CN107778427A - A kind of benzoxazine colophony containing cyanate group and preparation method thereof - Google Patents
A kind of benzoxazine colophony containing cyanate group and preparation method thereof Download PDFInfo
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- CN107778427A CN107778427A CN201711148021.8A CN201711148021A CN107778427A CN 107778427 A CN107778427 A CN 107778427A CN 201711148021 A CN201711148021 A CN 201711148021A CN 107778427 A CN107778427 A CN 107778427A
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- benzoxazine
- cyanate group
- preparation
- containing cyanate
- 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 & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a kind of benzoxazine colophony containing cyanate group and preparation method thereof, molecular structural formula is as follows,Monomer structure prepared by the present invention is confirmed through analysis methods such as infrared spectrum, differential scanning calorimetries, the benzoxazine monomer containing cyanate group synthesized using this method, the glass transition temperature Tg of its resin is 286 305 DEG C after solidification, the defects of present invention exists for benzoxazine colophony, cyanate group is introduced into benzoxazine, make that there is very low-k and dielectric loss, and the kept stable in very wide frequency range and temperature range.
Description
Technical field
The present invention relates to a kind of thermosetting resin and its manufacture method, more particularly to a kind of Ben Bing Evil containing cyanate group
Piperazine resin and preparation method thereof.
Background technology
Polybenzoxazine be applied to various fields, such as electronic packaging materials, Aero-Space and other transport applications materials with
And ballistics.It is latent with extraordinary development from the angle of environmental protection because benzoxazine reaction does not produce accessory substance
Power.Cubical contraction is also the advantages of one is very big close to zero.Traditional benzoxazine colophony in preparation process often
Oligomer accessory substance can be produced, and the phenolic hydroxyl group in the oligomer can cause benzoxazine ring curing reaction, cause resin to be not easy
Storage, shelf-life are shorter.And if obtaining the benzoxazine colophony of high-purity by purification processes, it can not only improve preparation process
Production cost, the defects of also bringing resin cure temperature higher.
Cyanate ester resin is a kind of new type resin to grow up the 1970s, because it has well comprehensive
Can and electrical insulation capability and be widely applied to the fields such as Aero-Space, electronic equipment and adhesive.Chinese patent application《It is a kind of
Xin type benzoxazine colophony method for toughening》(publication number:CN106832922A the method for) disclosing Yi Zhong oxazine resin toughenings, though
So it is capable of the toughness of a certain degree of put forward Gao oxazine resins, but preparation technology operation is complex, is unfavorable for answering in industry
With popularization.
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
New benzoxazine colophony containing cyanate group and preparation method thereof, it is set to have more practicality.By constantly studying, setting
Meter, 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 new benzoxazine colophony containing cyanate group and preparation method thereof, improves Ben Bing Evil
The heat endurance and chemical stability of piperazine resin.
The present invention is realized using following scheme：
Benzoxazine colophony proposed by the present invention containing cyanate group, molecular structural formula is as follows,
As preferable, the glass transition temperature of the benzoxazine colophony containing cyanate group is 286-305 DEG C.
The preparation method of the foregoing benzoxazine colophony containing cyanate group, including following operating procedure,
Step 1, benzoxazine monomer is synthesized with solventless method with bisphenol-A, aniline and paraformaldehyde, paraformaldehyde easily divides
For solution, it is necessary to appropriate excessive, its chemical equation is as follows：
Step 2, benzoxazine prepared by solventless method in step 1 are anti-with cyanogen bromide using triethylamine as catalyst
Should, catalyst of triethylamine will be slowly added dropwise, and reaction equation is as follows：
Step 3, by the heating of gained solid, solidification in step 2, obtain the benzoxazine colophony containing cyanate group.
As preferable, the preparation method of the benzoxazine colophony containing cyanate group, bisphenol-A, benzene in the step 1
The mol ratio of amine and paraformaldehyde is 1：2：4-4.4.
As preferable, the preparation method of the benzoxazine colophony containing cyanate group, the step 1 is solvent-free
Under the conditions of reacted, reaction temperature be 90-110 DEG C, reaction time 0.5-6h.
As preferable, the preparation method of the benzoxazine colophony containing cyanate group, benzoxazine in the step 2,
Cyanogen bromide, the mol ratio of triethylamine is 1：1-1.8：1-1.4.
As preferable, the preparation method of the benzoxazine colophony containing cyanate group, the step 2 reaction is in solvent
Under the conditions of carry out, the reaction dissolvent is acetone, the part intensive polar solvent such as DMF, DMAc.
As preferable, the preparation method of the benzoxazine colophony containing cyanate group, the step 2 reaction is in nitrogen
Carried out under atmosphere and under ice bath, completely cut off air and water, carry out at low temperature, reaction time 2-6h；Reaction solution is poured into
In ionized water, the precipitation of precipitation is washed, dried, that is, obtains the target product of step 2.
As preferable, the preparation method of the benzoxazine colophony containing cyanate group, solid heats up in the step 3
Temperature is 220-260 DEG C.
The beneficial functional of the present invention is：
Monomer structure prepared by the present invention is confirmed through analysis methods such as infrared spectrum, differential scanning calorimetries, uses
The benzoxazine monomer containing cyanate group of this method synthesis, the glass transition temperature Tg of its resin is 286- after solidification
305 DEG C, reason is because cyanate group carries out thermal cyclization trimerization under appropriate reaction condition, forms stable triazine net
Network, improve the glass transition temperature of resin.The defects of present invention exists for benzoxazine colophony, cyanate group is drawn
Enter benzoxazine, make it have very low-k and dielectric loss, and 102-106HZ frequency ranges and -50-200 temperature
Kept stable in the range of degree.Its mechanical property and heat resistance is also very outstanding.Meanwhile it also has saturation hydroscopicity
It is low, the features such as fabulous humidity resistance and excellent processing technology.
Brief description of the drawings
Fig. 1 is the infrared spectrogram for the benzoxazine colophony that embodiment 1 obtains；
Fig. 2 is the DSC spectrograms for the benzoxazine that embodiment 1 obtains.
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.
Operating procedure：
By bisphenol-A, aniline, paraformaldehyde in molar ratio 1：2：4.4 mixing, are added in flask, are stirred in oil bath pan
And reaction, temperature are slowly raised to 90-110 DEG C from room temperature, react 0.5-6h, after stopping reaction, obtained solid is dried.
The benzoxazine that solventless method is obtained, cyanogen bromide, triethylamine in molar ratio 1：1.2：1.1 weigh, in ice bath bar
Under part and nitrogen atmosphere, benzoxazine and cyanogen bromide are first added in acetone soln, stirs and triethylamine is slowly added dropwise, about
Half an hour is dripped off, and reacts 2 hours, and obtained mixture is filtered, filtrate is poured into a large amount of cold water, true after precipitation is filtered
It is drying for one day in empty drying box, obtain product.
Embodiment 1
By 10g bisphenol-As, 8.158g aniline, 5.263g paraformaldehydes are added in three-necked flask, connect condenser pipe and stirring fills
Put, temperature is slowly raised to 110 DEG C, half an hour is reacted, reactant is taken out, obtains 19.120g benzoxazine solids.
By 5g benzoxazine solids obtained above, 4.130g 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.2.405g 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 5.820g solids.
Be made target product infrared spectrogram and DSC figure as depicted in figs. 1 and 2, Fig. 1 be from infrared spectrogram, wherein
940cm-1Left and right be benzoxazine characteristic peak, 2230cm-1Left and right is cyano group characteristic peak, it was confirmed that the structure of prepared resin.
Fig. 2 is the DSC figures obtained by differential scanning calorimetry, it can be seen that the curing reaction peak temperature of the benzoxazine colophony is at 230 DEG C
Left and right, there is relatively low solidification temperature, reduce further preparation cost.
Embodiment 2
By 10g bisphenol-As, 8.158g aniline, 5.789g paraformaldehydes are added in three-necked flask, connect condenser pipe and stirring fills
Put, temperature is slowly raised to 105 DEG C, half an hour is reacted, reactant is taken out, obtains 20.150g benzoxazine solids.
2.294g cyanogen bromide solids are dissolved in 30ml acetone, add 2.186g triethylamines.Three-necked flask is poured into, is passed through nitrogen
Gas shielded, it is placed in ice bath.Obtained benzoxazine taking-up 5g 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 5.730g solids.
Embodiment 3
By 8g bisphenol-As, 6.526g aniline, 4.632g paraformaldehydes are added in three-necked flask, connect condenser pipe and stirring fills
Put, temperature is slowly raised to 105 DEG C, half an hour is reacted, reactant is taken out, obtains 16.12g benzoxazine solids.
2.478g cyanogen bromide solids are dissolved in 30ml acetone, add 1.443g 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 3.455g solids.
Embodiment 4
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, half an hour is reacted, reactant is taken out, obtains 10.505g benzoxazine solids.
By 3g benzoxazine solids obtained above, 1.377g 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.1.312g 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 3.150g 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, the plexiglas transition temperature Tg after solidification is up to 286-305 DEG C, improves the physical of material
Energy and heat resistance, improve the processability of material.
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 (9)
- A kind of 1. benzoxazine colophony containing cyanate group, it is characterised in that：Molecular structural formula is as follows,
- 2. the benzoxazine colophony according to claim 1 containing cyanate group, it is characterised in that：Glass transition temperature is 286-305℃。
- 3. the preparation method of the benzoxazine colophony according to claim 1 or 2 containing cyanate group, it is characterised in that： Including following operating procedure,Step 1, benzoxazine monomer is synthesized with solventless method with bisphenol-A, aniline and paraformaldehyde, its chemical equation 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 the heating of gained solid, solidification in step 2, obtain the benzoxazine colophony containing cyanate group.
- 4. the preparation method of the benzoxazine colophony according to claim 3 containing cyanate group, it is characterised in that：It is described The mol ratio of bisphenol-A, aniline and paraformaldehyde is 1 in step 1：2：4-4.4.
- 5. the preparation method of the benzoxazine colophony according to claim 3 containing cyanate group, it is characterised in that：It is described Step 1 is reacted in the absence of a solvent, and reaction temperature is 90-110 DEG C, reaction time 0.5-6h.
- 6. the preparation method of the benzoxazine colophony according to claim 3 containing cyanate group, it is characterised in that：It is described Benzoxazine in step 2, cyanogen bromide, the mol ratio of triethylamine is 1：1-1.8：1-1.4.
- 7. the preparation method of the benzoxazine colophony according to claim 3 containing cyanate group, it is characterised in that：It is described Step 2 reaction is carried out under solvent condition, reaction dissolvent be acetone, DMF or DMAc it is therein any one.
- 8. the preparation method of the benzoxazine colophony according to claim 3 containing cyanate group, it is characterised in that：It is described Step 2 reaction is carried out under nitrogen atmosphere and under ice bath, reaction time 2-6h；Reaction solution is poured into deionized water, will The precipitation washing of precipitation, dries, that is, obtains the target product of step 2.
- 9. the preparation method of the benzoxazine colophony according to claim 3 containing cyanate group, it is characterised in that：It is described Solid warming temperature is 220-260 DEG C in step 3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711148021.8A CN107778427A (en) | 2017-11-17 | 2017-11-17 | A kind of benzoxazine colophony containing cyanate group and preparation method thereof |
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| CN201711148021.8A CN107778427A (en) | 2017-11-17 | 2017-11-17 | A kind of benzoxazine colophony containing cyanate group 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 |
| CN1139104A (en) * | 1995-06-23 | 1997-01-01 | 四川联合大学 | Granular polybenzoxazine intermediate and its preparation |
| CN1181763A (en) * | 1995-01-27 | 1998-05-13 | 联合信号公司 | Process for prodn. of multicyanate esters |
| CN1477136A (en) * | 2003-07-08 | 2004-02-25 | 北京玻璃钢研究设计院 | Phenolic cyanate resin and its synthesis method and phenolic cyanate ablative material composite |
-
2017
- 2017-11-17 CN CN201711148021.8A patent/CN107778427A/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 |
| CN1181763A (en) * | 1995-01-27 | 1998-05-13 | 联合信号公司 | Process for prodn. of multicyanate esters |
| CN1139104A (en) * | 1995-06-23 | 1997-01-01 | 四川联合大学 | Granular polybenzoxazine intermediate and its preparation |
| CN1477136A (en) * | 2003-07-08 | 2004-02-25 | 北京玻璃钢研究设计院 | Phenolic cyanate resin and its synthesis method and phenolic cyanate ablative material composite |
Non-Patent Citations (2)
| Title |
|---|
| 第1401–1411页: "（"Study of the Characterization and Curing of a Phenyl Benzoxazine Using 15N Solid-State Nuclear Magnetic Resonance Spectroscopy"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 贾红兵等: "《高分子材料》", 30 November 2009, 南京大学出版社 * |
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Application publication date: 20180309 |
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