CN107868196A - A kind of benzoxazine colophony containing propargyl and preparation method thereof - Google Patents
A kind of benzoxazine colophony containing propargyl and preparation method thereof Download PDFInfo
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- CN107868196A CN107868196A CN201711147967.2A CN201711147967A CN107868196A CN 107868196 A CN107868196 A CN 107868196A CN 201711147967 A CN201711147967 A CN 201711147967A CN 107868196 A CN107868196 A CN 107868196A
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- Prior art keywords
- benzoxazine
- preparation
- propargyl
- benzoxazine colophony
- containing propargyl
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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
-
- 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)
- Phenolic Resins Or Amino Resins (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention provides a kind of benzoxazine colophony containing 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 containing propargyl
Resin and preparation method thereof.
Background technology
Benzoxazine be it is a kind of by phenols, formaldehyde, primary amine by reaction obtain containing aerobic, nitrogen hexa-atomic annelation
Compound, in a heated condition, ring-opening polymerisation can occur, generate Nitrogen element, and similar to the crosslinking net knot of phenolic resin
Structure.Benzoxazine ring-opening reaction produces without small molecule by-product, and cure shrinkage is almost nil.Benzoxazine both can with autohemagglutination,
Crosslinking copolymerization can be carried out with epoxy resin etc. again, at present, benzoxazine is widely used in very more fields.Its advantage exists
In very flexible MOLECULE DESIGN, good mechanical property, dielectric properties, fire resistance, heat resistance, and it is stronger viscous
Knot property, relatively low water absorption rate.
Change its performance currently in order to adapting to different field and can introduce different groups to the performance requirement of material.But specially
Research of the door for improving benzoxazine glass transition temperature has not been reported.
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 containing propargyl and preparation method thereof, it is set to have 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, its glass transition is improved
Temperature.
The present invention is realized using following scheme：
Benzoxazine colophony proposed by the present invention containing propargyl, there is the molecular structural formula of following structure：
N is the positive integer more than 1.
As the preferably benzoxazine colophony containing propargyl, glass transition temperature is 330-450 DEG C.
As the preferably benzoxazine colophony containing propargyl, at 800 DEG C, the Residual carbon of resin is 60.0-72.5%.
The preparation method of benzoxazine colophony containing propargyl, including following operating procedure：
Step 1, benzoxazine is synthesized with solventless method with bisphenol-A, aniline and paraformaldehyde, its reaction equation is as follows：
Formaldehyde is easily decomposed, it is necessary to appropriate excessive；
Step 2, it is dissolved in DMF or DMAc solvents, is occurred with 3- propargyl bromides anti-with the benzoxazine of gained in step 1
Should, reaction is as follows, obtains solid product：
Step 3, gained solid in step 2 is warming up to 220-260 DEG C of solidification 1-2h, obtains target product.
As preferable, the preparation method of the benzoxazine colophony containing propargyl, bisphenol-A in the step 1, aniline
Mol ratio with paraformaldehyde is 1：2：4.0-4.4.
As preferable, the preparation method of the benzoxazine colophony containing propargyl, 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 containing propargyl, benzoxazine in the step 2,3-
Propargyl bromide, the mol ratio of potassium carbonate is 1：1.0-1.8：1.0-2.0.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 containing propargyl, the step 2 is having the bar of solvent
Carried out under part, reaction dissolvent is the intensive polar solvents such as dimethylformamide or dimethyl acetamide.
As preferable, the preparation method of the benzoxazine colophony containing propargyl, the step 2 reaction temperature is 70-
90 DEG C, reaction time 12-24h；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 containing propargyl, the step 2 uses Carbon Dioxide
Potassium, solvent are removed water with molecular sieve.
The beneficial functional of the present invention is：
Alkynyl is introduced into benzoxazine colophony by chemical covalent bonds, resin can be improved by the cross-linking reaction again of alkynyl
The crosslink density of material, so as to improve the glass transition temperature of material.The cured rear detection of resin prepared by the present invention, its glass
Glass transition temperature is 330-450 DEG C, higher than similar resin material；In addition, propargyl contains nitrogen, benzo can be improved
The nitrogen content of oxazine solidfied material, so as to improve the anti-flammability of resin system.The benzoxazine colophony containing propargyl of the present invention
Preparation method use two-step method, the first step prepares intermediate, and second step is that intermediate is chemically modified, preparation process
Simply, environmentally friendly and cost is 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 benzoxazine colophony containing propargyl, in step 1, by bisphenol-A, aniline, paraformaldehyde massage
You are added in flask, the stirring reaction in oil bath pan, temperature is slowly raised to 90-110 DEG C from room temperature, reacts 0.5- than mixing
6h。
In step 2, by benzoxazine and 3- propargyl bromides, potassium carbonate is put into flask, reacts 12-24h at 70-90 DEG C,
Obtained mixture filtering will be reacted, filtrate will be poured into a large amount of cold water, will dry, and obtain in vacuum drying chamber after precipitation suction filtration
To product.Portion of product is solidified into 1-2h at 220-260 DEG C.
Embodiment 1
By 5g bisphenol-As, 4.079g aniline, 2.895g paraformaldehydes are added in three-necked flask, connect condenser pipe and stirring fills
Put, temperature is slowly raised to 110 DEG C, reacts 0.5 hour, reactant is taken out, obtains 8.572g benzoxazine solids.
By 3g benzoxazines, 0.904g 3- propargyl bromides, 1.223g 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.Portion of product is solidified into 1h at 220-260 DEG C.
2mg benzoxazines are placed in crucible, test DSC under nitrogen atmosphere, 5mg benzoxazines are placed in crucible,
Benzoxazine after 5mg is solidified is placed in crucible, carries out thermogravimetric analysis under nitrogen atmosphere.
Embodiment 2
By 4g bisphenol-As, 3.263g aniline, 7.015g paraformaldehydes are added in three-necked flask, connect condenser pipe and stirring fills
Put, temperature is slowly raised to 90 DEG C, reacts 2 hours, reactant is taken out, obtains 7.015g benzoxazine solids.
By 3g benzoxazines, 0.904g 3- propargyl bromides, 1.223g 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 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 3.765g
Product.Portion of product is solidified into 1h at 220-260 DEG C.
2mg benzoxazines are placed in crucible, test DSC under nitrogen atmosphere, 5mg benzoxazines are placed in crucible,
Benzoxazine after 5mg is solidified is placed in crucible, carries out thermogravimetric analysis under nitrogen atmosphere.
Embodiment 3
By 3g bisphenol-As, 2.447g aniline, 1.737g paraformaldehydes are added in three-necked flask, connect condenser pipe and stirring fills
Put, temperature is slowly raised to 110 DEG C, reacts 6 hours, reactant is taken out, obtains 5.873g benzoxazine solids.
By 2g benzoxazines, 0.603g3- propargyl bromides, 0.815g Anhydrous potassium carbonates are placed in three-necked flask, add 30ml bis-
Methylacetamide, flask is placed in oil bath pan and stirred, reacted 24h at 80 DEG C, reacted product is filtered, filtrate is poured into
In substantial amounts of water, solid product is filtered out, and washed several times, is placed in drying for one day in vacuum drying chamber, obtains 2.668g productions
Thing.Portion of product is solidified into 1h at 220-260 DEG C.
2mg benzoxazines are placed in crucible, test DSC under nitrogen atmosphere, 5mg benzoxazines are placed in crucible,
Benzoxazine after 5mg is solidified is placed in crucible, carries out thermogravimetric analysis under nitrogen atmosphere.
Embodiment 4
By 2g bisphenol-As, 1.632g aniline, 3.262g paraformaldehydes are added in three-necked flask, connect condenser pipe and stirring fills
Put, temperature is slowly raised to 90 DEG C, reacts 6 hours, reactant is taken out, obtains 3.262g benzoxazine solids.
By 2g benzoxazines, 0.603g 3- propargyl bromides, 0.815g 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.Portion of product is solidified into 1h at 220-260 DEG C.
2mg benzoxazines are placed in crucible, test DSC under nitrogen atmosphere, 5mg benzoxazines are placed in crucible,
Benzoxazine after 5mg is solidified is placed in crucible, carries out thermogravimetric analysis under nitrogen atmosphere.
The benzoxazine monomer containing propargyl prepared using the inventive method, yield are up to more than 80%, simultaneously because
Propargyl is introduced, improves the physical property of material, 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 containing propargyl, it is characterised in that：Molecular structural formula with following structure：
- 2. the benzoxazine colophony according to claim 1 containing propargyl, it is characterised in that：Glass transition temperature is 330-450℃。
- 3. the benzoxazine colophony according to claim 1 containing propargyl, it is characterised in that：At 800 DEG C, resin it is residual Carbon rate is 60.0-72.5%.
- 4. the preparation method of the benzoxazine colophony containing propargyl according to any one of claims 1 to 3, its feature exist In：Including following operating procedure：Step 1, benzoxazine is synthesized with solventless method with bisphenol-A, aniline and paraformaldehyde, its reaction equation is as follows：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, obtain solid product：Step 3, gained solid in step 2 is warming up to 220-260 DEG C of solidification 1-2h, obtains target product.
- 5. the preparation method of the benzoxazine colophony according to claim 4 containing propargyl, it is characterised in that：The step The mol ratio of bisphenol-A in rapid one, aniline and paraformaldehyde is 1：2：4.0-4.4.
- 6. the preparation method of the benzoxazine colophony containing 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 containing propargyl, it is characterised in that：The step Benzoxazine in rapid two, 3- propargyl bromides, the mol ratio of potassium carbonate is 1：1.0-1.8：1.0-2.0.
- 8. the preparation method of the benzoxazine colophony according to claim 4 containing 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 according to claim 4 containing propargyl, it is characterised in that：The step Rapid two reaction temperature is 70-90 DEG C, reaction time 12-24h；Reaction solution is poured into deionized water after reaction, by precipitation Precipitation washing, is dried, that is, obtains the target product of step 2.
- 10. the preparation method of the benzoxazine colophony according to claim 4 containing 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 |
|---|---|---|---|
| CN201711147967.2A CN107868196A (en) | 2017-11-17 | 2017-11-17 | A kind of benzoxazine colophony containing propargyl and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711147967.2A CN107868196A (en) | 2017-11-17 | 2017-11-17 | A kind of benzoxazine colophony containing propargyl and preparation method thereof |
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| CN107868196A true CN107868196A (en) | 2018-04-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582939A (en) * | 2021-08-06 | 2021-11-02 | 北京理工大学 | Secondary amino benzoxazine monomer and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070191555A1 (en) * | 2004-03-30 | 2007-08-16 | Hatsuo Ishida | Thermosetting resin composition and its article |
| 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 CN201711147967.2A patent/CN107868196A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070191555A1 (en) * | 2004-03-30 | 2007-08-16 | Hatsuo Ishida | Thermosetting resin composition and its article |
| 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》 * |
| 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》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582939A (en) * | 2021-08-06 | 2021-11-02 | 北京理工大学 | Secondary amino benzoxazine monomer and application thereof |
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Application publication date: 20180403 |
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