CN103483331A - Preparation method for maleimide-containing biphenol type benzoxazine - Google Patents
Preparation method for maleimide-containing biphenol type benzoxazine Download PDFInfo
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- CN103483331A CN103483331A CN201310430857.2A CN201310430857A CN103483331A CN 103483331 A CN103483331 A CN 103483331A CN 201310430857 A CN201310430857 A CN 201310430857A CN 103483331 A CN103483331 A CN 103483331A
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- C07—ORGANIC CHEMISTRY
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- 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
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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Abstract
A preparation method for a benzoxazine intermediate adopting a maleimide-containing biphenol type structure comprises the following steps: (1) synthetic reaction 1: firstly, adding an aldehyde compound and a solvent into a reaction vessel at the indoor temperature and under normal pressure to be uniformly mixed, then adding an amine compound into the vessel while stirring, reacting for at least 10 hours under the normal pressure and at the temperature of 0-100 DEG C, after the reaction is completed, pouring the reaction liquid into a washing liquid to be washed, filtering and collecting a solid substance, and drying the solid substance at the temperature of 30-100 DEG C, so as to obtain an intermediate containing a triazine structure; (2) synthetic reaction 2: sequentially adding the obtained solid substance (triazine) as well as the aldehyde compound, biphenol, and 1, 4-dioxane intt the reaction vessel to be uniformly mixed, heating up to the temperature of 110 DEG C and carrying out a backflow reaction for 30 hours to obtain a reaction liquid containing earthy yellow precipitation, pouring the reaction liquid into deionized water, fully stirring, precipitating, leaching, washing for multiple times by using the deionized water and ethyl alcohol, and then drying in a dryer, so as to obtain the earthy yellow powder solid target product.
Description
Technical field:
The invention belongs to the preparation field of the intermediate of benzoxazine monomer, particularly a kind of preparation method of the benzoxazine intermediate containing maleimide '-biphenyl diphenol type structure.
Background technology:
Benzoxazine is a kind of novel phenolic resin modified product.It is to take phenolic compound, aminated compounds and aldehyde compound as the intermediate of the synthetic class of raw material containing heterocycle structure, under heating and catalyst action, ring-opening polymerization occurs, and generates the reticulation of nitrogenous similar resol, i.e. benzoxazine colophony.The structural formula of benzoxazine monomer is as follows:
When the advantage of benzoxazine colophony is the thermotolerance that both had common heat-reactive phenolic resin or novolac resin, flame retardant resistance, resin does not have small molecules to discharge in the forming and hardening process, and the goods porosity is low, approaches zero and shrinks, stress is little, there is no tiny crack.Adding the benzoxazine colophony ring-opening polymerization front is low relative molecular mass, low viscous cyclic monomer, and solvability is good, has good processing performance, can be used as the body material for preparing matrix material; Can also utilize active group and other resin reactions on the benzoxazine molecule, carry out various modifications, the benzoxazine colophony after modification has more good over-all properties, in fields such as electronics, aviations, has been widely used.The Application Areas of every general resol, all available benzoxazine colophony replaces, and particularly requires high performance field, the low space of goods preferentially to be applied.
Since phase late 1940s, Americanized scholar has just carried out than systematic research phenolic compound, aminated compounds and formaldehyde reaction, and nineteen forty-four, Holly and Cope be the unexpected benzoxazine compound of finding in synthetic Mannich reaction product.Since 1949, the people Dui benzoxazines such as Burke synthetic carried out comparatively deep research, synthesized a series of compounds containing benzoxazine structure.1973, Germanization scholar Schreiber reported first adopted the research work of the synthetic phenolic polymkeric substance of benzoxazine route, and has applied for patent.1985, Higginbottom applied for the patent of bifunctional benzoxazine and has carried out Application and Development.After nineteen ninety, Hatsuo Ishide starts systematically to study synthetic, performance characterization, processing and the application of benzoxazine, and has applied for tens patents.At home, the Gu Yi of Sichuan University etc. just started to carry out the correlative study of benzoxazine from 1993, its achievement in research has been applied for four China national patents: (1) ZL94111852.5 claims disclosed ring-opening polymerization resol and fibre reinforced composites to have good preparation and forming process, physical and mechanical properties is good, applicable high-temperature-resistant structure material and the electrically insulating material of making 150-180 ℃ of life-time service.(2) " granular polybenzoxazine intermediate and preparation method " reacting balance that ZL95111413.1 discloses, the cyclisation rate is high, product yield is high, solvent-free, environmental pollution is little, be easy to realize serialization production, the granular solids intermediate can be directly used in manufactures various high performance phenoplast goods.(3) ZL99114603.4 disclosed " plant oil modified benzoxazine intermediate and preparation method and purposes " claims the method reacting balance, and forming process is good, and intrinsic toughening has obviously improved condensate performance.(4) ZL0311779.4 discloses a kind of " can be used for modifying benzoxazine resin of RTM and preparation method thereof ", the method is under heating and/or catalyst action, between the low viscosity benzoxazine intermediate or with other modified copolymers and catalyzer blending reaction, obtains can be used for the modifying benzoxazine resin of RTM.
In sum, a large amount of research has been carried out in the preparation of Chinese scholars Dui benzoxazine intermediate and resin thereof, but has not yet to see any report and the patent of research aspect of the synthetic and curing performance of maleimide '-biphenyl diphenol type benzoxazine intermediate and resin thereof.Owing to containing a two key on the maleimide ring, therefore this kind of novel benzoxazine intermediate and resin thereof will have special purposes, both can be used as monomer and prepared polymkeric substance, can be used as again properties-correcting agent and other polymer blendings to obtain the macromolecular material of some property.The successful research and development of this product, will enlarge the production application field of traditional resol, promotes further developing of this industry.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of the benzoxazine intermediate containing maleimide '-biphenyl diphenol type structure, not only productive rate is high for this kind of method, and technique is simple, environmental protection, and range of reaction temperature is wide, is conducive to suitability for industrialized production.
The preparation method of the benzoxazine intermediate containing maleimide '-biphenyl diphenol type structure of the present invention, processing step is as follows successively:
(1) building-up reactions 1
The mol ratio of aldehyde compound and aminated compounds is at least 1, and solvent is at least a kind of in clean water, methyl alcohol, ethanol, Virahol, ethyl acetate,
At first in room temperature (Indoor Natural temperature, 0～35 ℃), normal pressure adds reaction vessel to mix aldehyde compound and solvent, then under agitation aminated compounds is added to reaction vessel, be mixed with the aldehyde mass concentration and be not more than 95% mixed solution, after reinforced, normal pressure, 0～100 ℃, at least react 10 hours;
(2) filter washing
After building-up reactions completes, pour reaction solution in washings agitator treating, solid collected by filtration material then, washings is at least one solvent described in step (1); Perhaps the reaction solution direct filtration is collected to solid matter:
(3) drying
Step (2) solid matter that obtains is carried out to drying at 30～100 ℃, (drying can be carried out under condition of normal pressure or vacuum condition to obtain benzoxazine intermediate containing triazine structure, the powder that form favorable dispersity with product time of drying is limited), productive rate 82%～99%.
(4) building-up reactions 2
With aldehyde compound, '-biphenyl diphenol, add successively reaction vessel to mix step (3) solid matter that obtains (triazine), its mol ratio is at least 1: 1: 1, add appropriate 1, the 4-dioxane, be warming up to 110 ℃ at back flow reaction 20h at least, obtain the reaction solution containing the khaki color precipitation.
(5) washing, drying
Step (4) gained reaction solution is poured in deionized water and fully stirred, precipitation, suction filtration after repeatedly washing with deionized water and ethanol, is dried in baking oven, obtains khaki color powdery solid target product, product yield 40%～58%.
In the method for the invention, aminated compounds is N-(4-aminophenyl) maleimide, and aldehyde compound is formalin or paraformaldehyde.
The structure of the benzoxazine intermediate containing maleimide '-biphenyl diphenol type structure of the present invention is:
The structure of aminated compounds N-(4-aminophenyl) maleimide is:
Intermediate product 1,3, the structure of 5-tri-(4-(maleimide) phenyl)-1,3,5-triazines (TMIPT) is:
Embodiment
Embodiment 1
In the present embodiment, contain the preparation method of the benzoxazine intermediate of maleimide '-biphenyl diphenol type structure, its processing step is as follows successively:
(1) building-up reactions 1
By formalin 14g, APMI17g, ethyl acetate 800mL, water 100mL, be sequentially added at the bottom of the 1000mL garden in flask, under room temperature, the about 10h of reaction, then be equipped with the reaction solution impouring in the beaker of 1000mL water and precipitate, vacuum filtration, the tap water washing, put into baking oven and dry 4h under 60 ℃, obtaining TMIPT is lurid pressed powder, and productive rate is in 96% left and right.
(2) building-up reactions 2
By paraformaldehyde 3.0g, TMIPT19.5g, '-biphenyl diphenol 12.0g, Isosorbide-5-Nitrae-dioxane 1000mL joins at the bottom of the 1500mL garden in flask successively, is warming up to 110 ℃ of back flow reaction 27h, obtain the reaction solution containing the khaki color precipitation, the gained reaction solution is poured in deionized water and fully stirred, precipitation, suction filtration, after repeatedly washing with deionized water and ethanol, dry in baking oven, obtain khaki color powdery solid product, product yield 45%.
Embodiment 2
In the present embodiment, contain the preparation method of the benzoxazine intermediate of maleimide '-biphenyl diphenol type structure, its processing step is as follows successively:
(1) building-up reactions 1
By formalin 21g, APMI25.5g, ethyl acetate 1200mL, water 150mL, be sequentially added at the bottom of the 1500mL garden in flask, under room temperature, the about 13h of reaction, then be equipped with the reaction solution impouring in the beaker of 2000mL water and precipitate, vacuum filtration, the tap water washing, put into baking oven and dry 6h under 60 ℃, obtaining TMIPT is lurid pressed powder, and productive rate is in 92% left and right.
(2) building-up reactions 2
By paraformaldehyde 4.5g, TMIPT29.5g, '-biphenyl diphenol 18.0g, Isosorbide-5-Nitrae-dioxane 1200mL joins at the bottom of the 1500mL garden in flask successively, is warming up to 110 ℃ of back flow reaction 30h, obtain the reaction solution containing the khaki color precipitation, the gained reaction solution is poured in deionized water and fully stirred, precipitation, suction filtration, after repeatedly washing with deionized water and ethanol, dry in baking oven, obtain khaki color powdery solid product, product yield 52%.
Embodiment 3
In the present embodiment, contain the preparation method of the benzoxazine intermediate of maleimide '-biphenyl diphenol type structure, its processing step is as follows successively:
(1) building-up reactions 1
By formalin 22.4g, APMI27.2g, ethyl acetate 1280mL, water 160mL, be sequentially added at the bottom of the 1500mL garden in flask, under room temperature, the about 14h of reaction, then be equipped with the reaction solution impouring in the beaker of 1500mL water and precipitate, vacuum filtration, the tap water washing, put into baking oven and dry 4h under 60 ℃, obtaining TMIPT is lurid pressed powder, and productive rate is in 94% left and right.
(2) building-up reactions 2
By paraformaldehyde 4.8g, TMIPT31.2g, '-biphenyl diphenol 19.2g, Isosorbide-5-Nitrae-dioxane 1300mL joins at the bottom of the 1500mL garden in flask successively, is warming up to 110 ℃ of back flow reaction 32h, obtain the reaction solution containing the khaki color precipitation, the gained reaction solution is poured in deionized water and fully stirred, precipitation, suction filtration, after repeatedly washing with deionized water and ethanol, dry in baking oven, obtain khaki color powdery solid product, product yield 56%.
Embodiment 4
In the present embodiment, contain the preparation method of the benzoxazine intermediate of maleimide '-biphenyl diphenol type structure, its processing step is as follows successively:
(1) building-up reactions 1
By formalin 18.2g, APMI22.1g, ethyl acetate 1040mL, water 130mL, be sequentially added at the bottom of the 1500mL garden in flask, under room temperature, the about 11h of reaction, then be equipped with the reaction solution impouring in the beaker of 1500mL water and precipitate, vacuum filtration, the tap water washing, put into baking oven and dry 4h under 60 ℃, obtaining TMIPT is lurid pressed powder, and productive rate is in 95% left and right.
(2) building-up reactions 2
By paraformaldehyde 3.9g, TMIPT25.3g, '-biphenyl diphenol 15.6g, Isosorbide-5-Nitrae-dioxane 1000mL joins at the bottom of the 1500mL garden in flask successively, is warming up to 110 ℃ of back flow reaction 28h, obtain the reaction solution containing the khaki color precipitation, the gained reaction solution is poured in deionized water and fully stirred, precipitation, suction filtration, after repeatedly washing with deionized water and ethanol, dry in baking oven, obtain khaki color powdery solid product, product yield 52%.
Embodiment 5
In the present embodiment, contain the preparation method of the benzoxazine intermediate of maleimide '-biphenyl diphenol type structure, its processing step is as follows successively:
(1) building-up reactions 1
By formalin 25.2g, APMI30.6g, ethyl acetate 1440mL, water 180mL, be sequentially added at the bottom of the 2000mL garden in flask, under room temperature, the about 15h of reaction, then be equipped with the reaction solution impouring in the beaker of 2000mL water and precipitate, vacuum filtration, the tap water washing, put into baking oven and dry 4h under 60 ℃, obtaining TMIPT is lurid pressed powder, and productive rate is in 94.9% left and right.
(2) building-up reactions 2
By paraformaldehyde 5.4g, TMIPT35.1g, '-biphenyl diphenol 21.6g, Isosorbide-5-Nitrae-dioxane 1500mL joins at the bottom of the 2000mL garden in flask successively, is warming up to 110 ℃ of back flow reaction 35h, obtain the reaction solution containing the khaki color precipitation, the gained reaction solution is poured in deionized water and fully stirred, precipitation, suction filtration, after repeatedly washing with deionized water and ethanol, dry in baking oven, obtain khaki color powdery solid product, product yield 48%.
Embodiment 6
In the present embodiment, contain the preparation method of the benzoxazine intermediate of maleimide '-biphenyl diphenol type structure, its processing step is as follows successively:
(1) building-up reactions 1
By formalin 28g, APMI34g, ethyl acetate 1600mL, water 200mL, be sequentially added at the bottom of the 2000mL garden in flask, under room temperature, the about 18h of reaction, then be equipped with the reaction solution impouring in the beaker of 2000mL water and precipitate, vacuum filtration, the tap water washing, put into baking oven and dry 4h under 60 ℃, obtaining TMIPT is lurid pressed powder, and productive rate is in 95% left and right.
(2) building-up reactions 2
By paraformaldehyde 6.0g, TMIPT39.0g, '-biphenyl diphenol 24.0g, Isosorbide-5-Nitrae-dioxane 1500mL joins at the bottom of the 2000mL garden in flask successively, is warming up to 110 ℃ of back flow reaction 37h, obtain the reaction solution containing the khaki color precipitation, the gained reaction solution is poured in deionized water and fully stirred, precipitation, suction filtration, after repeatedly washing with deionized water and ethanol, dry in baking oven, obtain khaki color powdery solid product, product yield 51%.
Claims (3)
1. the preparation method containing the benzoxazine intermediate of maleimide '-biphenyl diphenol type structure is characterized in that processing step is as follows successively:
(1) building-up reactions 1
The mol ratio of aldehyde compound and aminated compounds is at least 1, solvent is at least one or both in clean water, methyl alcohol, ethanol, Virahol, ethyl acetate, at first in room temperature (Indoor Natural temperature, 0～35 ℃), add reaction vessel to mix aldehyde compound and solvent under normal pressure, then under agitation aminated compounds is added to reaction vessel, after reinforced, normal pressure, 0～100 ℃, at least react 10 hours;
(2) filter washing
After building-up reactions completes, pour reaction solution in washings agitator treating, solid collected by filtration material then, washings is at least one solvent described in step (1);
(3) drying
Step (2) solid matter that obtains is carried out to drying at 30～100 ℃, obtain the benzoxazine intermediate (drying can be carried out under condition of normal pressure or vacuum condition, and the powder that form favorable dispersity with product time of drying is limited) containing triazine structure;
(4) building-up reactions 2
By obtained solid matter (triazine intermediate) and aldehyde compound, '-biphenyl diphenol, 1, the 4-dioxane adds reaction vessel to mix successively, be warming up at least 30h of 110 ℃ of back flow reaction, obtain the reaction solution containing the khaki color precipitation, the gained reaction solution is poured in deionized water and fully stirred, precipitation, suction filtration, after repeatedly washing with deionized water and ethanol, in baking oven, dry, obtain khaki color powdery solid target product (a kind of benzoxazine intermediate containing maleimide '-biphenyl diphenol type structure).
2. the preparation method of the benzoxazine intermediate containing triazine structure according to claim 1, is characterized in that aminated compounds is N-(4-aminophenyl) maleimide.
3. the preparation method of the benzoxazine intermediate containing triazine structure according to claim 1, is characterized in that aldehyde compound is formalin or paraformaldehyde.
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| CN201310430857.2A CN103483331A (en) | 2013-09-22 | 2013-09-22 | Preparation method for maleimide-containing biphenol type benzoxazine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356083A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Preparation method of benzoxazine compound |
| CN109748279A (en) * | 2019-02-21 | 2019-05-14 | 南京大学 | One kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application |
| CN110627779A (en) * | 2019-10-28 | 2019-12-31 | 成都师范学院 | Preparation method of maleimide biphenyl diphenol type benzoxazine monomer |
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2013
- 2013-09-22 CN CN201310430857.2A patent/CN103483331A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356083A (en) * | 2014-10-22 | 2015-02-18 | 苏州太湖电工新材料股份有限公司 | Preparation method of benzoxazine compound |
| CN109748279A (en) * | 2019-02-21 | 2019-05-14 | 南京大学 | One kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application |
| CN110627779A (en) * | 2019-10-28 | 2019-12-31 | 成都师范学院 | Preparation method of maleimide biphenyl diphenol type benzoxazine monomer |
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Application publication date: 20140101 |