CN107629082A - A kind of novel siliceous benzoxazine and preparation method thereof - Google Patents
A kind of novel siliceous benzoxazine and preparation method thereof Download PDFInfo
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- CN107629082A CN107629082A CN201710906729.9A CN201710906729A CN107629082A CN 107629082 A CN107629082 A CN 107629082A CN 201710906729 A CN201710906729 A CN 201710906729A CN 107629082 A CN107629082 A CN 107629082A
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Abstract
The invention discloses a kind of novel siliceous benzoxazine monomer and preparation method thereof, benzoxazine monomer containing silicon is reacted under the conditions of solvent refluxing and synthesized by the siliceous biphenol of raw material, aminated compounds and paraformaldehyde；Siliceous biphenol is reacted by phenol halides and chlorosilane to be made；The preparation method of benzoxazine monomer containing silicon：Siliceous biphenol, aminated compounds, paraformaldehyde are added in the round-bottomed flask for filling benzene, toluene or chloroform, are heated to reflux, after reaction completely, separating treatment, obtain benzoxazine monomer containing silicon.Silicon benzoxazine monomer will be contained to be put into circular aluminum mold, be placed in Constant Temp. Oven that cured in stages obtains the Polybenzoxazine of ring-opening polymerisation at different temperatures.The benzoxazine containing silicon of the present invention has high heat endurance, high carbon yield, excellent anti-flammability, dielectric type and antiseptic property, can be used for the fields such as ablation resistant material, fire proofing, anti-corrosion material, Electronic Packaging.
Description
Technical field
The present invention relates to a kind of Xin types benzoxazine monomer and its polymer, and in particular to a kind of list of benzoxazine containing silicon
Body, Polybenzoxazine and corresponding preparation method.
Background technology
Benzoxazine is the new type resin developed on the basis of traditional phenolic resin.It is by phenols, formaldehyde or
The 6-membered heterocyclic compound that paraformaldehyde, primary amine are obtained by Mannich condensation reactions.Benzoxazine is through high temperature ring-opening polymerisation institute
The benzoxazine colophony of generation and other thermosetting resin (such as epoxy resin, phenolic resin, bimaleimide resin) phases
Than benzoxazine colophony not only has high temperature resistant, fire-retardant, the good dielectric properties and mechanical property of traditional phenolic resin, also
Catalyst is not needed with carbon yield height, glass transition temperature height, good stability of the dimension, solidification process, is released without small molecule,
The advantages that low water absorbable and very strong MOLECULE DESIGN, it is more suitable as resin base material and prepares various composite material parts.Cause
This, benzoxazine colophony has broader practice prospect.But the heat resistance of existing Bing oxazines resin, dielectric properties, glass
Glass conversion temperature etc. has much room for improvement, and then improves the property of high performance structures material, ablation resistant material, fire proofing and dielectric material
Energy.
It is well known that silicon-containing compound has high specific surface energy, excellent fire resistance, dielectric properties and ablation resistance
Energy.So silicon-containing compound is widely used in dielectric material, fire proofing, anti-corrosion material etc..It is single that element silicon is incorporated into
Report in benzoxazine is also seldom.Most commonly benzoxazine and silicon-containing compound are blended at present.Such as benzoxazine
It is blended with nano silicon, benzoxazine and siloxane polymer blending etc..Although blending can improve fire-retardant, the dielectric of material
And surface property, but inevitably reduce the mechanical property of material.Therefore, related researcher directly uses anilino- POSS
To synthesize benzoxazine, but anilino- POSS costs are very expensive, are unfavorable for mass producing.Now, people turn to sight
Amine propyl-siloxane and its oligomer, for example synthesized with diamine propyl-siloxane oligomer, amine propyl trimethoxy silicon etc.
Benzoxazine.Resulting benzoxazine has excellent interface performance, but due to the introducing of alkyl chain, reduces system
Heat endurance and mechanical property.Also have using the diphenol of poly(silicon aether) type to synthesize the report of benzoxazine, but this method synthesis step
It is rapid excessively cumbersome, it is unfavorable for actual large-scale application.
The content of the invention
It is an object of the invention to solve at least the above and/or defect, and provide at least will be described later it is excellent
Point.
A further object of the invention is that solve poor mechanical property, heat endurance existing for existing benzoxazine containing silicon
Difference, fire resistance and not good etc. enough technical problem of dielectric properties, there is provided a kind of heat endurance is good, the Ben containing silicon of high fixing carbon Bing Evil
Piperazine.
It is a still further object of the present invention to provide the preparation method of a kind of benzoxazine monomer containing silicon and its polymer, work
Skill step is simple, and yield is high, reproducible.
A further object of the invention is, fire resistance not good enough for benzoxazine colophony heat endurance in the prior art
Not good enough, dielectric properties are not good enough, and glass transition temperature is not high enough, it is impossible to meet ablation resistant material, fire proofing, electronics device
Part is to tolerance high-temperature, fire resistance, the technical requirements present situation of dielectric properties, there is provided a kind of heat resistance, anti-flammability, dielectricity
It is good, the high benzoxazine colophony of glass transition temperature.
In order to realize these purposes and further advantage of the invention, the invention provides a kind of novel siliceous benzoxazine list
Body, it is reacted under the conditions of solvent refluxing and synthesized by the siliceous biphenol of raw material, aminated compounds and paraformaldehyde.
Preferably, for the siliceous biphenol using phenol halides as raw material, tetrahydrofuran is solvent, is deposited in n-BuLi
It is made under conditions with chlorosilane reaction, the general structure of siliceous biphenol is as follows：
In formula, R1And R2One kind respectively in methyl, phenyl, ethyl, vinyl.
Preferably, the aminated compounds is monoamine compound, siliceous biphenol, monoamine compound, poly first
The mol ratio of aldehyde is 1:2:4.1~4.4, the general structure of the benzoxazine monomer containing silicon of synthesis is as follows：
In formula, R3For methyl, ethyl, the tert-butyl group, pi-allyl, 2- hydroxyethyls, cyclohexyl, pyridine radicals, furfuryl, benzyl
Base, phenyl, o-methyl-phenyl, an aminomethyl phenyl, p-methylphenyl, 3,5- 3,5-dimethylphenyls, to ethynyl phenyl, to propargyl
Phenyl, p-fluorophenyl, o-fluorophenyl, 2,6- difluorophenyls, 2- methyl -6- fluorophenyls, p-nitrophenyl, m-nitro base, neighbour
Nitrobenzophenone, 3,5- dinitrophenyls, to cyano-phenyl, fluoro- 4 cyano-phenyls of 3-, 4- nitro -2- cyano-phenyls, 4- nitro -2,
3- dicyanos phenyl, to carboxyl phenyl, to carboxyl sodium phenyl, adjacent carboxyl phenyl, to formic acid ester group phenyl, p-sulfonic acid sodium phenyl,
P-sulfonic acid phenyl, 2,4- disulfonic acid base phenyl one kind therein.
It may further be preferable that the monoamine compound is aniline, siliceous biphenol is double (p-hydroxybenzene) diformazans
Base silicon, the structural formula of benzoxazine monomer containing silicon of synthesis are as follows：
Preferably, the aminated compounds is double aminated compounds, siliceous biphenol, double aminated compounds, poly first
The mol ratio of aldehyde is 1:1:4.1~4.4, the general structure of the benzoxazine monomer containing silicon of synthesis is as follows：
In formula, R4For phenyl, polyether-based, propyl group polysiloxanes, polyethyleneimine amido, 4,4 '-diphenyl-methane, 4,4 '-two
One kind of phenyl ether.
It may further be preferable that double aminated compounds are 4,4 '-MDA, siliceous biphenol is double
(p-hydroxybenzene) dimethyl-silicon, the structural formula of benzoxazine monomer containing silicon of synthesis are as follows：
A kind of preparation method of novel siliceous benzoxazine monomer, step are：By siliceous biphenol, aminated compounds, more
Polyformaldehyde is added in the round-bottomed flask for filling benzene, toluene or chloroform, is heated to reflux, and after reaction completely, separating treatment, is obtained
Benzoxazine monomer containing silicon.
Preferably, the preparation method of novel siliceous benzoxazine monomer, step are：At ambient temperature, will be double (to hydroxyl
Base phenyl) dimethyl-silicon or double (hydroxy phenyl) diphenyl silicon, aniline, paraformaldehyde be added to the round-bottomed flask for filling chloroform
In, heating reflux reaction 1 day, after reaction completely, after Rotary Evaporators solvent evaporated, column chromatography obtains the list of benzoxazine containing silicon
Body.
Preferably, the preparation method of novel siliceous benzoxazine monomer, step are：At ambient temperature, will be double (to hydroxyl
Base phenyl) dimethyl-silicon or double (hydroxy phenyl) diphenyl silicon, 4,4 '-MDA, paraformaldehyde, which are added to, to be filled
In the round-bottomed flask of chloroform, heating reflux reaction 6h, filtering, benzoxazine monomer containing silicon is obtained.
A kind of method that ring-opening polymerisation of benzoxazine monomer containing silicon prepares Polybenzoxazine, step are as follows：By siliceous benzo
Oxazine monomer is put into circular aluminum mold, is placed in Constant Temp. Oven that cured in stages obtains open loop at different temperatures
The Polybenzoxazine of polymerization, elevated cure process are：200 DEG C of 2~3h of heat cure are warming up to first, then heat to 220 DEG C of heat
Solidify 2~3h, be finally warming up to 240 DEG C of 2~3h of heat cure.
Compared with prior art, the present invention is advantageous in that：
One, using siliceous biphenol as raw material prepare benzoxazine containing silicon, due in the molecular structure of benzoxazine containing silicon not
Alkyl chain be present, there is excellent heat endurance and mechanical property, while make it that benzoxazine has excellent for the introducing of silicon atom
Dielectric properties, fire resistance and antiseptic property.
Secondly, benzoxazine containing silicon be heated to reflux preparing by siliceous biphenol and aminated compounds, paraformaldehyde, technique
Simply, yield is high, reproducible.
Thirdly, siliceous biphenol can be reacted and be made by phenol halides and chlorosilane, raw material is cheap and easy to get, effectively reduces
Financial cost.
Four, the chemical stability of the obtained benzoxazine containing silicon, heat endurance is good, carbon yield is high, monomer can be used as
It is used alone or is used in mixed way with other benzoxazine monomers or phenolic resin or epoxy resin, while the silicon in benzoxazine has
Beneficial to improve carbon yield, dielectric properties, fire resistance, interface performance, can be applied to high performance structures material, ablation resistant material,
The fields such as fire proofing, electronic package material.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
Research and the time of invention and be understood by the person skilled in the art.
Brief description of the drawings
Fig. 1 double (hydroxy phenyl) dimethyl-silicon, the infrared spectrums of aniline type benzoxazine.
Fig. 2 double (hydroxy phenyl) dimethyl-silicon, the nucleus magnetic hydrogen spectrums of aniline type benzoxazine.
Fig. 3 double (hydroxy phenyl) dimethyl-silicon, the DSC spectrograms of aniline type benzoxazine.
Double (hydroxy phenyl) the diphenyl silicon of Fig. 4, the nucleus magnetic hydrogen spectrum of aniline type benzoxazine.
Double (hydroxy phenyl) the diphenyl silicon of Fig. 5, the DSC spectrograms of aniline type benzoxazine.
Embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that described herein preferred real
Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment 1
Under room temperature condition, 2.44g double (hydroxy phenyl) dimethyl-silicon, 1.86ml aniline and 1.23g paraformaldehydes are added
Into the round-bottomed flask for filling 30ml chloroforms, the mol ratio of double (hydroxy phenyl) dimethyl-silicons, aniline and paraformaldehyde is 1：2：
4.1, heating reflux reaction 1 day, after reaction completely, chloroform is evaporated with Rotary Evaporators, column chromatography for separation obtains the Bing of Ben containing silicon Evil
Piperazine monomer.Reaction principle is：
The benzoxazine monomer containing silicon of the above-mentioned preparations of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the Polybenzoxazine of ring-opening polymerisation at different temperatures, and elevated cure process is：200 DEG C are warming up to first
Heat cure 3h, then heat to 220 DEG C of heat cures 3h, finally heated to 240 DEG C heat cure 3h.
Embodiment 2
Under room temperature condition, 2.44g double (hydroxy phenyl) dimethyl-silicon, 1.86ml aniline and 1.26g paraformaldehydes are added
Into the round-bottomed flask for filling 30ml toluene, the mol ratio of double (hydroxy phenyl) dimethyl-silicons, aniline and paraformaldehyde is 1：2：
4.2, heating reflux reaction 1 day, after reaction completely, toluene is evaporated with Rotary Evaporators, column chromatography for separation obtains the Bing of Ben containing silicon Evil
Piperazine monomer.Reaction principle is：
The benzoxazine monomer containing silicon of the above-mentioned preparations of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the Polybenzoxazine of ring-opening polymerisation at different temperatures, and elevated cure process is：200 DEG C are warming up to first
Heat cure 3h, then heat to 220 DEG C of heat cures 3h, finally heated to 240 DEG C heat cure 3h.
Embodiment 3
Under room temperature condition, 2.44g double (hydroxy phenyl) dimethyl-silicon, 1.86ml aniline and 1.29g paraformaldehydes are added
Into the round-bottomed flask for filling 30ml benzene, the mol ratio of double (hydroxy phenyl) dimethyl-silicons, aniline and paraformaldehyde is 1：2：
4.3, heating reflux reaction 1 day, after reaction completely, benzene is evaporated with Rotary Evaporators, column chromatography for separation obtains benzoxazine containing silicon
Monomer.Reaction principle is：
The benzoxazine monomer containing silicon of the above-mentioned preparations of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the Polybenzoxazine of ring-opening polymerisation at different temperatures, and elevated cure process is：200 DEG C are warming up to first
Heat cure 3h, then heat to 220 DEG C of heat cures 3h, finally heated to 240 DEG C heat cure 3h.
Benzoxazine monomer containing silicon prepared by embodiment 1,2,3 carries out proton nmr spectra, infrared spectrum, DSC spectrograms
Etc. a series of analyses, the same performance sign collection of illustrative plates of 3 obtained embodiments is identical, and specific test result is identical, illustrates 3 realities
Apply that example is prepared for same silicon benzoxazine monomer.Concrete outcome is shown in Fig. 1~3.
Fig. 1 is examination of infrared spectrum result (KBr, cm-1)：940cm-1The phenyl ring characteristic peak that Wei is connected Yu oxazine ring,
1094cm-1For C-Si characteristic absorption peaks, 1495cm-1And 1598cm-1For C=C characteristic peaks, 2954cm on phenyl ring-1For CH3、CH2
Characteristic peak.
Fig. 2 is proton nmr spectra test result1H NMR (600MHz, CDCl3, ppm)：7.27-7.18(m,6H,Ar-
H),7.11-7.08(m,6H,Ar-H),6.93-6.83(m,4H,Ar-H),6.80-6.78(m,2H,Ar-H),5.31(s,4H,
O-CH2-N),4.60(s,4H,Ar-CH2- N), 0.45 (s, 6H ,-CH3)。
Fig. 3 is DSC spectrograms (10 DEG C/min of heating rate)：Initial cure temperature：215℃；Peak Curing Temp：251℃.
Confirm that products therefrom is object benzoxazine monomer containing silicon with reference to proton nmr spectra and infrared spectrum.
Embodiment 4
Under room temperature condition, 3.68g double (hydroxy phenyl) diphenyl silicon, 1.86ml aniline and 1.23g paraformaldehydes are added
Into the round-bottomed flask for filling 30ml toluene, the mol ratio of double (hydroxy phenyl) diphenyl silicon, aniline and paraformaldehyde is 1：2：
4.1, it is heated to reflux point water and reacts 2 days, after reaction completely, is evaporated toluene with Rotary Evaporators, column chromatography for separation obtains siliceous benzene
Bing oxazine monomers.Reaction principle is：
The benzoxazine monomer containing silicon of the above-mentioned preparations of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the Polybenzoxazine of ring-opening polymerisation at different temperatures, and elevated cure process is：200 DEG C are warming up to first
Heat cure 2h, then heat to 220 DEG C of heat cure 2h.
Embodiment 5
Under room temperature condition, 3.68g double (hydroxy phenyl) diphenyl silicon, 1.86ml aniline and 1.26g paraformaldehydes are added
Into the round-bottomed flask for filling 30ml benzene, the mol ratio of double (amido phenoxy group) diphenyl silicon, aniline and paraformaldehyde is 1：2：
4.2, it is heated to reflux point water and reacts 1 day, after reaction completely, is evaporated benzene with Rotary Evaporators, column chromatography for separation obtains siliceous benzo
Oxazine monomer.Reaction principle is：
The benzoxazine monomer containing silicon of the above-mentioned preparations of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the Polybenzoxazine of ring-opening polymerisation at different temperatures, and elevated cure process is：200 DEG C are warming up to first
Heat cure 2.5h, then heat to 220 DEG C of heat cure 2.5h.
Embodiment 6
Under room temperature condition, 3.68g double (hydroxy phenyl) diphenyl silicon, 1.86ml aniline and 1.29g paraformaldehydes are added
Into the round-bottomed flask for filling 30ml chloroforms, the mol ratio of double (amido phenoxy group) diphenyl silicon, aniline and paraformaldehyde is 1：
2：4.3, it is heated to reflux point water and reacts 1 day, after reaction completely, is evaporated chloroform with Rotary Evaporators, column chromatography for separation obtains siliceous
Benzoxazine monomer.Reaction principle is：
The benzoxazine monomer containing silicon of the above-mentioned preparations of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the Polybenzoxazine of ring-opening polymerisation at different temperatures, and elevated cure process is：200 DEG C are warming up to first
Heat cure 2.5h, then heat to 220 DEG C of heat cure 2.5h.
Benzoxazine monomer prepared by embodiment 4,5,6 carries out proton nmr spectra and DSC spectrum analysis, 3 obtained
The same performance of individual embodiment characterizes that collection of illustrative plates is identical, and specific test result is identical, illustrate that 3 embodiments are prepared to be same
Kind material.Concrete outcome is shown in Fig. 4,5.
Fig. 4, proton nmr spectra test result1H NMR (600MHz, CDCl3, ppm)：7.62-7.60 (m, 8H, Ar-H),
7.44-7.33(m,10H,Ar-H),7.28-7.24(m,8H,Ar-H),7.10-7.08(m,4H,Ar-H),5.31(s,4H,O-
CH2-N),4.60(s,4H,Ar-CH2-N)。
Fig. 5, DSC spectrogram (10 DEG C/min of heating rate)：Initial cure temperature：195℃；Peak Curing Temp：230℃.
Embodiment 7
Under room temperature condition, by double (hydroxy phenyl) the diphenyl silicon of 3.68g, 1.98g 4,4'- MDAs and
1.26g paraformaldehydes are added in the round-bottomed flask for filling 30ml chloroforms, double (amido phenoxy group) diphenyl silicon, 4,4'- diaminos
The mol ratio of base diphenyl-methane and paraformaldehyde is 1：1：4.2, a point water reaction 0.6h is heated to reflux, after reaction completely, is filtered
To benzoxazine monomer containing silicon.Reaction principle is：
The benzoxazine monomer containing silicon of the above-mentioned preparations of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the Polybenzoxazine of ring-opening polymerisation at different temperatures, and elevated cure process is：200 DEG C are warming up to first
Heat cure 2.5h, then heat to 220 DEG C of heat cure 2.5h.
Research test result shows：Benzoxazine containing silicon prepared by the present invention, alkyl chain is not present in molecular structure, has
Excellent heat endurance and mechanical property, while the introducing of silicon atom causes benzoxazine to have excellent dielectric properties, fire-retardant
Performance and antiseptic property.After our benzoxazines containing silicon to synthesis carry out curing process, TGA and glass transition temperature have been carried out
Degree test, the results showed that the initial decomposition temperature of polymer is more than 400 DEG C, and 800 DEG C of carbon yield is more than 75%.Glass is bad to be changed
Temperature is more than 300 DEG C.And benzoxazine polymer has very high ph stability.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit according to the present invention
Any simple modification, equivalent change and modification made to above example, in the range of still falling within technical solution of the present invention.
Claims (10)
1. a kind of novel siliceous benzoxazine monomer, it is characterised in that by the siliceous biphenol of raw material, aminated compounds and poly first
Aldehyde reacts synthesis under the conditions of solvent refluxing.
2. novel siliceous benzoxazine monomer as claimed in claim 1, it is characterised in that the siliceous biphenol is with phenol halogen
It is raw material for thing, tetrahydrofuran is solvent, is made under n-BuLi existence condition with chlorosilane reaction, the knot of siliceous biphenol
Structure formula is as follows：
In formula, R1And R2One kind respectively in methyl, phenyl, ethyl, vinyl.
3. novel siliceous benzoxazine monomer as claimed in claim 2, it is characterised in that the aminated compounds is monoamine
Compound, siliceous biphenol, monoamine compound, the mol ratio of paraformaldehyde are 1:2:4.1~4.4, the siliceous benzo of synthesis
The general structure of oxazine monomer is as follows：
In formula, R3For methyl, ethyl, the tert-butyl group, pi-allyl, 2- hydroxyethyls, cyclohexyl, pyridine radicals, furfuryl, benzyl, benzene
Base, o-methyl-phenyl, an aminomethyl phenyl, p-methylphenyl, 3,5- 3,5-dimethylphenyls, to ethynyl phenyl, to propargyl phenyl,
P-fluorophenyl, o-fluorophenyl, 2,6- difluorophenyls, 2- methyl -6- fluorophenyls, p-nitrophenyl, m-nitro base, ortho-nitrophenyl
Base, 3,5- dinitrophenyls, to cyano-phenyl, fluoro- 4 cyano-phenyls of 3-, 4- nitro -2- cyano-phenyls, 4- nitro -2,3- dicyan
Base phenyl, to carboxyl phenyl, to carboxyl sodium phenyl, adjacent carboxyl phenyl, to formic acid ester group phenyl, p-sulfonic acid sodium phenyl, p-sulfonic acid
Phenyl, 2,4- disulfonic acid base phenyl one kind therein.
4. novel siliceous benzoxazine monomer as claimed in claim 3, it is characterised in that the monoamine compound is benzene
Amine, siliceous biphenol are double (p-hydroxybenzene) dimethyl-silicons, and the structural formula of benzoxazine monomer containing silicon of synthesis is as follows：
5. novel siliceous benzoxazine monomer as claimed in claim 2, it is characterised in that the aminated compounds is diamine class
Compound, siliceous biphenol, double aminated compounds, the mol ratio of paraformaldehyde are 1:1:4.1~4.4, the siliceous benzo of synthesis
The general structure of oxazine monomer is as follows：
In formula, R4For phenyl, polyether-based, propyl group polysiloxanes, polyethyleneimine amido, 4,4 '-diphenyl-methane, 4,4 '-diphenyl ether
One kind.
6. novel siliceous benzoxazine monomer as claimed in claim 5, it is characterised in that double aminated compounds are 4,
4 '-MDA, siliceous biphenol are double (p-hydroxybenzene) dimethyl-silicons, the knot of benzoxazine monomer containing silicon of synthesis
Structure formula is as follows：
7. a kind of preparation method of novel siliceous benzoxazine monomer, it is characterised in that preparation process is：By siliceous biphenol,
Aminated compounds, paraformaldehyde are added in the round-bottomed flask for filling benzene, toluene or chloroform, are heated to reflux, after reaction completely,
Separating treatment, obtain benzoxazine monomer containing silicon.
8. the preparation method of novel siliceous benzoxazine monomer as claimed in claim 7, it is characterised in that preparation process is：
At ambient temperature, will double (p-hydroxybenzene) dimethyl-silicons or double (hydroxy phenyl) diphenyl silicon, aniline, paraformaldehyde addition
Into the round-bottomed flask for filling chloroform, heating reflux reaction 1 day, after reaction completely, after Rotary Evaporators solvent evaporated, post layer
Analysis obtains benzoxazine monomer containing silicon.
9. the preparation method of novel siliceous benzoxazine monomer as claimed in claim 7, it is characterised in that preparation process is：
At ambient temperature, will double (p-hydroxybenzene) dimethyl-silicons or double (hydroxy phenyl) diphenyl silicon, 4,4 '-diaminourea hexichol first
Alkane, paraformaldehyde are added in the round-bottomed flask for filling chloroform, heating reflux reaction 6h, filtering, obtain the list of benzoxazine containing silicon
Body.
10. a kind of method that ring-opening polymerisation of benzoxazine monomer containing silicon prepares Polybenzoxazine, it is characterised in that step is as follows：
Silicon benzoxazine monomer will be contained to be put into circular aluminum mold, be placed in Constant Temp. Oven solid stage by stage at different temperatures
Change obtains the Polybenzoxazine of ring-opening polymerisation, and elevated cure process is：200 DEG C of 2~3h of heat cure are warming up to first, are then heated up
To 220 DEG C of 2~3h of heat cure, 240 DEG C of 2~3h of heat cure are finally warming up to.
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| CN109942894A (en) * | 2019-02-23 | 2019-06-28 | 河南大学 | A kind of the halogen-free expanded flame-retardant system and its fire-retardant thermoplastic resin of the carbon forming agent containing benzoxazine |
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| CN108997548A (en) * | 2018-09-06 | 2018-12-14 | 西南石油大学 | A kind of photolytic activity benzoxazine resin and preparation method thereof |
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