is characterized in that: saidly contain 1; 3,4-oxadiazole structure bismaleimides is by containing 1,3; 4-oxadiazole structure aromatic diamine and maleic anhydride reaction generate span and come amido acid, under the effect of catalyzer, dewatering agent, carry out imide cyclisation reaction then and make.
3. preparation according to claim 2 contains 1; 3, the method for 4-oxadiazole structure bismaleimides is characterized in that: said span come amido acid be by the mole proportioning be 1: 2～1: 2.5 contain 1; 3; 4-oxadiazole structure aromatic diamine and maleic anhydride react in non-protonic solvent and make, and temperature of reaction is 0～60 ℃, and the reaction times is 2～10 hours.
4. preparation according to claim 3 contains 1; 3; The method of 4-oxadiazole structure bismaleimides; It is characterized in that: described non-protonic solvent is acetone, THF, ETHYLE ACETATE, N, a kind of in dinethylformamide, DMAC N,N and the N-Methyl pyrrolidone.
5. preparation according to claim 2 contains 1; 3, the method for 4-oxadiazole structure bismaleimides is characterized in that: said span comes the imide cyclisation of amido acid to be reflected in the non-protonic solvent to carry out; Use diacetyl oxide to be dewatering agent; Acetate and triethylamine are catalyzer, and temperature of reaction is 20～80 ℃, and the reaction times is 2～10 hours.
6. preparation according to claim 5 contains 1; 3, the method for 4-oxadiazole structure bismaleimides is characterized in that: said non-protonic solvent is acetone, N; The mixed solvent of one or more in dinethylformamide, DMAC N,N, the N-Methyl pyrrolidone.
7. preparation according to claim 5 contains 1,3, and the method for 4-oxadiazole structure bismaleimides is characterized in that: described acetate is one or more mixture of sodium-acetate, magnesium acetate, nickel acetate and Cobaltous diacetate.
8. preparation according to claim 5 contains 1; 3; The method of 4-oxadiazole structure bismaleimides; It is characterized in that: the consumption of said dewatering agent diacetyl oxide is 2～4 times that span comes amido acid, and the consumption of said catalyst of triethylamine is 0.1～2.5 times that span comes amido acid, and the consumption of acetate is that every mole of span of 0.1～3g comes amido acid.
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| CN102942564A (en) * | 2012-11-20 | 2013-02-27 | 沈阳航空航天大学 | Asymmetric bismaleimide containing 1, 3, 4-oxadiazole structure and preparation method thereof |
| CN104447869B (en) * | 2014-10-27 | 2019-03-01 | 复旦大学 | It is a kind of containing DOPO and the asymmetric bismaleimide of molecular structure, preparation method and in the application prepared in compound resin |
| CN104629052B (en) * | 2015-01-16 | 2017-02-01 | 沈阳航空航天大学 | Bismaleimide resin containing cyano group and phthalidyl side group and preparation method thereof |
| CN106905483B (en) * | 2015-12-23 | 2019-09-17 | 大连理工常熟研究院有限公司 | A kind of cyclic olefine copolymer and preparation method thereof |
| CN113234006A (en) * | 2021-04-22 | 2021-08-10 | 沈阳化工大学 | Synthesis method of bismaleimide containing adamantane side group triarylamine |
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Address after: 116024 Liaoning, Dalian, Ganjingzi Ling Road, No. 2 Patentee after: Dalian University of Technology Patentee after: Shenyang Aerospace University Address before: 110136 Shenyang Province, moral economic development zone, moral, South Street, No. 37, No. Patentee before: Shenyang Aerospace University Patentee before: Dalian University of Technology |
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Granted publication date: 20120321 Termination date: 20210629 |