CN106220620A - A kind of ortho position maleimide monofunctional benzoxazine monomer and preparation method thereof - Google Patents
A kind of ortho position maleimide monofunctional benzoxazine monomer and preparation method thereof Download PDFInfo
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- CN106220620A CN106220620A CN201610762806.3A CN201610762806A CN106220620A CN 106220620 A CN106220620 A CN 106220620A CN 201610762806 A CN201610762806 A CN 201610762806A CN 106220620 A CN106220620 A CN 106220620A
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- maleimide
- ortho position
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- benzoxazine monomer
- monofunctional benzoxazine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The present invention open a kind of ortho position maleimide monofunctional benzoxazine monomer and preparation method thereof, monomer molecule formula is as follows,Formula is one of having structure:
Description
Technical field
The present invention relates to a kind of thermosetting resin and preparation method thereof, particularly relate to a kind of ortho position maleimide simple function
Change benzoxazine monomer and preparation method thereof.
Background technology
Now, grown up on the basis of traditional phenolic resin the resin benzimidazole dihydrochloride tree of a kind of novel high-performance
Fat, it is to be generated hexa-member heterocycle by phenolic compound, aminated compounds and aldehyde compound through reaction of shrinking to prepare, then in heat
And/or under catalyst action, benzimidazole dihydrochloride intermediate generation ring-opening polymerisation, generate the netted knot of nitrogenous and similar phenolic resin
Structure.This kind of novel hot setting resin except have high temperature resistant, corrosion-resistant, ageing-resistant, the anti-flammability suitable with tradition phenolic resin,
Outside good mechanical characteristic, improve that phenolic resin fragility is big the most to a certain extent, solidification time have little molecule to release, volume is received
The shortcomings such as shrinkage is big, the most concerned.
Benzoxazine compounds, its usual structural formula is:
Chinese scholar have also been made many effort in terms of benzoxazine resins.Publication No. CN1472205A " containing N-alkene
The benzimidazole dihydrochloride intermediate of propyl group and compositions and preparation method thereof " provide the system of benzimidazole dihydrochloride intermediate containing N-pi-allyl
Preparation Method, product has excellent resistance to elevated temperatures, mechanical property, fire resistance and processing characteristics.Patent No.
The Chinese invention patent " granular many benzimidazole dihydrochlorides intermediate and preparation method thereof " of ZL95111413.1 (Authorization Notice No.:
CN1059909C), disclose by polyhydric phenols, monoamine and formalin, with water as disperse medium, under suspending agent effect, close
Become granular many benzimidazole dihydrochlorides intermediate；The application for a patent for invention of Application No. 200410052834.3 discloses a kind of sweet-smelling alkynyl
Poly(silicon aether) benzoxazine resins of end-blocking and preparation method thereof, its product has good heat stability and preferable processability.
The application for a patent for invention of Application No. 200910097549.6 discloses a kind of double benzimidazole dihydrochlorides containing imide structure and system thereof
Preparation Method, prepared benzimidazole dihydrochloride is heat-resist, excellent in mechanical performance, can do the resin matrix of high-performance composite materials.Application
Number be 201010152849.2 application for a patent for invention provide the bisphenol-A benzoxazine resins preparation side that a kind of stability is high
Method.The benzimidazole dihydrochloride of bifunctionality (such as bisphenol A-type) is though useful as high performance material, but due to the spy of molecular structure self
Point, causes the shortcomings such as the crosslinking density of benzimidazole dihydrochloride polymer is low, property is crisp, toughness is poor.
Maleimide, as a kind of polymerisable group, due to the existence of its rigidity imide ring, is widely used
In many polymerization systems, and thereby is achieved a series of high performance polymer resin.As Chinese invention patent application is open
" a kind of benzimidazole dihydrochloride containing maleimide and allyl ether and preparation method thereof (publication number: CN 11235033A) ", application
It is will to introduce allyl ether on the basis of existing para-position maleimide base group.But up to the present, it is not yet reported that relate to ortho position
The synthesis of maleimide-functionalised benzimidazole dihydrochloride and use.
Because the defect that above-mentioned existing benzoxazine resins exists, the present inventor is based on being engaged in this type of product design system
Make for many years abundant practical experience and Professional knowledge, and coordinate the utilization of scientific principle, the most in addition research and innovation, to founding one
Novel ortho position maleimide monofunctional benzoxazine monomer and preparation method thereof so that it is have more practicality.Through constantly
Research, design, and through repeatedly study sample and improve after, finally create the present invention having practical value.
Summary of the invention
Present invention is primarily targeted at, overcome the defect that existing benzoxazine resins exists, and provide a kind of novel
Ortho position maleimide monofunctional benzoxazine monomer and preparation method thereof, simplifies preparation technology, makes up benzimidazole dihydrochloride higher
Defect, thus more suitable for practicality, and there is the value in industry.
The object of the invention to solve the technical problems realizes by the following technical solutions.Propose according to the present invention
The benzoxazine monomer of a kind of ortho position maleimide monofunctional, molecular formula is as follows:
In formulaFor any one in having structure:
The benzoxazine monomer of aforesaid ortho position maleimide monofunctional, the vitrification point of this compound is 250
～400 DEG C.
The preparation method of the benzoxazine monomer of aforesaid ortho position maleimide monofunctional, comprises the following steps:
Step one, synthesizes the maleimide-functionalised phenol in ortho position with Ortho-Aminophenol and maleic anhydride, and reaction is expressed as:
Step 2, makes in low polar solvent with the maleimide-functionalised phenol in ortho position, aminated compounds and paraformaldehyde
The standby benzimidazole dihydrochloride containing maleimide base group, reaction is expressed as follows:
Then by reactant liquor through removing solvent, alkali liquor alkali cleaning, washing, obtain required product after drying.In formula
For any one in having structure:
The preparation method of the benzoxazine monomer of aforesaid ortho position maleimide monofunctional, in described step one, 2-
The mol ratio of amino-phenol and maleic anhydride is 1: 1, and reaction dissolvent is DMF (DMF), P2O5As except water
Agent, H2SO4As catalyst, in nitrogen or other inert protective gas atmosphere, reacting 6 hours, reaction temperature is 70 DEG C, instead
After should, reactant liquor be poured in deionized water, through filtering, washing, after drying, obtain the maleimide-functionalised phenol in ortho position.
The preparation method of the benzoxazine monomer of aforesaid ortho position maleimide monofunctional, in described step 2, adjacent
The mol ratio of the maleimide-functionalised phenol in position, aminated compounds and paraformaldehyde is 1: 1: 2, is 120 DEG C of bars in reaction temperature
React 5 hours under part, then by reactant liquor through removing solvent, alkali liquor alkali cleaning, wash, be dried etc. operate after obtain required product
Thing.
The preparation method of the benzoxazine monomer of aforesaid ortho position maleimide monofunctional, low pole in described step 2
Property solvent is toluene or dimethylbenzene.
The preparation method of the benzoxazine monomer of aforesaid ortho position maleimide monofunctional, alkali liquor used is hydroxide
Any in sodium solution, potassium hydroxide solution, sodium carbonate liquor, sodium bicarbonate solution, solution of potassium carbonate or potassium bicarbonate solution
A kind of.
By technique scheme, the ortho position maleimide monofunctional benzoxazine monomer of the present invention and preparation side thereof
Method at least has the advantage that
Ortho position maleimide monofunctional benzoxazine monomer structure prepared by the present invention is through nuclear magnetic resonance, NMR, infrared light
Point analysis method such as spectrum, elementary analysis is confirmed, the ortho position maleimide monofunctional benzoxazine monomer of present invention synthesis
After cured, the glass transition temperature Tg of its resin is up to 250～400 DEG C.
The present invention introduces maleimide base group at benzimidazole dihydrochloride ortho position, is effectively shortened the time of being synthesized；Additionally, benzene
And piperazine not only piperazine ring curing reaction crosslinking when solidification, and maleimide base group can obtain one with secondary cross-linking
Planting the finest and close double cross-linked network structures, substantially increase the heat stability of resin, the machinability of resin also increases.
Use the preparation method of the present invention, reduce the stump base ratio of benzoxazine resins, effectively raise the mechanical property of resin
Energy and heat stability, be suitable for high-performance composite materials matrix, manufacture various high-temperature-resistant structure material and electrically insulating material, with
Time the method preparation technology simple, low for equipment requirements, can mass production.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of description, after describing in detail such as with presently preferred embodiments of the present invention below.
Detailed description of the invention
By further illustrating the technological means and effect that the present invention taked by reaching predetermined goal of the invention, to according to this
The ortho position maleimide monofunctional benzoxazine monomer that invention proposes and preparation method thereof its detailed description of the invention and feature,
After describing in detail such as.
Embodiment 1
The preparation method of ortho position of the present invention maleimide monofunctional benzoxazine monomer:
Ortho-Aminophenol 30.6g, maleic anhydride 30g are joined in the ice bath system of 80mL dimethylformamide (DMF),
It is added thereto to 15g phosphorus pentoxide and the 8g concentrated sulphuric acid being dissolved in 50mL DMF afterwards, after reacting 30 minutes, by reaction unit
In dislocation oil bath 70 DEG C, reaction 6 hours.After reaction terminates, reactant liquor pours 200ml deionized water into, is precipitated in a large number.Sucking filtration
After, by a large amount of water and washing with alcohol three times, put into 50 DEG C of vacuum tanks and be dried, obtain the maleimide-functionalised phenol in product ortho position
43.5g, yield is 82%.
Weigh by previous step gained ortho position maleimide phenol 30g, and aniline 14.8g, paraformaldehyde 9.5g, toluene
70ml is added separately in the reaction bulb equipped with agitator, thermometer and condensing tube, is heated to 120 DEG C with the speed of 10 DEG C/h,
Reaction 5h.After reaction terminates, reactant liquor adds deionized water and carries out precipitating, precipitated in a large number, by precipitate with 5%
Sodium hydroxide solution washs 3 times, then through washing, filters, and be dried under vacuum 12 hours, obtain product 38.9g, yield
80%.
Embodiment 2
The preparation technology reference example 1 of ortho position maleimide phenol.
Again by ortho position maleimide phenol 30g and 3-aminobenzene acetylene 18.6g, paraformaldehyde 9.5g, the diformazan of preparation
Benzene 70ml is added separately in the reaction bulb equipped with agitator, thermometer and condensing tube, is heated to 120 DEG C with the speed of 10 DEG C/h
Reaction 5h.After reaction terminates, reactant liquor adds deionized water and carries out precipitating, precipitated in a large number, by precipitate with 5%
Sodium hydroxide solution washs 3 times, then through washing, filters, and be dried under vacuum 12 hours, obtain product 44.0g, and yield is
84%.
Embodiment 3
The preparation technology reference example 1 of ortho position maleimide phenol.
Again by ortho position maleimide phenol 30g and m-aminophenyl first cyanogen 18.7g, paraformaldehyde 9.5g, the diformazan of preparation
Benzene 70ml is added separately in the reaction bulb equipped with agitator, thermometer and condensing tube, is heated to 120 with the speed of 10 DEG C/h
DEG C, react 5h.After reaction terminates, reactant liquor adds deionized water and carries out precipitating, precipitated in a large number, precipitate is used
The sodium hydroxide solution of 5% washs 3 times, then through washing, filters, and be dried under vacuum 12 hours, obtain product 41.0g, receives
Rate is 78%.
Embodiment 4
The preparation technology reference example 1 of ortho position maleimide phenol.
Again by ortho position maleimide phenol 30g and p-aminophenyl first cyanogen 18.7g, paraformaldehyde 9.5g, dimethylbenzene 70ml
It is added separately in the reaction bulb equipped with agitator, thermometer and condensing tube, is heated to 120 DEG C of reactions with the speed of 10 DEG C/h
5h.Reaction terminate after, in reactant liquor add deionized water carry out precipitating, precipitated in a large number, by precipitate with 5% hydrogen-oxygen
Changing sodium solution to wash 3 times, then through washing, filter, and be dried under vacuum 12 hours, obtain product 42.6g, yield is 81%.
Use the ortho position maleimide monofunctional benzoxazine monomer yield prepared of the present invention higher, reach 78% with
On, its structure of the resin obtained by solidification is fine and close network structure, has good mechanical property and heat stability.
The above, be only presently preferred embodiments of the present invention, and the present invention not makees any pro forma restriction, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any technology people being familiar with this specialty
Member, in the range of without departing from technical solution of the present invention, when the technology contents of available the disclosure above makes a little change or modification
For the Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit of the foundation present invention
Any simple modification, equivalent variations and the modification being made above example, all still falls within the range of technical solution of the present invention.
Claims (7)
1. an ortho position maleimide monofunctional benzoxazine monomer, it is characterised in that: molecular formula is as follows,
In formulaFor one of having structure:
Ortho position the most according to claim 1 maleimide monofunctional benzoxazine monomer, it is characterised in that: vitrification
Temperature is 250～400 DEG C.
The preparation method of ortho position the most according to claim 1 maleimide monofunctional benzoxazine monomer, its feature
It is: include following operating procedure,
Step one, synthesizes the maleimide-functionalised phenol in ortho position with Ortho-Aminophenol and maleic anhydride, and reaction is expressed as:
Step 2, prepares in low polar solvent with the maleimide-functionalised phenol in ortho position, aminated compounds and paraformaldehyde and contains
The benzimidazole dihydrochloride of maleimide base group, reaction is expressed as follows:
Then by reactant liquor through removing solvent, alkali liquor alkali cleaning, washing, obtain required product after drying；
In formulaFor any one in having structure:
The preparation method of ortho position the most according to claim 3 maleimide monofunctional benzoxazine monomer, its feature
Being: in described step one, the mol ratio of Ortho-Aminophenol and maleic anhydride is 1: 1, and reaction dissolvent is N, N-dimethyl formyl
Amine (DMF), adds deicer, catalyst, in inert gas shielding atmosphere, after reaction, is poured into by reactant liquor in deionized water,
Filter, wash, be dried, obtain the maleimide-functionalised phenol in ortho position.
The preparation method of ortho position the most according to claim 3 maleimide monofunctional benzoxazine monomer, its feature
Being: in described step 2, the mol ratio of the maleimide-functionalised phenol in ortho position, aminated compounds and paraformaldehyde is 1: 1: 2,
After reacting by heating, reactant liquor is obtained required product after removing solvent, alkali liquor alkali cleaning, washing, drying process.
The preparation method of ortho position the most according to claim 3 maleimide monofunctional benzoxazine monomer, its feature
It is: the low polar solvent in described step 2 is toluene or dimethylbenzene.
7., according to the preparation method of the ortho position maleimide monofunctional benzoxazine monomer described in claim 3 or 5, it is special
Levy and be: described alkali liquor is sodium hydroxide solution, potassium hydroxide solution, sodium carbonate liquor, sodium bicarbonate solution, solution of potassium carbonate
Or the one in potassium bicarbonate solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699748A (en) * | 2016-12-20 | 2017-05-24 | 江苏大学 | Norbornene group capping benzoxazine oligomer and preparation method thereof |
| CN107573334A (en) * | 2017-04-10 | 2018-01-12 | 江苏大学 | A kind of single function benzoxazine of the imide group containing alicyclic and preparation method thereof |
| CN109679048A (en) * | 2019-01-16 | 2019-04-26 | 江苏大学 | A kind of backbone chain type benzoxazine resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004101509A2 (en) * | 2003-05-06 | 2004-11-25 | Case Western Reserve University | Functionalized benzoxazines, polymers and copolymers thereof |
| CN102827095A (en) * | 2012-09-07 | 2012-12-19 | 成都金桨高新材料有限公司 | Benzoxazine resin mid-body containing arylamine and preparation method thereof |
| CN103524500A (en) * | 2013-07-16 | 2014-01-22 | 四川职业技术学院 | Preparation method of benzoxazine containing maleimide bisphenol A-type structure |
| JP2016074871A (en) * | 2014-03-04 | 2016-05-12 | 四国化成工業株式会社 | Bismaleimide resin composition and use of the same |
-
2016
- 2016-08-30 CN CN201610762806.3A patent/CN106220620A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004101509A2 (en) * | 2003-05-06 | 2004-11-25 | Case Western Reserve University | Functionalized benzoxazines, polymers and copolymers thereof |
| CN102827095A (en) * | 2012-09-07 | 2012-12-19 | 成都金桨高新材料有限公司 | Benzoxazine resin mid-body containing arylamine and preparation method thereof |
| CN103524500A (en) * | 2013-07-16 | 2014-01-22 | 四川职业技术学院 | Preparation method of benzoxazine containing maleimide bisphenol A-type structure |
| JP2016074871A (en) * | 2014-03-04 | 2016-05-12 | 四国化成工業株式会社 | Bismaleimide resin composition and use of the same |
Non-Patent Citations (5)
| Title |
|---|
| AYYAVU CHANDRAMOHAN ET AL.: "Polysilsesquioxane-reinforced phosphorous containing bis(4-maleimidophenyl)benzoxazine hybrid nanocomposites", 《HIGH PERFORMANCE POLYMERS》 * |
| KAN ZHANG ET AL.: "Synthesis of High Thermal Stability Polybenzoxazoles via Ortho-Imide-Functional Benzoxazine Monomers", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
| SHIN-CHEN LIN ET AL.: "Reaction mechanism and synergistic anticorrosion property of reactive blends of maleimide containing benzoxazine and amine-capped aniline trimer", 《POLYM. CHEM.》 * |
| YU GAO ET AL.: "Synthesis and Characterization of a Novel Acetylene- and Maleimide-Terminated Benzoxazine and Its High-Performance Thermosets", 《J. APPL. POLYM. SCI.》 * |
| YUANRONG CHENG ET AL.: "Highly cross-linked thermosetting resin of maleimidobenzoxazine functionalized with benzocyclobutene", 《POLYMER》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699748A (en) * | 2016-12-20 | 2017-05-24 | 江苏大学 | Norbornene group capping benzoxazine oligomer and preparation method thereof |
| CN106699748B (en) * | 2016-12-20 | 2019-03-05 | 江苏大学 | A kind of norbornene end-sealed type benzoxazine oligomer and preparation method thereof |
| CN107573334A (en) * | 2017-04-10 | 2018-01-12 | 江苏大学 | A kind of single function benzoxazine of the imide group containing alicyclic and preparation method thereof |
| CN107573334B (en) * | 2017-04-10 | 2021-02-12 | 江苏大学 | Monofunctional benzoxazine containing alicyclic hydrocarbon imide group and preparation method thereof |
| CN109679048A (en) * | 2019-01-16 | 2019-04-26 | 江苏大学 | A kind of backbone chain type benzoxazine resin and preparation method thereof |
| CN109679048B (en) * | 2019-01-16 | 2021-06-22 | 江苏大学 | Main chain type benzoxazine resin and preparation method thereof |
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