CN107674171A - A kind of benzoxazine colophony for introducing propargyl and preparation method thereof - Google Patents
A kind of benzoxazine colophony for introducing propargyl and preparation method thereof Download PDFInfo
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- CN107674171A CN107674171A CN201711147032.4A CN201711147032A CN107674171A CN 107674171 A CN107674171 A CN 107674171A CN 201711147032 A CN201711147032 A CN 201711147032A CN 107674171 A CN107674171 A CN 107674171A
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- Prior art keywords
- propargyl
- benzoxazine
- preparation
- benzoxazine colophony
- introducing
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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)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a kind of benzoxazine colophony for introducing propargyl and preparation method thereof, 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 benzoxazine for introducing propargyl
Resin and preparation method thereof.
Background technology
In recent years, benzoxazine is as a kind of new material, because of its excellent heat endurance, good fire resistance,
Low water absorption, during solidification volume contraction close to zero-sum discharged without small molecule the advantages that and cause the wide of academia and industrial circle
General interest.However, benzoxazine will be in printed circuit board (PCB), aviation and building trade application, its fire resistance needs further to carry
It is high.The method for improving anti-flammability at present is mainly that ignition-proof element, such as N are added in benzoxazine monomer, Br, Si and P etc., still
The problem of certain all be present,
In order to improve the insulating properties of benzoxazine colophony, prior art modifies benzoxazine using propargyl, as in
State's patent application《Aromatic diamines type benzoxazine colophony containing propargyl and preparation method thereof》(publication number：CN102516537B it is) public
Opened it is a kind of prepare the benzoxazine colophony containing propargyl, although a certain degree of improve anti-flammability, preparation technology
Operate complex, higher to temperature and technological requirement, using three-step approach, the first step prepares dinitro compound, the step palpus
Use higher temperature (140-145 degree)；Second step is to carry out reduction to nitro to prepare diamine compound, and course of reaction need to be used and urged
Agent, reaction is complicated, easily brings environmental problem, and by the 3rd step He into Bei oxazines resin processed, step is complicated, and cost is high and to ring
Border has an impact.And up to the present, also without the related report that propargyl modification is carried out for bisphenol-f type benzoxazine colophony
Road.
The defects of existing in view of above-mentioned existing benzoxazine monomer, the present inventor are based on being 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
Benzoxazine colophony of propargyl and preparation method thereof is introduced, it is had more practicality.By constantly research, design, and
After studying sample repeatedly and improving, the present invention having practical value is created finally.
The content of the invention
The invention provides a kind of benzoxazine colophony containing propargyl and preparation method thereof, improves its insulating properties, drop
Low-dielectric loss.
The present invention is realized using following scheme：
Present invention introduces the benzoxazine colophony of propargyl, the molecular structural formula with following structure：
As the benzoxazine colophony for being preferably introduced propargyl, glass transition temperature is 280-360 DEG C.
As the benzoxazine colophony for being preferably introduced propargyl, at 800 DEG C, the Residual carbon of resin is 62.1-73.6%.
Introduce the preparation method of the benzoxazine colophony of propargyl, including following operating procedure：
Step 1, benzoxazine is synthesized with solventless method with Bisphenol F, to cyano-aniline and paraformaldehyde, its reaction equation is such as
Shown in lower：Formaldehyde is easily decomposed, it is necessary to appropriate excessive；
Step 2, it is dissolved in solvent with the benzoxazine of gained in step 1, is reacted with 3- propargyl bromides, reaction is as follows
It is shown：
Reactant is filtered, filtrate is poured into cold water, is precipitated, precipitation is filtered out and is being dried in vacuo；
Step 3, gained solid in step 2 is warming up to 220-270 DEG C of solidification 1-2h, obtains target product.
As preferable, the preparation method of the benzoxazine colophony of propargyl is introduced, Bisphenol F in the step 1, to cyanogen
The mol ratio of base aniline and paraformaldehyde is 1：2：4.0-4.6.
As preferable, the preparation method of the benzoxazine colophony of propargyl is introduced, the step 1 reaction is solvent-free
Under conditions of carry out, reaction temperature be 90-110 DEG C, reaction time 0.5-6h.
As preferable, the preparation method of the benzoxazine colophony of propargyl is introduced, benzoxazine in the step 2,3-
The mol ratio of propargyl bromide and potassium carbonate is 1：1.0-1.6：1.0-2.0.The effect of potassium carbonate be neutralization reaction generation acid, it is necessary to
It is appropriate excessive.
As preferable, the preparation method of the benzoxazine colophony of propargyl is introduced, the step 2 is having the bar of solvent
Carried out under part, reaction dissolvent is dimethylformamide or dimethyl acetamide.
As preferable, the preparation method of the benzoxazine colophony of propargyl is introduced, the step 2 reaction temperature is 80-
100 DEG C, reaction time 8-24h；Reaction solution is poured into deionized water after reaction, the precipitation of precipitation is washed, dries, produces
To the target product of step 2.
As preferable, the preparation method of the benzoxazine colophony of propargyl is introduced, the step 2 uses Carbon Dioxide
Potassium, solvent are removed water with molecular sieve.
The beneficial functional of the present invention is：
By chemical covalent bonds, never strand different parts are introduced into multiple alkynyl groups into benzoxazine colophony, can lead to
The cross-linking reaction again for crossing alkynyl improves the crosslink density of resin material, so as to improve the heat of material, mechanical property.In addition, through handing over
Resin after solidification crosslinking, because the space structure for being crosslinked unordered causes the insulating properties of material to improve, it is unfavorable for the transmission of electronics.
Benzoxazine colophony prepared by the inventive method after testing, has preferable insulating properties, relatively low dielectric loss, propargyl contains
There is nitrogen, the nitrogen content of benzoxazine solidfied material can be improved, so as to improve the anti-flammability of resin system, electrical insulation capability is excellent
Show, industrial production is convenient, and yield is high, has very strong industrial value and actual application value.The present invention containing propargyl
The preparation method of benzoxazine colophony uses two-step method, and the first step prepares intermediate, and second step is to carry out chemistry to intermediate
Modification, preparation process is simple, environmental protection and cost are low.
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 the benzoxazine colophony of foregoing introducing propargyl, in step 1, by Bisphenol F, to cyano-aniline,
Paraformaldehyde mixes in molar ratio, is added in flask, and the stirring reaction in oil bath pan, temperature is slowly raised to 90-110 from room temperature
DEG C, react 0.5-6 hours.
The preparation method of the benzoxazine colophony of foregoing introducing propargyl, in the step 2, by benzoxazine and 3-
Propargyl bromide, potassium carbonate are put into flask, and 8-24 hours are reacted at 80-100 DEG C, and the mixture that reaction is obtained filters, and will filter
Liquid is poured into a large amount of cold water, is dried after precipitation is filtered in vacuum drying chamber, is obtained product.
Embodiment 1
By 5g Bisphenol Fs, 5.900g is added in three-necked flask to cyano-aniline, 3.300g paraformaldehydes, connect condenser pipe and
Agitating device, temperature is slowly raised to 110 DEG C, reacts 0.5 hour, reactant is taken out, obtains 8.572g benzoxazine solids.
By 3g benzoxazines, 0.753g 3- propargyl bromides, 1.020g Anhydrous potassium carbonates are placed in three-necked flask, add 30ml
Dimethylformamide, flask is placed in oil bath pan and stirred, reacted 24h at 80 DEG C, reacted product is filtered, filtrate is fallen
Enter in substantial amounts of water, solid product is filtered out, and wash several times, be placed in drying for one day in vacuum drying chamber, obtain 3.917g
Product.
Embodiment 2
By 4g Bisphenol Fs, 4.720g is added in three-necked flask to cyano-aniline, 2.640g paraformaldehydes, connect condenser pipe and
Agitating device, temperature is slowly raised to 90 DEG C, reacts 2 hours, reactant is taken out, obtains 7.015g benzoxazine solids.
By 3g benzoxazines, 0.753g 3- propargyl bromides, 1.020g Anhydrous potassium carbonates are placed in three-necked flask, add 30ml
Dimethyl acetamide, flask is placed in oil bath pan and stirred, reacted 24h at 90 DEG C, reacted product is filtered, filtrate is fallen
Enter in substantial amounts of water, solid product is filtered out, and wash several times, be placed in drying for one day in vacuum drying chamber, obtain 3.765g
Product.
Embodiment 3
By 3g Bisphenol Fs, 3.540g is added in three-necked flask to cyano-aniline, 1.980g paraformaldehydes, connect condenser pipe and
Agitating device, temperature is slowly raised to 110 DEG C, reacts 6 hours, reactant is taken out, obtains 5.873g benzoxazine solids.
By 2g benzoxazines, 0.503g3- propargyl bromides, 0.680g Anhydrous potassium carbonates are placed in three-necked flask, add 30ml bis-
Methylacetamide, flask is placed in oil bath pan and stirred, reacted 12h at 100 DEG C, reacted product is filtered, filtrate is fallen
Enter in substantial amounts of water, solid product is filtered out, and wash several times, be placed in drying for one day in vacuum drying chamber, obtain 2.668g
Product.
Embodiment 4
By 2g Bisphenol Fs, 2.360g is added in three-necked flask to cyano-aniline, 1.320g paraformaldehydes, connect condenser pipe and
Agitating device, temperature is slowly raised to 90 DEG C, reacts 6 hours, reactant is taken out, obtains 3.262g benzoxazine solids.
By 2g benzoxazines, 0.503g 3- propargyl bromides, 0.608g Anhydrous potassium carbonates are placed in three-necked flask, add 20ml
Dimethylformamide, flask is placed in oil bath pan and stirred, reacted 24h at 80 DEG C, reacted product is filtered, filtrate is fallen
Enter in substantial amounts of water, solid product is filtered out, and wash several times, be placed in drying for one day in vacuum drying chamber, obtain 2.544g
Product.
The benzoxazine monomer of the introducing propyl group prepared using the inventive method, yield are up to more than 80%, simultaneously because
Propargyl is introduced, improves the anti-flammability of resin, it is had more industrial value.
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 all be included within the scope of the present invention.
Claims (10)
- A kind of 1. benzoxazine colophony for introducing propargyl, it is characterised in that：Molecular structural formula with following structure：
- 2. the benzoxazine colophony according to claim 1 for introducing propargyl, it is characterised in that：Glass transition temperature is 280-360℃。
- 3. the benzoxazine colophony according to claim 1 for introducing propargyl, it is characterised in that：At 800 DEG C, resin it is residual Carbon rate is 62.1-73.6%.
- 4. the preparation method of the benzoxazine colophony of the introducing propargyl according to any one of claims 1 to 3, its feature exist In：Including following operating procedure：Step 1, benzoxazine, the following institute of its reaction equation are synthesized with solventless method with Bisphenol F, to cyano-aniline and paraformaldehyde Show：Step 2, it is dissolved in DMF or DMAc solvents, is reacted with 3- propargyl bromides, instead with the benzoxazine of gained in step 1 It should look like this：Reactant is filtered, filtrate is poured into cold water, is precipitated, precipitation is filtered out and is being dried in vacuo；Step 3, gained solid in step 2 is warming up to 220-270 DEG C of solidification 1-2h, obtains target product.
- 5. the preparation method of the benzoxazine colophony according to claim 4 for introducing propargyl, it is characterised in that：The step Bisphenol F in rapid one, it is 1 to the mol ratio of cyano-aniline and paraformaldehyde：2：4.0-4.6.
- 6. the preparation method of the benzoxazine colophony of the introducing propargyl according to claim 4 or 5, it is characterised in that：Institute State step 1 reaction to carry out in the absence of a solvent, reaction temperature is 90-110 DEG C, reaction time 0.5-6h.
- 7. the preparation method of the benzoxazine colophony according to claim 4 for introducing propargyl, it is characterised in that：The step The mol ratio of benzoxazine in rapid two, 3- propargyl bromides and potassium carbonate is 1：1.0-1.6：1.0-2.0.
- 8. the preparation method of the benzoxazine colophony according to claim 4 for introducing propargyl, it is characterised in that：The step Rapid two are carried out under conditions of having solvent, and reaction dissolvent is dimethylformamide or dimethyl acetamide.
- 9. the preparation method of the benzoxazine colophony of the introducing propargyl according to claim 7 or 8, it is characterised in that：Institute It is 80-100 DEG C to state step 2 reaction temperature, reaction time 8-24h；Reaction solution is poured into deionized water after reaction, will be analysed The precipitation washing gone out, dries, that is, obtains the target product of step 2.
- 10. the preparation method of the benzoxazine colophony according to claim 4 for introducing propargyl, it is characterised in that：It is described Step 2 uses Anhydrous potassium carbonate, and solvent is removed water with molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711147032.4A CN107674171A (en) | 2017-11-17 | 2017-11-17 | A kind of benzoxazine colophony for introducing propargyl and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711147032.4A CN107674171A (en) | 2017-11-17 | 2017-11-17 | A kind of benzoxazine colophony for introducing propargyl and preparation method thereof |
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| CN201711147032.4A Pending CN107674171A (en) | 2017-11-17 | 2017-11-17 | A kind of benzoxazine colophony for introducing propargyl and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747288A (en) * | 2009-12-21 | 2010-06-23 | 山东大学 | Monocyclic benzoxazine intermediate with low viscosity and a plurality of functional groups and synthesis method thereof |
| CN101857677A (en) * | 2010-06-08 | 2010-10-13 | 华东理工大学 | Silicon-containing alkyne aryl ether resin and preparation method thereof |
| US8802846B1 (en) * | 2013-04-22 | 2014-08-12 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D | Preparation and application of propargyl ether-containing benzoxazine with high-TG characteristic |
-
2017
- 2017-11-17 CN CN201711147032.4A patent/CN107674171A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747288A (en) * | 2009-12-21 | 2010-06-23 | 山东大学 | Monocyclic benzoxazine intermediate with low viscosity and a plurality of functional groups and synthesis method thereof |
| CN101857677A (en) * | 2010-06-08 | 2010-10-13 | 华东理工大学 | Silicon-containing alkyne aryl ether resin and preparation method thereof |
| US8802846B1 (en) * | 2013-04-22 | 2014-08-12 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D | Preparation and application of propargyl ether-containing benzoxazine with high-TG characteristic |
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》 * |
| 赵沙沙: "双酚A/对氨基苯腈型苯并噁嗪的合成与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
| CN110818868B (en) * | 2019-11-29 | 2023-12-12 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer, monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer resin and preparation method of monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer |
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