CN107915818A - A kind of thermosetting resin containing cyano group and preparation method thereof - Google Patents
A kind of thermosetting resin containing cyano group and preparation method thereof Download PDFInfo
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- CN107915818A CN107915818A CN201711145731.5A CN201711145731A CN107915818A CN 107915818 A CN107915818 A CN 107915818A CN 201711145731 A CN201711145731 A CN 201711145731A CN 107915818 A CN107915818 A CN 107915818A
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- Prior art keywords
- cyano group
- benzoxazine
- reaction
- preparation
- benzoxazine colophony
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention provides a kind of thermosetting resin containing cyano group and preparation method thereof, its molecular structural formula is as follows：
Description
Technical field
The present invention relates to a kind of thermosetting resin and its manufacture method, more particularly to a kind of thermosetting resin containing cyano group
And preparation method thereof.
Background technology
Benzoxazine colophony is a kind of thermosetting resin occurred in recent years, passes through heating or catalyst , oxazine lists
Body open loop polycondensation forms the resin that structure is similar to phenolic aldehyde；Discharged during reaction without small molecule, the net structure formed after polymerization
Densification, water absorption rate is low, and volume contraction is similar to zero, and comprehensive performance is better than the tree such as phenolic resin, epoxy resin and maleimide
Fat, its main application aspect are the fields such as ablation resistant material, aerospace material, medical material and electronic material.Ben Bing Evil
Piperazine has flexible MOLECULE DESIGN so that it has wide application and development space.
Traditional benzoxazine colophony often produces oligomer accessory substance in preparation process, and the phenol in the oligomer
Hydroxyl can cause benzoxazine ring curing reaction, cause resin to be not easy to store, the shelf-life is shorter.And if obtained by purification processes
To the benzoxazine colophony of high-purity, the production cost of preparation process can be not only improved, can also bring resin cure temperature higher
The defects of.New functionalization group is introduced in a kind of important method Shi oxazine structures that benzoxazine colophony is modified.
Chinese patent application《Aromatic diamine type cyano group-containing benzoxazine colophony and preparation method thereof》(publication number
CN102516537B a kind of benzoxazine colophony preparation process of cyano-containing) is disclosed, using three-step approach, the first step prepares dinitro
Based compound, the step must use higher temperature (140-145 degree)；Second step is to carry out reduction to nitro to prepare two amine compounds
Thing, reaction process need to use catalyst, and reaction is complicated, easily brings environmental problem, could Bei oxazines tree processed by the synthesis of the 3rd step
Fat, step is complicated in general, of high cost and not environmentally, and the product yield prepared is not high.
In view of above-mentioned existing benzoxazine monomer there are the defects of, the present inventor be based on be engaged in such product design system
Abundant for many years practical experience and professional knowledge are made, and coordinates the utilization of scientific principle, is actively subject to research and innovation, to found one kind
Thermosetting resin containing cyano group and preparation method thereof, makes it have more practicality.By constantly research, design, and through anti-
After retrial is made sample and improved, the present invention having practical value is created finally.
The content of the invention
The present invention provides a kind of thermosetting resin containing cyano group and preparation method thereof, the production of benzoxazine colophony is improved
Rate.
The present invention is realized using following scheme：
Benzoxazine colophony proposed by the present invention containing cyano group, has following molecular structural formula,
As preference, the benzoxazine colophony containing cyano group, cure peak temperature is 185-203 DEG C.
As preference, the benzoxazine colophony containing cyano group, at 800 DEG C, the Residual carbon of resin is 73.2-79.8%.
The preparation method of benzoxazine colophony containing cyano group, including following operating procedure：
Step 1, synthesizes benzoxazine, its reaction equation is such as with Bisphenol F, a cyano-aniline and paraformaldehyde with solventless method
Shown in lower：
Step 2, is dissolved in 1-methyl-2-pyrrolidinone, with 4- nitrophthalonitriles with the benzoxazine of gained in step 1
Reaction, reaction equation are as follows：
Step 3, is warming up to 200-240 DEG C of curing by obtained solid in step 2, obtains target product.
As preference, the preparation method of the benzoxazine colophony containing cyano group, Bisphenol F in the step 1, a cyano group
The molar ratio of aniline and paraformaldehyde is 1：2：4-4.8.
As preference, the preparation method of the benzoxazine colophony containing cyano group, the step 1 reaction is solvent-free
Under the conditions of carry out, reaction temperature be 80-120 DEG C, reaction time 0.5-6h.
As preference, the preparation method of the benzoxazine colophony containing cyano group, benzoxazine in the step 2,4- nitre
The molar ratio of base phthalonitrile and potassium carbonate is 1：1.0-2.0：1.0-3.0.
As preference, the preparation method of the benzoxazine colophony containing cyano group, Carbon Dioxide is used in the step 2
Potassium, solvent are removed water with molecular sieve.
As preference, the preparation method of the benzoxazine colophony containing cyano group, the step 2 reaction at room temperature and
Carried out under nitrogen atmosphere, react 8-36h；Then reaction solution is poured into deionized water, the precipitation of precipitation is washed, it is dry, i.e.,
Obtain the target product of step 2.
The beneficial functional of the present invention is：
The benzoxazine monomer of cyano-containing prepared by method using the present invention, first step solventless method synthesis benzoxazine
Monomer, since no product is lost in, and reaction is easy to carry out, and the extent of reaction is very high, can almost obtain the amount of equal material
Benzoxazine, second step reaction is equally easy to carry out, the filtrate after reaction, which is poured into water, can separate out most precipitations,
Mixed solution after filtering can also be separated water and 1-methyl-2-pyrrolidinone by distilling, so as to recycle.With this side
Not only excellent performance, its yield are more up to more than 88% to the benzoxazine of method production.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Concrete operation step：
The preparation method of benzoxazine colophony containing cyano group, in step 1, by Bisphenol F, a cyano-aniline, paraformaldehyde
Mix, be added in flask in molar ratio, stir and react in oil bath pan, temperature is reacted after slowly being raised from room temperature.
In step 2, by benzoxazine and 4- nitrophthalonitriles, potassium carbonate is put into flask, under nitrogen atmosphere room
When temperature reaction 8-36 is small, the mixture that reaction is obtained filters, and filtrate is poured into a large amount of cold water, will precipitate after filtering in vacuum
Drying, obtains product in drying box.
Embodiment 1
By 2.5g Bisphenol Fs, cyano-aniline between 2.950g, 1.650g paraformaldehydes are added in three-necked flask, connect condenser pipe
And agitating device, temperature is slowly raised to 110 DEG C, when reaction 6 is small, reactant is taken out, obtains 6.150g benzoxazine solids.
By 2g benzoxazines, 0.731g 4- nitrophthalonitriles, 0.659g Anhydrous potassium carbonates are placed in three-necked flask,
30ml 1-methyl-2-pyrrolidinones are added, under the protection of nitrogen, 36h is reacted at room temperature, the material after reaction is filtered, by filtrate
Pour into substantial amounts of water, solid is filtered out, and wash several times, it is dry, obtain 2.411g products；Yield reaches after testing
90%.
Embodiment 2
By 2.5g Bisphenol Fs, cyano-aniline between 2.950g, 1.650g paraformaldehydes are added in three-necked flask, connect condenser pipe
And agitating device, temperature is slowly raised to 100 DEG C, when reaction 2 is small, reactant is taken out, obtains 6.065g benzoxazine solids.
By 2g benzoxazines, 0.731g 4- nitrophthalonitriles, 2.285g Anhydrous potassium carbonates are placed in three-necked flask,
30ml 1-methyl-2-pyrrolidinones are added, under the protection of nitrogen, 8h is reacted at room temperature, the material after reaction is filtered, filtrate is fallen
Enter in substantial amounts of water, solid is filtered out, and wash several times, it is dry, 2.285g products are obtained, yield reaches 91% after testing.
Embodiment 3
By 1.5g Bisphenol Fs, cyano-aniline between 1.770g, 0.990g paraformaldehydes are added in three-necked flask, connect condenser pipe
And agitating device, temperature is slowly raised to 90 DEG C, when reaction 6 is small, reactant is taken out, obtains 3.582g benzoxazine solids.
By 1g benzoxazines, 0.365g 4- nitrophthalonitriles, 0.330g Anhydrous potassium carbonates are placed in three-necked flask,
20ml 1-methyl-2-pyrrolidinones are added, under the protection of nitrogen, 12h is reacted at room temperature, the material after reaction is filtered, by filtrate
Pour into substantial amounts of water, solid is filtered out, and wash several times, it is dry, obtain 1.196g products；Yield reaches after testing
89%.
Embodiment 4
By 1.5g Bisphenol Fs, cyano-aniline between 1.770g, 0.990g paraformaldehydes are added in three-necked flask, connect condenser pipe
And agitating device, temperature is slowly raised to 110 DEG C, when reaction 0.5 is small, reactant is taken out, 3.571g benzoxazines is obtained and consolidates
Body.
By 1g benzoxazines, 0.365g 4- nitrophthalonitriles, 0.330g Anhydrous potassium carbonates are placed in three-necked flask,
15ml 1-methyl-2-pyrrolidinones are added, under the protection of nitrogen, 24h is reacted at room temperature, the material after reaction is filtered, by filtrate
Pour into substantial amounts of water, solid is filtered out, and wash several times, it is dry, obtain 1.205g products；Yield reaches after testing
92%.
The benzoxazine monomer of cyano-containing prepared by method using the present invention, yield are up to more than 88%, operate at the same time
Step is relatively simple, has preferable application prospect.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
- A kind of 1. benzoxazine colophony containing cyano group, it is characterised in that：With following molecular structural formula,
- 2. the benzoxazine colophony according to claim 1 containing cyano group, it is characterised in that：Cure peak temperature is 185- 203℃。
- 3. the benzoxazine colophony according to claim 1 containing cyano group, it is characterised in that：At 800 DEG C, the carbon residue of resin Rate is 73.2-79.8%.
- 4. containing the preparation method of the benzoxazine colophony of cyano group according to claims 1 to 3 any one of them, its feature exists In：Including following operating procedure：Step 1, benzoxazine, the following institute of its reaction equation are synthesized with Bisphenol F, a cyano-aniline and paraformaldehyde with solventless method Show：Step 2, is dissolved in 1-methyl-2-pyrrolidinone with the benzoxazine of gained in step 1, is reacted with 4- nitrophthalonitriles, Reaction equation is as follows：Step 3, is warming up to 200-240 DEG C of curing by obtained solid in step 2, obtains target product.
- 5. the preparation method of the benzoxazine colophony according to claim 4 containing cyano group, it is characterised in that：The step The molar ratio of Bisphenol F in one, a cyano-aniline and paraformaldehyde is 1：2：4.0-4.8.
- 6. the preparation method of the benzoxazine colophony according to claim 4 containing cyano group, it is characterised in that：The step One reaction carries out in the absence of a solvent, and reaction temperature is 80-120 DEG C, reaction time 0.5-6h.
- 7. the preparation method of the benzoxazine colophony according to claim 4 containing cyano group, it is characterised in that：The step The molar ratio of benzoxazine in two, 4- nitrophthalonitriles and potassium carbonate is 1：1.0-2.0：1.0-3.0.
- 8. the preparation method of the benzoxazine colophony according to claim 7 containing cyano group, it is characterised in that：The step Anhydrous potassium carbonate is used in two, solvent is removed water with molecular sieve.
- 9. the preparation method of the benzoxazine colophony according to claim 4 containing cyano group, it is characterised in that：The step Two reactions carry out at room temperature and under nitrogen atmosphere, react 8-36h；Then reaction solution is poured into deionized water, by precipitation Precipitation washing, it is dry, that is, obtain the target product of step 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711145731.5A CN107915818A (en) | 2017-11-17 | 2017-11-17 | A kind of thermosetting resin containing cyano group and preparation method thereof |
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| CN201711145731.5A CN107915818A (en) | 2017-11-17 | 2017-11-17 | A kind of thermosetting resin containing cyano group and preparation method thereof |
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| CN107915818A true CN107915818A (en) | 2018-04-17 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254878A (en) * | 2015-10-16 | 2016-01-20 | 中科院广州化学有限公司南雄材料生产基地 | Polybenzoxazine connected bisphthalonitrile monomer as well as preparation method and application thereof |
-
2017
- 2017-11-17 CN CN201711145731.5A patent/CN107915818A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254878A (en) * | 2015-10-16 | 2016-01-20 | 中科院广州化学有限公司南雄材料生产基地 | Polybenzoxazine connected bisphthalonitrile monomer as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| VERNON M. RUSSELL ET AL.: "Study of the Characterization and Curing of a Phenyl Benzoxazine Using 15N Solid-State Nuclear Magnetic Resonance Spectroscopy", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 韩东明: "双酚AF型苯并噁嗪的合成及性能研究", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
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Application publication date: 20180417 |