CN107629082B - 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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Abstract
The invention discloses a kind of novel siliceous benzoxazine monomer and preparation method thereof, siliceous benzoxazine monomer is reacted under the conditions of solvent refluxing by the siliceous biphenol of raw material, aminated compounds and paraformaldehyde and is synthesized；Siliceous biphenol, which is reacted by phenol halides with chlorosilane, to be made；Siliceous benzoxazine method for preparing monomer: siliceous biphenol, aminated compounds, paraformaldehyde being added in the round-bottomed flask for filling benzene, toluene or chloroform, are heated to reflux, and after fully reacting, separating treatment obtains siliceous benzoxazine monomer.Siliceous benzoxazine monomer is put into circular aluminum mold, is placed in Constant Temp. Oven that cured in stages obtains the polybenzoxazine of ring-opening polymerisation at different temperatures.Siliceous benzoxazine of the invention has high thermal stability, 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 novel benzoxazine monomer and its polymer, and in particular to a kind of siliceous benzoxazine list
Body, polybenzoxazine and corresponding preparation method.
Background technique
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 reaction.Benzoxazine is through high temperature ring-opening polymerisation institute
The benzoxazine resin of generation and other thermosetting resin (such as epoxy resin, phenolic resin, bimaleimide resin) phases
Than the high temperature resistant, fire-retardant, good dielectric properties and mechanical property that, benzoxazine resin not only has 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, is more suitable as resin base material and prepares various composite material parts.Cause
This, benzoxazine resin has broader practice prospect.But existing and oxazines resin heat resistance, dielectric properties, glass
Glass conversion temperature etc. is to be improved, 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 flame retardant property, dielectric properties and ablation resistance
Energy.So silicon-containing compound dielectric material, fire proofing, in terms of be widely used.It is single that element silicon is introduced into
Report in benzoxazine is also seldom.Most commonly benzoxazine is blended with silicon-containing compound at present.For example, benzoxazine
It is blended with nano silica, benzoxazine is blended with siloxane polymer.Although fire-retardant, the dielectric that can improve material is blended
And surface property, but inevitably reduce the mechanical property of material.Therefore, related researcher directly uses anilino- POSS
Benzoxazine is synthesized, but anilino- POSS cost is very expensive, be unfavorable for being mass produced.Now, people turn to sight
Amine propyl-siloxane and its oligomer, such as with diamine propyl-siloxane oligomer, amine propyl trimethoxy silicon etc. synthesize
Benzoxazine.Obtained benzoxazine has excellent interface performance, but due to the introducing of alkyl chain, reduces system
Thermal stability and mechanical property.Also there are using the diphenol of poly(silicon aether) type the report for synthesizing benzoxazine, but this method synthesis step
It is rapid excessively cumbersome, it is unfavorable for practical large-scale application.
Summary of the invention
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later
Point.
A further object of the invention is to solve poor mechanical property, thermal stability existing for existing siliceous benzoxazine
Difference, flame retardant property and not good etc. enough technical problems of dielectric properties, provide that a kind of thermal stability is good, siliceous benzo of high fixing carbon is disliked
Piperazine.
It is a still further object of the present invention to provide the preparation method of a kind of siliceous benzoxazine monomer and its polymer, works
Skill step is simple, and yield is high, reproducible.
A further object of the invention is, flame retardant property not good enough for benzoxazine resin thermal stability in the prior art
Not good enough, dielectric properties are not good enough, and glass transition temperature is not high enough, are not able to satisfy ablation resistant material, fire proofing, electronics device
Part provides a kind of heat resistance, anti-flammability, dielectricity to tolerance high-temperature, flame retardant property, the technical requirements status of dielectric properties
It is good, the high benzoxazine resin of glass transition temperature.
In order to realize these purposes and other advantages of the invention, the present invention provides a kind of novel siliceous benzoxazine lists
Body is reacted under the conditions of solvent refluxing by the siliceous biphenol of raw material, aminated compounds and paraformaldehyde and is synthesized.
Preferably, for the siliceous biphenol using phenol halides as raw material, tetrahydrofuran is solvent, is deposited in n-BuLi
It reacts and is made with chlorosilane under conditions, the general structure of siliceous biphenol is as follows:
In formula, R1And R2Respectively one of methyl, phenyl, ethyl, vinyl.
Preferably, the aminated compounds is monoamine compound, siliceous biphenol, monoamine compound, poly first
The molar ratio of aldehyde is 1:2:4.1~4.4, and the general structure of the siliceous benzoxazine monomer of synthesis is as follows:
In formula, R3For methyl, ethyl, tert-butyl, allyl, 2- hydroxyethyl, cyclohexyl, pyridyl group, furfuryl, benzyl
Base, phenyl, o-methyl-phenyl, aminomethyl phenyl, p-methylphenyl, 3,5- 3,5-dimethylphenyl, to ethynyl phenyl, to propargyl
Phenyl, p-fluorophenyl, o-fluorophenyl, 2,6- difluorophenyl, 2- methyl -6- fluorophenyl, p-nitrophenyl, m-nitro base, neighbour
Nitrobenzophenone, 3,5- dinitrophenyl, to cyano-phenyl, fluoro- 4 cyano-phenyl of 3-, 4- nitro -2- cyano-phenyl, nitro -2 4-,
3- dicyano 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 are one such.
It may further be preferable that the monoamine compound is aniline, siliceous biphenol is bis- (p-hydroxybenzene) diformazans
The siliceous benzoxazine monomer structure formula of base silicon, synthesis is as follows:
Preferably, the aminated compounds is double aminated compounds, siliceous biphenol, double aminated compounds, poly first
The molar ratio of aldehyde is 1:1:4.1~4.4, and the general structure of the siliceous benzoxazine monomer of synthesis is as follows:
In formula, R4For phenyl, polyether-based, propyl polysiloxanes, polyethyleneimine amido, 4,4 '-diphenyl-methanes, 4,4 '-two
One kind of phenyl ether.
It may further be preferable that double aminated compounds are 4,4 '-diaminodiphenylmethane, siliceous biphenol is double
The siliceous benzoxazine monomer structure formula of (p-hydroxybenzene) dimethyl-silicon, synthesis is as follows:
A kind of preparation method of novel siliceous benzoxazine monomer, step are as follows: 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 fully reacting, separating treatment is obtained
Siliceous benzoxazine monomer.
Preferably, the preparation method of novel siliceous benzoxazine monomer, step are as follows: will be bis- (to hydroxyl at room temperature
Base phenyl) dimethyl-silicon or bis- (hydroxy phenyl) diphenyl silicon, aniline, paraformaldehyde be added to the round-bottomed flask for filling chloroform
In, heating reflux reaction 1 day, after fully reacting, after Rotary Evaporators solvent evaporated, column chromatographed to obtain siliceous benzoxazine list
Body.
Preferably, the preparation method of novel siliceous benzoxazine monomer, step are as follows: will be bis- (to hydroxyl at room temperature
Base phenyl) dimethyl-silicon or bis- (hydroxy phenyl) diphenyl silicon, 4,4 '-diaminodiphenylmethane, paraformaldehyde be added to and fill
In the round-bottomed flask of chloroform, heating reflux reaction 6h, filtering obtains siliceous benzoxazine monomer.
A kind of method that siliceous benzoxazine monomer ring-opening polymerisation prepares polybenzoxazine, steps are as follows: by siliceous benzo
Oxazines 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 as follows: be warming up to 200 DEG C of 2~3h of heat cure first, then heat to 220 DEG C of heat
Solidify 2~3h, is finally warming up to 240 DEG C of 2~3h of heat cure.
Compared with prior art, the invention has the beneficial effects that:
One prepares siliceous benzoxazine by raw material of siliceous biphenol, due in siliceous benzoxazine molecular structure not
There are alkyl chain, there is excellent thermal stability and mechanical property, at the same silicon atom introducing so that benzoxazine have it is excellent
Dielectric properties, flame retardant property and antiseptic property.
Secondly, siliceous benzoxazine preparation, technique is heated to reflux by siliceous biphenol and aminated compounds, paraformaldehyde
Simply, yield is high, reproducible.
Thirdly, siliceous biphenol can be reacted by phenol halides with chlorosilane be made, raw material is cheap and easy to get, effectively reduces
Economic cost.
Four, the chemical stability of siliceous benzoxazine obtained, thermal stability is good, carbon yield is high, can be used as monomer
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
Conducive to improve carbon yield, dielectric properties, flame retardant property, 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 feature of the invention will be partially reflected by the following instructions, and part will also be by this
Research and the time of invention and be understood by the person skilled in the art.
Detailed description of the invention
The infrared spectroscopy of bis- (hydroxy phenyl) dimethyl-silicons of Fig. 1, aniline type benzoxazine.
The nucleus magnetic hydrogen spectrum of bis- (hydroxy phenyl) dimethyl-silicons of Fig. 2, aniline type benzoxazine.
The DSC spectrogram of bis- (hydroxy phenyl) dimethyl-silicons of Fig. 3, aniline type benzoxazine.
The nucleus magnetic hydrogen spectrum of bis- (hydroxy phenyl) the diphenyl silicon of Fig. 4, aniline type benzoxazine.
The DSC spectrogram of bis- (hydroxy phenyl) the diphenyl silicon of Fig. 5, aniline type benzoxazine.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1
Under room temperature, bis- (hydroxy phenyl) dimethyl-silicons of 2.44g, 1.86ml aniline and 1.23g paraformaldehyde are added
Into the round-bottomed flask for filling 30ml chloroform, the molar ratio of bis- (hydroxy phenyl) dimethyl-silicons, aniline and paraformaldehyde is 1:2:
4.1, heating reflux reaction 1 day, after fully reacting, it is evaporated chloroform with Rotary Evaporators, column chromatography for separation obtains siliceous benzo and dislikes
Piperazine monomer.Reaction principle are as follows:
The siliceous benzoxazine monomer of the above-mentioned preparation of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the polybenzoxazine of ring-opening polymerisation, elevated cure process at different temperatures are as follows: is warming up to 200 DEG C first
Heat cure 3h then heats to 220 DEG C of heat cures 3h, finally heated to 240 DEG C heat cure 3h.
Embodiment 2
Under room temperature, bis- (hydroxy phenyl) dimethyl-silicons of 2.44g, 1.86ml aniline and 1.26g paraformaldehyde are added
Into the round-bottomed flask for filling 30ml toluene, the molar ratio of bis- (hydroxy phenyl) dimethyl-silicons, aniline and paraformaldehyde is 1:2:
4.2, heating reflux reaction 1 day, after fully reacting, it is evaporated toluene with Rotary Evaporators, column chromatography for separation obtains siliceous benzo and dislikes
Piperazine monomer.Reaction principle are as follows:
The siliceous benzoxazine monomer of the above-mentioned preparation of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the polybenzoxazine of ring-opening polymerisation, elevated cure process at different temperatures are as follows: is warming up to 200 DEG C first
Heat cure 3h then heats to 220 DEG C of heat cures 3h, finally heated to 240 DEG C heat cure 3h.
Embodiment 3
Under room temperature, bis- (hydroxy phenyl) dimethyl-silicons of 2.44g, 1.86ml aniline and 1.29g paraformaldehyde are added
Into the round-bottomed flask for filling 30ml benzene, the molar ratio of bis- (hydroxy phenyl) dimethyl-silicons, aniline and paraformaldehyde is 1:2:
4.3, heating reflux reaction 1 day, after fully reacting, it is evaporated benzene with Rotary Evaporators, column chromatography for separation obtains siliceous benzoxazine
Monomer.Reaction principle are as follows:
The siliceous benzoxazine monomer of the above-mentioned preparation of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the polybenzoxazine of ring-opening polymerisation, elevated cure process at different temperatures are as follows: is warming up to 200 DEG C first
Heat cure 3h then heats to 220 DEG C of heat cures 3h, finally heated to 240 DEG C heat cure 3h.
Siliceous benzoxazine monomer prepared by embodiment 1,2,3 carries out nuclear magnetic resonance spectroscopy, infrared spectroscopy, DSC spectrogram
Etc. a series of analyses, the same performance characterization map of 3 obtained embodiments is identical, and specific test result is identical, illustrates 3 realities
Applying example and being prepared is same silicon benzoxazine monomer.Concrete outcome is shown in Fig. 1~3.
Fig. 1 is examination of infrared spectrum result (KBr, cm-1): 940cm-1For the phenyl ring characteristic peak being connected with oxazines ring,
1094cm-1For C-Si characteristic absorption peak, 1495cm-1And 1598cm-1For C=C characteristic peak, 2954cm on phenyl ring-1For CH3、CH2
Characteristic peak.
Fig. 2 is nuclear magnetic resonance spectroscopy 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 spectrogram (10 DEG C/min of heating rate): initial cure temperature: 215 DEG C；Peak Curing Temp: 251 DEG C.
Confirm that products therefrom is the siliceous benzoxazine monomer of object in conjunction with nuclear magnetic resonance spectroscopy and infrared spectroscopy.
Embodiment 4
Under room temperature, bis- (hydroxy phenyl) the diphenyl silicon of 3.68g, 1.86ml aniline and 1.23g paraformaldehyde are added
Into the round-bottomed flask for filling 30ml toluene, the molar ratio of bis- (hydroxy phenyl) diphenyl silicon, aniline and paraformaldehyde is 1:2:
4.1, it is heated to reflux point water and reacts 2 days, after fully reacting, be evaporated toluene with Rotary Evaporators, column chromatography for separation obtains siliceous benzene
And oxazines monomer.Reaction principle are as follows:
The siliceous benzoxazine monomer of the above-mentioned preparation of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the polybenzoxazine of ring-opening polymerisation, elevated cure process at different temperatures are as follows: is warming up to 200 DEG C first
Heat cure 2h then heats to 220 DEG C of heat cure 2h.
Embodiment 5
Under room temperature, bis- (hydroxy phenyl) the diphenyl silicon of 3.68g, 1.86ml aniline and 1.26g paraformaldehyde are added
Into the round-bottomed flask for filling 30ml benzene, the molar ratio of bis- (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 fully reacting, be evaporated benzene with Rotary Evaporators, column chromatography for separation obtains siliceous benzo
Oxazines monomer.Reaction principle are as follows:
The siliceous benzoxazine monomer of the above-mentioned preparation of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the polybenzoxazine of ring-opening polymerisation, elevated cure process at different temperatures are as follows: is warming up to 200 DEG C first
Heat cure 2.5h then heats to 220 DEG C of heat cure 2.5h.
Embodiment 6
Under room temperature, bis- (hydroxy phenyl) the diphenyl silicon of 3.68g, 1.86ml aniline and 1.29g paraformaldehyde are added
Into the round-bottomed flask for filling 30ml chloroform, the molar ratio of bis- (amido phenoxy group) diphenyl silicon, aniline and paraformaldehyde is 1:
2:4.3 is heated to reflux point water and reacts 1 day, after fully reacting, is evaporated chloroform with Rotary Evaporators, column chromatography for separation obtains siliceous
Benzoxazine monomer.Reaction principle are as follows:
The siliceous benzoxazine monomer of the above-mentioned preparation of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the polybenzoxazine of ring-opening polymerisation, elevated cure process at different temperatures are as follows: is warming up to 200 DEG C first
Heat cure 2.5h then heats to 220 DEG C of heat cure 2.5h.
Benzoxazine monomer prepared by embodiment 4,5,6 carries out nuclear magnetic resonance spectroscopy and DSC spectrum analysis, 3 obtained
The same performance characterization map of a embodiment is identical, and specific test result is identical, and it is same for illustrating that 3 embodiments are prepared
Kind substance.Concrete outcome is shown in Fig. 4,5.
Fig. 4, nuclear magnetic resonance spectroscopy 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 DEG C；Peak Curing Temp: 230 DEG C.
Embodiment 7
Under room temperature, by bis- (hydroxy phenyl) the diphenyl silicon of 3.68g, 1.98g 4,4'- diaminodiphenylmethane and
1.26g paraformaldehyde is added in the round-bottomed flask for filling 30ml chloroform, bis- (amido phenoxy group) diphenyl silicon, 4,4'- diamino
The molar ratio of base diphenyl-methane and paraformaldehyde is 1:1:4.2, is heated to reflux a point water reaction 0.6h, after fully reacting, filters
To siliceous benzoxazine monomer.Reaction principle are as follows:
The siliceous benzoxazine monomer of the above-mentioned preparation of 2g is poured into circular aluminum mold, is placed in Constant Temp. Oven
Cured in stages obtains the polybenzoxazine of ring-opening polymerisation, elevated cure process at different temperatures are as follows: is warming up to 200 DEG C first
Heat cure 2.5h then heats to 220 DEG C of heat cure 2.5h.
Research test result shows: siliceous benzoxazine prepared by the present invention, and alkyl chain is not present in molecular structure, has
Excellent thermal stability and mechanical property, while the introducing of silicon atom is so that benzoxazine has excellent dielectric properties, fire-retardant
Performance and antiseptic property.After we carry out curing process to the siliceous benzoxazine of synthesis, TGA and glass transition temperature have been carried out
Degree test, the results showed that the initial decomposition temperature of polymer is greater than 400 DEG C, and 800 DEG C of carbon yield is greater than 75%.Glass is bad to be changed
Temperature is greater than 300 DEG C.And benzoxazine polymer has very high ph stability.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
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, but anything that does not depart from the technical scheme of the invention content, according to the technical essence of the invention
Any simple modification, equivalent change and modification to the above embodiments, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of novel siliceous benzoxazine monomer, which is characterized in that general formula of molecular structure is shown in formula (I) or formula (II):
Formula (I):
Formula (II):
In formula, R1And R2Respectively one of methyl, phenyl, ethyl, vinyl, R3For methyl or phenyl, R4The group of representative
Structure are as follows:
2. novel siliceous benzoxazine monomer as described in claim 1, which is characterized in that by the siliceous biphenol of raw material, amine
Compound and paraformaldehyde react synthesis under the conditions of solvent refluxing；The siliceous biphenol is original with phenol halides
Material, tetrahydrofuran is solvent, reacts and is made with chlorosilane under n-BuLi existence condition, the general structure of siliceous biphenol is such as
Under:
In formula, R1And R2Respectively one of methyl, phenyl, ethyl, vinyl.
3. novel siliceous benzoxazine monomer as claimed in claim 2, which is characterized in that the aminated compounds is monoamine
Compound, siliceous biphenol, monoamine compound, paraformaldehyde molar ratio be 1:2:4.1~4.4, the siliceous benzo of synthesis
The general structure of oxazines monomer is formula (I):
4. novel siliceous benzoxazine monomer as claimed in claim 3, which is characterized in that the monoamine compound is benzene
Amine, siliceous biphenol are bis- (p-hydroxybenzene) dimethyl-silicons, and the siliceous benzoxazine monomer structure formula of synthesis is as follows:
5. novel siliceous benzoxazine monomer as claimed in claim 2, which is characterized in that the aminated compounds is diamine class
Compound, siliceous biphenol, double aminated compounds, paraformaldehyde molar ratio be 1:1:4.1~4.4, the siliceous benzo of synthesis
The general structure of oxazines monomer is formula (II):
6. novel siliceous benzoxazine monomer as claimed in claim 5, which is characterized in that double aminated compounds are 4,
4 '-diaminodiphenylmethane, siliceous biphenol are bis- (p-hydroxybenzene) dimethyl-silicons, the siliceous benzoxazine monomer knot of synthesis
Structure formula is as follows:
7. a kind of preparation method of siliceous benzoxazine monomer as claimed in any one of claims 1 to 6, which is characterized in that system
Standby step are as follows: siliceous biphenol, aminated compounds, paraformaldehyde are added to the round-bottomed flask for filling benzene, toluene or chloroform
In, it is heated to reflux, after fully reacting, separating treatment obtains siliceous benzoxazine monomer.
8. the preparation method of novel siliceous benzoxazine monomer as claimed in claim 7, which is characterized in that preparation step are as follows:
At room temperature, will be bis- (p-hydroxybenzene) dimethyl-silicon or bis- (hydroxy phenyl) diphenyl silicon, aniline, paraformaldehyde be added
Into the round-bottomed flask for filling chloroform, heating reflux reaction 1 day, after fully reacting, after Rotary Evaporators solvent evaporated, column layer
Analysis obtains siliceous benzoxazine monomer.
9. the preparation method of novel siliceous benzoxazine monomer as claimed in claim 7, which is characterized in that preparation step are as follows:
At room temperature, will be bis- (p-hydroxybenzene) dimethyl-silicon or bis- (hydroxy phenyl) diphenyl silicon, 4,4 '-diamino hexichol first
Alkane, paraformaldehyde are added in the round-bottomed flask for filling chloroform, heating reflux reaction 6h, and filtering obtains siliceous benzoxazine list
Body.
10. a kind of siliceous benzoxazine monomer ring-opening polymerisation as claimed in any one of claims 1 to 6 prepares polybenzoxazine
Method, which is characterized in that steps are as follows: siliceous benzoxazine monomer being put into circular aluminum mold, electric heating constant temperature is placed in
Cured in stages obtains the polybenzoxazine of ring-opening polymerisation, elevated cure process are as follows: rise first at different temperatures in drying box
Temperature then heats to 220 DEG C of 2~3h of heat cure, is finally warming up to 240 DEG C of 2~3h of heat cure to 200 DEG C of 2~3h of heat cure.
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