CN107814892A - A kind of oligomerization temperature benzoxazine colophony and preparation method thereof - Google Patents
A kind of oligomerization temperature benzoxazine colophony and preparation method thereof Download PDFInfo
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- CN107814892A CN107814892A CN201711145733.4A CN201711145733A CN107814892A CN 107814892 A CN107814892 A CN 107814892A CN 201711145733 A CN201711145733 A CN 201711145733A CN 107814892 A CN107814892 A CN 107814892A
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- benzoxazine
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- 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 Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a kind of oligomerization temperature benzoxazine colophony and preparation method thereof, the molecular structural formula with following structure：
Description
Technical field
The present invention relates to a kind of thermosetting resin and its manufacture method, more particularly to a kind of oligomerization temperature benzoxazine tree
Fat and preparation method thereof.
Background technology
Polybenzoxazine is a kind of novel hot setting resin to grow up on the basis of traditional phenolic resin.Monomer
It is oxygen-containing, nitrogen the 6-membered heterocyclic compound obtained by primary amine class, phenols and formaldehyde by Mannich condensation reactions, passes through
Different types of phenol and primary amino-compound is selected to synthesize the benzoxazine intermediate for meeting different needs.Benzoxazine monomer
Ring-opening polymerisation solidifies, and ultimately forms the Polybenzoxazine resin of similar phenolic resin cross-linked structure.With high temperature resistant, fire-retardant, good
The advantages that dielectric properties and mechanical property for getting well.
But in order to preferably apply in a certain field, it is necessary to do further modification to it, such as《A kind of Xin types Ben Bing Evil
Piperazine resin toughening method》(publication number:CN106832922A the method for toughening of resin) is disclosed.There is presently no specifically for benzene
Bing oxazines reduce the report and the not no relevant report on bisphenol-f type cyanate benzoxazine of its polymerization temperature.
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
The preparation method of oligomerization temperature benzoxazine colophony, it is set to 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 invention provides a kind of preparation method of oligomerization temperature benzoxazine colophony, its polymerization temperature is reduced.
The present invention is realized using following scheme：
Oligomerization temperature benzoxazine colophony proposed by the present invention, there is the molecular structural formula of following structure：
N is the positive integer more than 1.
As preferable, oligomerization temperature benzoxazine colophony, glass transition temperature is 296-358 DEG C.
The preparation method of oligomerization temperature benzoxazine colophony, including following operating procedure：
Step 1, benzoxazine monomer is synthesized with solventless method with Bisphenol F, a cyano-aniline and paraformaldehyde, its chemistry
Reaction equation is as follows：Wherein paraformaldehyde is easily decomposed, it is necessary to appropriate excessive；
Paraformaldehyde is easily decomposed, it is necessary to appropriate excessive.
Step 2, benzoxazine prepared by solventless method in step 1 are anti-with cyanogen bromide using triethylamine as catalyst
Should, reaction equation is as follows：
Catalyst of triethylamine will be slowly added dropwise, and ensure that reaction uniformly, can be carried out sufficiently；
Step 3, by gained solid elevated cure in step 2, obtain target product.
As preferable, the preparation method of oligomerization temperature benzoxazine colophony, Bisphenol F, a cyano group in the step 1
The mol ratio of aniline and paraformaldehyde is 0.5~2：1~4：2.2~8.8.Each material can be more in this proportion
Sufficiently reacted, be advantageous to cost-effective.
As preferable, the preparation method of oligomerization temperature benzoxazine colophony, the step 1 reaction is solvent-free
Under the conditions of carry out, reaction temperature is 80-160 DEG C, reaction time 0.3-8h, reacts and fully carries out, accessory substance is less.
As preferable, the preparation method of oligomerization temperature benzoxazine colophony, benzoxazine, bromination in the step 2
The mol ratio of cyanogen and triethylamine is 0.5~2：0.6~2.4：0.7~2.8.In this proportion, material can be sufficient
Reacted.
As preferable, the preparation method of oligomerization temperature benzoxazine colophony, the step 2 reaction needs solvent, instead
It should carry out under nitrogen atmosphere and under ice bath, the reaction time is 1~5h, completely cuts off air and water, and carry out at low temperature；Instead
Reaction solution is poured into deionized water after answering, and the precipitation of precipitation is washed, and is dried, that is, obtains the target product of step 2.
As preferable, the preparation method of oligomerization temperature benzoxazine colophony, the reaction dissolvent is intensive polar solvent.
Preferably, intensive polar solvent is acetone, DMF or DMAc one kind therein.
Preferably, step 3 solidification warming temperature is 200~300 DEG C, is easy to resin rapid curing.
The beneficial functional of the present invention is：
The benzoxazine containing cyanate group synthesized using this method, its solidification temperature value is between 150-180 DEG C, phase
It is more much lower than in traditional benzoxazine colophony.The cyanate group of introducing can carry out being crosslinked instead before benzoxazine ring open loop
Should, and solventless method prepare benzoxazine in residual fraction hydroxyl can catalytic resin reaction so that the resin has
Relatively low solidification temperature.The glass transition temperature Tg of its resin is 296-358 DEG C after resin solidification.Cyano group is drawn by amine source
Enter in benzoxazine molecule, the heat resistance of benzoxazine can be improved.On this basis, the cyanate group being re-introduced into reduces
Dielectric constant and dielectric loss, and in very wide frequency range and temperature range kept stable.Cyanate group
Thermal cyclization trimerization is carried out under suitable condition, so as to form stable triazine structure so that the mechanical property of benzoxazine colophony
Can further it be lifted with heat resistance.Simple production process of the present invention, it is adapted to large-scale industrial production, obtained benzoxazine
Resin combination property is outstanding, there is very strong actual application value.
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
By Bisphenol F, a cyano-aniline, paraformaldehyde mixes in molar ratio, is added in flask, in oil bath pan stirring and
Reaction, temperature are slowly raised to 90-110 DEG C from room temperature, react 0.5-6h, and after stopping reaction, obtained solid is dried.
The benzoxazine that solventless method is obtained, cyanogen bromide, triethylamine weigh in molar ratio, in condition of ice bath and nitrogen
Under atmosphere, benzoxazine and cyanogen bromide are first added in acetone soln, stirs and triethylamine is slowly added dropwise, about half an hour drips
It is complete, react 2 hours, obtained mixture is filtered, filtrate is poured into a large amount of cold water, in vacuum drying chamber after precipitation is filtered
In it is drying for one day, obtain product.
Embodiment 1
By 5g Bisphenol Fs, cyano-aniline between 5.900g, 3.300g paraformaldehydes are added in three-necked flask, connect condenser pipe and
Agitating device, temperature is slowly raised to 110 DEG C, half an hour is reacted, reactant is taken out, obtains 8.764g benzoxazine solids.
By 3g benzoxazine solids obtained above, 0.672g cyanogen bromide solids are dissolved in 50ml acetone, pour into three mouthfuls of burnings
Bottle, nitrogen protection is passed through, is placed in ice bath.0.587g triethylamines are at the uniform velocity instilled into flask with dropping funel with half-hour period
In, then react two hours, reacted product is filtered, the filtrate after filtering is poured into cold water, is filtered what is obtained
Drying is precipitated, obtains 3.958g solids.
Embodiment 2
By 4g Bisphenol Fs, cyano-aniline between 4.720g, 2.640g paraformaldehydes are added in three-necked flask, connect condenser pipe and
Agitating device, temperature is slowly raised to 105 DEG C, half an hour is reacted, reactant is taken out, obtains 7.215g benzoxazine solids.
0.672g cyanogen bromide solids are dissolved in 30ml acetone, add 0.587g triethylamines.Three-necked flask is poured into, is passed through nitrogen
Gas shielded, it is placed in ice bath.Obtained benzoxazine taking-up 3g is dissolved in 20ml acetone, with dropping funel with half-hour period
At the uniform velocity instill in flask, then react two hours, reacted product is filtered, the filtrate after filtering is poured into cold water, will
It filters obtained precipitation drying, obtains 3.859g solids.
Embodiment 3
By 3g Bisphenol Fs, cyano-aniline between 3.540g, 1.980g paraformaldehydes are added in three-necked flask, connect condenser pipe and
Agitating device, temperature is slowly raised to 105 DEG C, reacts 6 hours, reactant is taken out, obtains 5.941g benzoxazine solids.
0.448g cyanogen bromide solids are dissolved in 20ml acetone, add 0.391g triethylamines.Three-necked flask is poured into, is passed through nitrogen
Gas shielded, it is placed in ice bath.Obtained benzoxazine taking-up 2g is dissolved in 20ml acetone, with dropping funel with half-hour period
At the uniform velocity instill in flask, then react two hours, reacted product is filtered, the filtrate after filtering is poured into cold water, will
It filters obtained precipitation drying, obtains 2.650g solids.
Embodiment 4
By 2g Bisphenol Fs, cyano-aniline between 2.360g, 1.320g paraformaldehydes are added in three-necked flask, connect condenser pipe and
Agitating device, temperature is slowly raised to 90 DEG C, reacts 6 hours, reactant is taken out, obtains 3.183g benzoxazine solids.
By 2g benzoxazine solids obtained above, 0.448g cyanogen bromide solids are dissolved in 50ml acetone, pour into three mouthfuls of burnings
Bottle, nitrogen protection is passed through, is placed in ice bath.0.391g triethylamines are at the uniform velocity instilled into flask with dropping funel with half-hour period
In, then react two hours, reacted product is filtered, the filtrate after filtering is poured into cold water, is filtered what is obtained
Drying is precipitated, obtains 2.551g solids.
The benzoxazine monomer containing cyanate prepared using the method for the present invention, yield are up to more than 80%, simultaneously because
Cyanate group is introduced, polymerization temperature is relatively low, and preparing cost reduces.
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. oligomerization temperature benzoxazine colophony, it is characterised in that：Molecular structural formula with following structure：
- 2. oligomerization temperature benzoxazine colophony according to claim 1, it is characterised in that：Glass transition temperature is 296- 358℃。
- 3. the preparation method of oligomerization temperature benzoxazine colophony according to claim 1 or 2, it is characterised in that：Including Following operating procedure：Step 1, benzoxazine monomer is synthesized with solventless method with Bisphenol F, a cyano-aniline and paraformaldehyde, it chemically reacts Formula is as follows：Step 2, benzoxazine prepared by solventless method in step 1, using triethylamine as catalyst, and cyanogen bromide reaction, instead Answer formula as follows：Step 3, by gained solid elevated cure in step 2, obtain target product.
- 4. the preparation method of oligomerization temperature benzoxazine colophony according to claim 3, it is characterised in that：The step The mol ratio of Bisphenol F, a cyano-aniline and paraformaldehyde is 0.5~2 in one：1~4：2.2~8.8.
- 5. the preparation method of oligomerization temperature benzoxazine colophony according to claim 3, it is characterised in that：The step One reaction is carried out in the absence of a solvent, and reaction temperature is 80-160 DEG C, reaction time 0.3-8h.
- 6. the preparation method of oligomerization temperature benzoxazine colophony according to claim 3, it is characterised in that：The step The mol ratio of benzoxazine, cyanogen bromide and triethylamine is 0.5~2 in two：0.6~2.4：0.7~2.8.
- 7. the preparation method of oligomerization temperature benzoxazine colophony according to claim 3, it is characterised in that：The step Two reactions need solvent, and reaction is carried out under nitrogen atmosphere and under ice bath, and the reaction time is 1~5h；Reaction solution falls after reaction Enter in deionized water, the precipitation of precipitation is washed, dry, that is, obtain the target product of step 2.
- 8. the preparation method of oligomerization temperature benzoxazine colophony according to claim 7, it is characterised in that：The reaction Solvent is intensive polar solvent.
- 9. the preparation method of oligomerization temperature benzoxazine colophony according to claim 8, it is characterised in that：The strong pole Property solvent is acetone, DMF or DMAc one kind therein.
- 10. the preparation method of oligomerization temperature benzoxazine colophony according to claim 3, it is characterised in that：The step Rapid three solidifications warming temperature is 200~300 DEG C.
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| CN201711145733.4A CN107814892A (en) | 2017-11-17 | 2017-11-17 | A kind of oligomerization temperature benzoxazine colophony and preparation method thereof |
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| CN201711145733.4A CN107814892A (en) | 2017-11-17 | 2017-11-17 | A kind of oligomerization temperature benzoxazine colophony and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543516A (en) * | 1994-05-18 | 1996-08-06 | Edison Polymer Innovation Corporation | Process for preparation of benzoxazine compounds in solventless systems |
| CN101824146A (en) * | 2010-04-15 | 2010-09-08 | 华烁科技股份有限公司 | Preparation method of bisphenol A benzoxazine resin with high stability |
| CN101831073A (en) * | 2010-04-15 | 2010-09-15 | 华烁科技股份有限公司 | Method for preparing bisphenol-A phenolic benzoxazine resin |
| CN102649838A (en) * | 2011-02-25 | 2012-08-29 | 华东理工大学 | Bisphenol benzoxazine modified silicon-contained aryne resin and preparation method thereof |
-
2017
- 2017-11-17 CN CN201711145733.4A patent/CN107814892A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543516A (en) * | 1994-05-18 | 1996-08-06 | Edison Polymer Innovation Corporation | Process for preparation of benzoxazine compounds in solventless systems |
| CN101824146A (en) * | 2010-04-15 | 2010-09-08 | 华烁科技股份有限公司 | Preparation method of bisphenol A benzoxazine resin with high stability |
| CN101831073A (en) * | 2010-04-15 | 2010-09-15 | 华烁科技股份有限公司 | Method for preparing bisphenol-A phenolic benzoxazine resin |
| CN102649838A (en) * | 2011-02-25 | 2012-08-29 | 华东理工大学 | Bisphenol benzoxazine modified silicon-contained aryne resin and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| SEISHI OHASHI ET AL.: "Synthesis and Characterization of Cyanate Ester Functional Benzoxazine and Its Polymer", 《MACROMOLECULES》 * |
| 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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