CN105111438B - A kind of polyethers amine type benzoxazine prepolymer and preparation method thereof - Google Patents
A kind of polyethers amine type benzoxazine prepolymer and preparation method thereof Download PDFInfo
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- CN105111438B CN105111438B CN201510627768.6A CN201510627768A CN105111438B CN 105111438 B CN105111438 B CN 105111438B CN 201510627768 A CN201510627768 A CN 201510627768A CN 105111438 B CN105111438 B CN 105111438B
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Abstract
The present invention relates to a kind of polyethers amine type benzoxazine prepolymer and preparation method thereof, aldehyde compound, bisphenol-A and polyether amine compound are added into reaction vessel, amido mol ratio of the aldehyde radical with the phenolic hydroxyl group in bisphenol-A, in polyether amine compound is 2~2.4 wherein in aldehyde compound：1~1.2：1~1.2, organic solvent dissolving is added, reacts 6~10h in 80~110 DEG C, reaction solution is poured into methanol solution and precipitated by reaction after terminating, milky suspension is obtained, removing supernatant liquor after standing obtains white precipitate, is ground after white precipitate is dried and obtains polyethers amine type benzoxazine prepolymer.The performed polymer, which finally solidifies obtained polyethers amine type benzoxazine colophony, has excellent heat resistance, mechanical property and dielectric properties, can be widely used in the composites such as copper-clad plate, laminate.
Description
Technical field
The present invention relates to high-molecular organic material technical field, and in particular to a kind of polyethers amine type benzoxazine prepolymer and
Its preparation method.
Background technology
Benzoxazine is six synthesized using phenolic compound, aminated compounds and aldehydes as raw material by Mannich reactions
Membered heterocyclic compound.Polybenzoxazine material is a kind of new thermosetting to grow up on the basis of traditional phenolic resin
Resin, it overcomes traditional phenolic aldehyde while the excellent hot property of traditional phenolic resin, anti-flammability and electrical insulating property is maintained
For resin discharge small molecule in processing solidification process the shortcomings that, products made thereby porosity is low, and volume is shunk close to zero, material tool
There are more excellent high-temperature thermal stability performance, fire resistance, mechanical property and chemical stability etc., and water imbibition is low and makes
Without strong acid or strong base catalyst during standby, the infringement to equipment is reduced.Therefore in fields such as building, electronics, Aero-Space
It is with a wide range of applications, causes the research interest of people.
But Polybenzoxazine resin also has the shortcomings that some are intrinsic, and such as most of benzoxazine monomer is solid, they
It is difficult to easily use as liquid thermosetting resin presoma in process；Obtained after common benzoxazine polymerization
Polybenzoxazine resin is more crisp, and mechanical performance is not very high.
The content of the invention
The technical problems to be solved by the invention are for above shortcomings in the prior art, there is provided one kind has excellent
Good heat resistance, polyethers amine type benzoxazine prepolymer easy to process and preparation method thereof.
In order to solve the above technical problems, technical scheme provided by the invention is：
A kind of polyethers amine type benzoxazine prepolymer is provided, it has below formula：
Wherein n=2.5~20.
The present invention also provides the preparation method of above-mentioned polyethers amine type benzoxazine prepolymer, and its step is as follows：Hold to reaction
Aldehyde compound, bisphenol-A and polyether amine compound are added in device, aldehyde radical and the phenol hydroxyl in bisphenol-A wherein in aldehyde compound
Amido mol ratio in base, polyether amine compound is 2~2.4：1~1.2：1~1.2, organic solvent dissolving is added, in 80~
Reaction solution is poured into methanol solution and precipitated after terminating by 110 DEG C of 6~10h of reaction, reaction, obtains milky suspension, after standing
Remove supernatant liquor and obtain white precipitate, ground after white precipitate is dried and obtain polyethers amine type benzoxazine prepolymer；Or
Aldehyde compound and polyether amine compound are added into reaction vessel, adds organic solvent, is added after being sufficiently stirred
Enter bisphenol-A, amido mol ratio of the aldehyde radical with the phenolic hydroxyl group in bisphenol-A, in polyether amine compound is 2 wherein in aldehyde compound
~2.4：1~1.2：1~1.2,6~10h is reacted in 80~110 DEG C, reaction, which pours into reaction solution in methanol solution after terminating, sinks
Form sediment, obtain milky suspension, removing supernatant liquor after standing obtains white precipitate, grinds and is gathered after white precipitate is dried
Ether amines type benzoxazine prepolymer.
By such scheme, the aldehyde compound is formaldehyde or paraformaldehyde.
By such scheme, the polyether amine compound is PPOX binary amine compound, and molecular structural formula is such as
Under：
Wherein n=2.5~20.
By such scheme, the organic solvent be toluene, dimethylbenzene, ethanol, chloroform, dimethylformamide, Isosorbide-5-Nitrae-
Any one or more in dioxane.
Preferably, the concentration of methanol solution is 50~90wt%.
The present invention also provides the application of above-mentioned polyethers amine type benzoxazine prepolymer, is specially：By the polyethers amine type benzene
Bing oxazine performed polymers are used for copper-clad plate, binding agent, laminate, printed circuit board (PCB), semiconductor packages material after being dissolved with butanone solvent
In material or composite, Polybenzoxazine resin is obtained in 100~220 DEG C of 4~24h of curing reaction.
The beneficial effects of the present invention are：1st, preparation technology of the present invention is simple, and raw material is easy to get, using bisphenol-A as phenol source, with poly-
Ether aminated compounds is amine source, polyethers amine type benzoxazine prepolymer has been synthesized using solvent method, by adjusting monomer aldehydes
The ratio of compound, bisphenol-A and polyether amine compound, the performed polymer is set finally to solidify obtained polyethers amine type benzoxazine colophony
With excellent heat resistance, mechanical property and dielectric properties, can be widely used in the composites such as copper-clad plate, laminate；2、
By selecting reaction monomers to make the polyethers amine type benzoxazine prepolymer of synthesis be backbone chain type benzoxazine, and the chain end hung
Density is small, and heat endurance is higher, and the benzoxazine prepolymer of backbone chain type is intended to be crosslinked and obtain outstanding toughness, and this
Pre-polymerization physical efficiency is dissolved in solvent, can also be processed in the molten state, the polyethers amine type benzoxazine colophony obtained after heating polymerization
For thermosetting polymer, the resin has the excellent heat resistance of thermosetting resin (180~280 DEG C of maximum operation (service) temperature) and thermoplastic concurrently
The property excellent mechanical performance of resin (100~125MPa of tensile strength), and the excellent (dielectric constant under 110MHz of dielectric properties
Between 2.5~3.5).
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the polyethers amine type benzoxazine prepolymer prepared by the embodiment of the present invention 1.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
The preparation of polyethers amine type benzoxazine prepolymer：
By 5.04g (0.023mol) polyetheramine, 5.28g (0.023mol) bisphenol-A, 2.78g (0.092mol) paraformaldehyde
Add and stirred, in the 250mL of thermometer three-necked flask equipped with condenser pipe, magneton, aldehyde radical, phenolic hydroxyl group and amidine functional group mole
Than for 2：1：1, add 51mL toluene/ethanols mixed solvent (toluene and ethanol volume ratio 2:1) 80 are heated to after, being well mixed
Reaction solution is poured into 100mL methanol solutions (concentration 50wt%) after terminating and precipitated by DEG C reaction 9h, reaction, and it is suspended to obtain milky
Liquid, 12h is stood, remove supernatant liquor and obtain white precipitate, white precipitate is dried in vacuo 8h at 50 DEG C, finally by drying
The powder that product grinds to obtain brown color is polyethers amine type benzoxazine prepolymer.
Polyetheramine molecular structural formula is used in the present embodiment：
It is the infrared spectrogram of polyethers amine type benzoxazine prepolymer manufactured in the present embodiment as shown in Figure 1, wherein
944cm-1The C-H out-of-plane bending vibration absworption peaks of the adjacent phenyl ring of Shi oxazine rings, 1234cm-1It is asymmetric flexible corresponding to C-O-C
Vibration peak.Other 1325cm-1It is-CH2Methylene characteristic absorption peak, 1502cm-1Belong to the characteristic absorption peak of triazine ring, table
The formation of bright triazine ring.To sum up, illustrate that the present embodiment synthetic product is polyethers amine type main chain benzoxazine prepolymer, its molecule knot
Structure formula is：
Embodiment 2
The preparation of polyethers amine type benzoxazine prepolymer：
8.40g (0.023mol) polyetheramine, 5.28g (0.023mol) bisphenol-A, 2.78g (0.092mol) formaldehyde are added
Stirred, in the three-necked flask of thermometer equipped with condenser pipe, magneton, aldehyde radical, phenolic hydroxyl group and amidine functional group mol ratio are 2：1：1,
It is solvent to add 51mL chloroforms, and 80 DEG C of reaction 10h are heated to after well mixed, and reaction pours into reaction solution after terminating
Precipitated in 100mL methanol solutions (concentration 60wt%), obtain milky suspension, stand 24h, removed supernatant liquor and obtain white
Precipitation, 6h is dried in vacuo by white precipitate at 60 DEG C, and the powder for finally grinding to obtain brown color by the product of drying is poly-
Ether amines type benzoxazine prepolymer.
Polyetheramine molecular structural formula is used in the present embodiment：
Embodiment 3
The preparation of polyethers amine type benzoxazine prepolymer：
9.71g (0.023mol) polyetheramine, 5.28g (0.023mol) bisphenol-A, 3.34g (0.11mol) formaldehyde are added and matched somebody with somebody
In the three-necked flask for having condenser pipe, magneton stirring, thermometer, aldehyde radical, phenolic hydroxyl group and amidine functional group mol ratio are 2.4：1：1,
It is solvent to add 51mL dimethylformamides, and 110 DEG C of reaction 6h are heated to after well mixed, and reaction falls reaction solution after terminating
Enter in 100mL methanol solutions (concentration 70wt%) and precipitate, obtain milky suspension, stand 12h, removing supernatant liquor obtains white
Color precipitates, and white precipitate is dried in vacuo into 8h at 50 DEG C, the powder that the product of drying finally is ground to obtain to brown color is
Polyethers amine type benzoxazine prepolymer.
Polyetheramine molecular structural formula is used in the present embodiment：
Embodiment 4
The preparation of polyethers amine type benzoxazine prepolymer：
18.73g (0.028mol) polyetheramine, 3.34g (0.11mol) paraformaldehyde are added and stirred equipped with condenser pipe, magneton
Mix, in the three-necked flask of thermometer, it is solvent to add 51mL toluene, and it is double that stirring adds 6.34g (0.028mol) after 30 minutes
Phenol A, wherein aldehyde radical, phenolic hydroxyl group and amidine functional group mol ratio are 2.4：1.2：1.2,100 DEG C of reaction 7h are heated to, reaction terminates
Reaction solution is poured into 100mL methanol solutions (concentration 80wt%) afterwards and precipitated, obtains milky suspension, stands 12h, in removing
Layer clear liquid obtains white precipitate, and white precipitate is dried in vacuo into 8h at 60 DEG C, finally grinds to obtain by the product of drying pale brown
The powder of color is polyethers amine type benzoxazine prepolymer.
Polyetheramine molecular structural formula is used in the present embodiment：
Embodiment 5
The preparation of polyethers amine type benzoxazine prepolymer：
21.71g (0.023mol) polyetheramine, 2.78g (0.092mol) paraformaldehyde are added and stirred equipped with condenser pipe, magneton
Mix, in the three-necked flask of thermometer, add 51mL1,4- dioxane is solvent, and stirring adds 6.34g after 30 minutes
(0.028mol) bisphenol-A, wherein aldehyde radical, phenolic hydroxyl group and amidine functional group mol ratio are 2：1.2：1,90 DEG C of reaction 8h are heated to,
Reaction solution is poured into 100mL methanol solutions (concentration 90wt%) and precipitated by reaction after terminating, and is obtained milky suspension, is stood
12h, remove supernatant liquor and obtain white precipitate, white precipitate is dried in vacuo 8h at 60 DEG C, finally ground the product of drying
The powder that mill obtains brown color is polyethers amine type benzoxazine prepolymer.
Polyetheramine molecular structural formula is used in the present embodiment：
Embodiment 6
The preparation of polyethers amine type benzoxazine prepolymer：
34.55g (0.028mol) polyetheramine, 2.78g (0.092mol) paraformaldehyde are added and stirred equipped with condenser pipe, magneton
Mix, in the three-necked flask of thermometer, it is solvent to add 51mL dimethylbenzene, and stirring adds 5.28g (0.023mol) after 30 minutes
Bisphenol-A, wherein aldehyde radical, phenolic hydroxyl group and amidine functional group mol ratio are 2：1：1.2,80 DEG C of reaction 8h are heated to, after reaction terminates
Reaction solution is poured into 100mL methanol solutions (concentration 50wt%) and precipitated, obtains milky suspension, stands 12h, removes upper strata
Clear liquid obtains white precipitate, and white precipitate is dried in vacuo into 8h at 60 DEG C, finally grinds to obtain brown color by the product of drying
Powder be polyethers amine type benzoxazine prepolymer.
Polyetheramine molecular structural formula is used in the present embodiment：
Embodiment 7
It is used for after polyethers amine type benzoxazine prepolymer prepared by embodiment 1 is dissolved in into butanone solvent in copper-clad plate, puts
Polyethers amine type main chain benzoxazine colophony is obtained in solidifying 24h at 100 DEG C in vacuum drying chamber, its glass transition temperature is
285 DEG C, 800 DEG C of carbon yields are up to 33%, and dielectric constant is 2.8 under tensile strength 105MPa, 110MHz.
Embodiment 8
It is used for after polyethers amine type benzoxazine prepolymer prepared by embodiment 2 is dissolved in into butanone solvent in laminate, puts
Polyethers amine type main chain benzoxazine colophony is obtained in solidifying 8h in vacuum drying chamber at 180 DEG C, its glass transition temperature is 296
DEG C, 800 DEG C of carbon yields are up to 31%, and dielectric constant is 2.5 under tensile strength 112MPa, 110MHz.
Embodiment 9
It is used for printed circuit board (PCB) after polyethers amine type benzoxazine prepolymer prepared by embodiment 6 is dissolved in into butanone solvent
Matrix resin, it is placed in vacuum drying chamber and obtains polyethers amine type main chain benzoxazine colophony in 220 DEG C of solidification 4h, its vitrifying turns
Temperature is 300 DEG C, and 800 DEG C of carbon yields are up to 34%, and dielectric constant is 3.0 under tensile strength 125MPa, 110MHz.
Claims (6)
1. a kind of polyethers amine type benzoxazine prepolymer, it is characterised in that there is below formula：
Wherein n=2.5~20；
Its preparation methods steps are as follows：
Aldehyde compound, bisphenol-A and polyether amine compound are added into reaction vessel, wherein in aldehyde compound aldehyde radical with it is double
The amido mol ratio in phenolic hydroxyl group, polyether amine compound in phenol A is 2~2.4：1~1.2：1~1.2, add organic solvent
Dissolving, 6~10h is reacted in 80~110 DEG C, and reaction solution is poured into methanol solution and precipitated, obtained milky and hang by reaction after terminating
Turbid, supernatant liquor is removed after standing and obtains white precipitate, after white precipitate is dried grinding obtain polyethers amine type benzoxazine
Performed polymer；Or
Aldehyde compound and polyether amine compound are added into reaction vessel, adds organic solvent, is added after being sufficiently stirred double
Phenolic hydroxyl group in phenol A, wherein aldehyde compound in aldehyde radical and bisphenol-A, the amido mol ratio in polyether amine compound for 2~
2.4：1~1.2：1~1.2,6~10h is reacted in 80~110 DEG C, reaction solution is poured into methanol solution and precipitated by reaction after terminating,
Milky suspension is obtained, removing supernatant liquor after standing obtains white precipitate, is ground after white precipitate is dried and obtains polyethers
Amine type benzoxazine prepolymer.
2. the preparation method of the polyethers amine type benzoxazine prepolymer described in a kind of claim 1, it is characterised in that step is as follows：
Aldehyde compound, bisphenol-A and polyether amine compound, aldehyde radical and bisphenol-A wherein in aldehyde compound are added into reaction vessel
In phenolic hydroxyl group, amido mol ratio in polyether amine compound be 2~2.4：1~1.2：1~1.2, it is molten to add organic solvent
Solution, 6~10h is reacted in 80~110 DEG C, reaction solution is poured into methanol solution and precipitated by reaction after terminating, and it is suspended to obtain milky
Liquid, supernatant liquor is removed after standing and obtains white precipitate, after white precipitate is dried grinding it is pre- to obtain polyethers amine type benzoxazine
Aggressiveness；Or
Aldehyde compound and polyether amine compound are added into reaction vessel, adds organic solvent, is added after being sufficiently stirred double
Phenolic hydroxyl group in phenol A, wherein aldehyde compound in aldehyde radical and bisphenol-A, the amido mol ratio in polyether amine compound for 2~
2.4：1~1.2：1~1.2,6~10h is reacted in 80~110 DEG C, reaction solution is poured into methanol solution and precipitated by reaction after terminating,
Milky suspension is obtained, removing supernatant liquor after standing obtains white precipitate, is ground after white precipitate is dried and obtains polyethers
Amine type benzoxazine prepolymer.
3. the preparation method of polyethers amine type benzoxazine prepolymer according to claim 2, it is characterised in that the aldehydes
Compound is formaldehyde or paraformaldehyde.
4. the preparation method of polyethers amine type benzoxazine prepolymer according to claim 2, it is characterised in that the polyethers
Aminated compounds is PPOX binary amine compound, and molecular structural formula is as follows：
Wherein n=2.5~20.
5. the preparation method of polyethers amine type benzoxazine prepolymer according to claim 2, it is characterised in that described organic
Solvent is any one or more in toluene, dimethylbenzene, ethanol, chloroform, dimethylformamide, Isosorbide-5-Nitrae-dioxane.
6. the application of polyethers amine type benzoxazine prepolymer according to claim 1, it is characterised in that：By the polyetheramine
Type benzoxazine prepolymer is used for copper-clad plate, binding agent, laminate, printed circuit board (PCB), semiconductor package after being dissolved with butanone solvent
In package material or composite, Polybenzoxazine resin is obtained in 100~220 DEG C of 4~24h of curing reaction.
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| CN105968350B (en) * | 2016-05-24 | 2018-07-31 | 合肥工业大学 | A kind of high tenacity polyethers urea type benzoxazine colophony and preparation method thereof |
| CN109456674B (en) * | 2018-10-23 | 2021-01-26 | 湖北大学 | Water-based epoxy resin coating and application thereof in automobile corrosion prevention |
| TWI694988B (en) * | 2019-04-08 | 2020-06-01 | 國家中山科學研究院 | Preparation of five-carbon epoxy nitrogen benzocyclohexane polyurethane damping material |
| CN111423580B (en) * | 2020-05-23 | 2021-06-18 | 苏州大学 | Shape memory resin based on biomass benzoxazine and preparation method and application thereof |
| CN117304450B (en) * | 2023-11-24 | 2024-02-13 | 西南石油大学 | Blending type light response benzoxazine material and preparation method thereof |
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| CN102093556B (en) * | 2011-01-19 | 2014-09-24 | 华东理工大学 | Preparation method of low viscosity benzoxazine |
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