CN104817821B - A kind of SiO2-TiO2inorganic hybridization thermosetting phenolic resin and preparation method thereof - Google Patents
A kind of SiO2-TiO2inorganic hybridization thermosetting phenolic resin and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of SiO2‑TiO2Inorganic hybridization thermosetting phenolic resin and preparation method thereof, this phenolic resin is according to mass fraction ratio, by 100~200 parts of phenol, 85~175 parts of formalins, 0.2~8 part of tetraethyl orthosilicate and 0.2~8 part of butyl titanate are as reactant, and prepare by adding the pH value of 0.3~2 part of barium hydroxide octahydrate and 0.5~2.5 part of phosphoric acid solution regulation reactant, the present invention solves physical doping silicon dioxide, titanium dioxide dispersion problem in phenolic resin, obtain dispersibility more preferable, more uniform phenolic resin material, and after phenolic resin curing, form the higher Si O key of bond energy and Ti O key, it is effectively improved the Residual carbon of phenolic resin;Improve anti-yaw damper performance and the mechanical property of its composite.
Description
Technical field
The present invention relates to a kind of SiO2-TiO2Inorganic hybridization thermosetting phenolic resin and preparation method thereof, for ablative thermal protection polymer matrix composites.
Background technology
Phenolic resin is to realize industrialized synthetic resin the most the earliest, because it is cheap, have excellent ablation resistance, heat resistance, fire resistance and be widely used in the fields such as space flight, aviation, military project.As the topmost matrix resin of ablation thermal protection composite material, phenolic resin can not be substituted in ablator field.But, the easy oxidized decomposition of the such as phenolic hydroxyl group, methylene of the weak link on phenolic resin structure, thus reduce the anti-yaw damper performance of its composite product, mechanical property, heat resistance to a certain extent.In the face of space flight, military industry field are to heat resistance to phenolic resin-base composite of the day by day harsh requirement of ablation thermal protection composite material and aviation field, the demand of fire resistance, the in recent years structurally-modified focus becoming this area research to phenolic resin.
The SiO reported at present2-TiO2The preparation of inorganic hybridization thermosetting phenolic resin mainly has chemical method and physical blending process, chemical method be form polytitanosiloxane gel by butyl titanate and tetraethyl orthosilicate dehydrating condensation after, join copolymerization in phenolic resin, but the method is relatively big because of phenolic resin strand and polytitanosiloxane strand, SiO in the hybrid phenol-formaldehyde resin formed after causing copolymerization2-TiO2There is dispersion problem in inorganic particle.Physical blending process is directly by SiO2And TiO2Nano-particle adds to phenolic resin, but easily causes nanoparticle agglomerates, and dispersibility is poor.
Summary of the invention
It is an object of the invention to overcome the drawbacks described above of prior art, it is provided that a kind of SiO2-TiO2Inorganic hybridization thermosetting phenolic resin, solve physical doping silicon dioxide, the titanium dioxide dispersion problem in phenolic resin, obtain dispersibility more preferable, more uniform phenolic resin material, improves the heat resistance of phenolic resin and the impact property of composite product thereof and tensile property simultaneously.
Another object of the present invention is to provide a kind of SiO2-TiO2The preparation method of inorganic hybridization thermosetting phenolic resin.
The above-mentioned purpose of the present invention is mainly achieved by following technical solution:
A kind of SiO2-TiO2Inorganic hybridization thermosetting phenolic resin, according to mass fraction ratio, by 100~200 parts of phenol, 85~175 parts of formalins, 0.2~8 part of tetraethyl orthosilicate and 0.2~8 part of butyl titanate as reactant, and prepare by adding the pH value of 0.3~2 part of barium hydroxide octahydrate and 0.5~2.5 part of phosphoric acid solution regulation reactant.
At above-mentioned SiO2-TiO2In inorganic hybridization thermosetting phenolic resin, reactant includes 110~170 parts of phenol, 105~165 parts of formaldehyde, 1~6 part of tetraethyl orthosilicate and 1~6 part of butyl titanate, and adds 0.75~1.5 part of barium hydroxide octahydrate and 1~2 part of phosphoric acid solution regulation pH value.
At above-mentioned SiO2-TiO2In inorganic hybridization thermosetting phenolic resin, reactant includes that 120~140 parts of phenol, 130~150 parts of formaldehyde, 3~5 parts of tetraethyl orthosilicates and 3~5 parts of butyl titanates are made, and adds 1~1.2 part of barium hydroxide octahydrate and 1.2~1.4 parts of phosphoric acid solution regulation pH values.
At above-mentioned SiO2-TiO2In inorganic hybridization thermosetting phenolic resin, in formalin, the mass concentration of formaldehyde is 35~37%.
At above-mentioned SiO2-TiO2In inorganic hybridization thermosetting phenolic resin, in phosphoric acid solution, the mass concentration of phosphoric acid is 10~50%.
A kind of SiO2-TiO2The preparation method of inorganic hybridization thermosetting phenolic resin, comprises the steps:
(1), it is dissolved in formalin than by phenol by mass fraction, and it being sequentially added into tetraethyl orthosilicate, butyl titanate, 40~50 DEG C of stirring in water bath, the pH value adding barium hydroxide octahydrate regulation solution afterwards is 8~9, it is to slowly warm up to 60~70 DEG C, carries out isothermal reaction;
(2), the solution obtained in step (1) is to slowly warm up to 85~98 DEG C by 60~70 DEG C, carries out isothermal reaction;
(3), adding phosphoric acid solution, the pH value of the solution that set-up procedure (2) obtains is 5~6, after stirring 10~20min, under vacuum condition, and water-bath 85~98 DEG C of stirring dehydrations 1~3h, prepare SiO2-TiO2Inorganic hybridization thermosetting phenolic resin.
At above-mentioned SiO2-TiO2In the preparation method of inorganic hybridization thermosetting phenolic resin, stirring in water bath 10~30min in step (1);Isothermal reaction 1~3h.
At above-mentioned SiO2-TiO2In the preparation method of inorganic hybridization thermosetting phenolic resin, isothermal reaction 1~3h in step (2).
At above-mentioned SiO2-TiO2In the preparation method of inorganic hybridization thermosetting phenolic resin, in step (1) and step (2), heating rate is 0.16~0.33 DEG C/min.
At above-mentioned SiO2-TiO2In the preparation method of inorganic hybridization thermosetting phenolic resin, in formalin, the mass concentration of formaldehyde is 35~37%;In phosphoric acid solution, the mass concentration of phosphoric acid is 10~50%.
The present invention compared with prior art has the advantages that
(1), the present invention utilizes four hydroxy functional groups that butyl titanate and tetraethyl orthosilicate generate after hydrolyzing, in position during novolak resin, participate in the dehydration condensation between methylol, thus silicon atom, titanium atom are incorporated in resin backbone structure, solve physical doping silicon dioxide, the titanium dioxide dispersion problem in phenolic resin, obtain dispersibility more preferable, more uniform phenolic resin material, form the higher Si-O key of bond energy and Ti-O key after phenolic resin curing, be effectively improved the Residual carbon of phenolic resin;
(2), the present invention uses nano silicon that situ aggregation method is introduced in molecular structure presented in complex, can have an effect with the electron cloud of unsaturated bond in resin, and then it is combined with each other into space network with the macromole in phenolic resin, thus increasing substantially the heat resistance of phenolic resin, the glassy state pottery simultaneously formed after ablation improves phenolic resin-base composite anti-yaw damper performance;Equally, the nano titanium oxide being present in molecular structure with complex form, can effectively weaken the polarity between macromolecular chain and connect, improve the mechanical property of its composite product, such as, significantly improve impact property and the tensile property of its composite;
(3), a large number of experiments show that, SiO of the present invention2-TiO2Inorganic hybridization thermosetting phenolic resin, rotary viscosity 5~100mPa s after 50% ethanol solution dilution, solids content is more than 80%, and 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3%;SiO of the present invention2-TiO2The heat release more common ba phenolic resin of composite hot strength prepared by inorganic hybridization thermosetting phenolic resin improves more than 5%, and the more common ba phenolic resin of impact strength improves more than 5%;
(4), SiO of the present invention2-TiO2Inorganic hybridization thermosetting phenolic resin preparation method technique is simple, operation is simple, equipment requirements performance is low, it is easy to popularization and application.
Accompanying drawing explanation
Fig. 1 is butyl titanate of the present invention and teos hydrolysis reaction schematic diagram;
Fig. 2 is SiO of the present invention2-TiO2The synthetic reaction schematic diagram of inorganic hybridization thermosetting phenolic resin;
Fig. 3 is SiO of the present invention2-TiO2The curing reaction schematic diagram of inorganic hybridization thermosetting phenolic resin;
Fig. 4 is common ba phenolic resin and SiO of the present invention2-TiO2Inorganic hybridization thermosetting phenolic resin infrared spectrum comparison diagram.
Detailed description of the invention
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings:
SiO of the present invention2-TiO2Inorganic hybridization thermosetting phenolic resin, according to mass fraction ratio, by 100~200 parts of phenol, 85~175 parts of formalins, 0.2~8 part of tetraethyl orthosilicate and 0.2~8 part of butyl titanate as reactant, and prepare by adding the pH value of 0.3~2 part of barium hydroxide octahydrate and 0.5~2.5 part of phosphoric acid solution regulation reactant.
Reactant is preferred: includes 105~180 parts of phenol, 100~170 parts of formalins, 0.5~7 part of tetraethyl orthosilicate and 0.5~7 part of butyl titanate, and adds 0.5~1.75 part of barium hydroxide octahydrate and 0.75~2.25 part of phosphoric acid solution regulation pH value.
Further preferred: to include 110~170 parts of phenol, 105~165 parts of formalins, 1~6 part of tetraethyl orthosilicate and 1~6 part of butyl titanate, and add 0.75~1.5 part of barium hydroxide octahydrate and 1~2 part of phosphoric acid solution regulation pH value.
The most preferred: to include 115~160 parts of phenol, 115~160 parts of formalins, 2~5.5 parts of tetraethyl orthosilicates and 2~5.5 parts of butyl titanates, and add 0.9~1.4 part of barium hydroxide octahydrate and 1.1~1.8 parts of phosphoric acid solution regulation pH values.
Most preferably: include 120~140 parts of phenol, 130~150 parts of formalins, 3~5 parts of tetraethyl orthosilicates and 3~5 parts of butyl titanates, and add 1~1.2 part of barium hydroxide octahydrate and 1.2~1.4 parts of phosphoric acid solution regulation pH values.
Wherein in formalin, the mass concentration of formaldehyde is 35~37%;In phosphoric acid solution, the mass concentration of phosphoric acid is 10~50%.
SiO of the present invention2-TiO2The preparation method of inorganic hybridization thermosetting phenolic resin, comprises the steps:
(1), it is dissolved in 85~175 parts of formalins than by 100~200 parts of phenol by mass fraction, and it is sequentially added into 0.2~8 part of tetraethyl orthosilicate, 0.2~8 part of butyl titanate, 40~50 DEG C of stirring in water bath 10~30min, the pH value adding barium hydroxide octahydrate regulation solution afterwards is 8~9, it is to slowly warm up to 60~70 DEG C, carries out isothermal reaction 1~3h;Heating rate is 0.16~0.33 DEG C/min;
(2), by 60~70 DEG C, the solution obtained in step (1) being to slowly warm up to 85~98 DEG C, carry out isothermal reaction 1~3h, heating rate is 0.16~0.33 DEG C/min;
(3), adding phosphoric acid solution, the pH value of the solution that set-up procedure (2) obtains is 5~6, after stirring 10~20min, under vacuum condition, after water-bath 85~98 DEG C of stirring dehydrations 1~3h, stand, precipitate, filter, it is cooled to room temperature, takes out upper strata virgin resin, i.e. obtain SiO2-TiO2Inorganic hybridization thermosetting phenolic resin.
If Fig. 1 is butyl titanate of the present invention and teos hydrolysis reaction schematic diagram;Fig. 2 is SiO of the present invention2-TiO2The synthetic reaction schematic diagram of inorganic hybridization thermosetting phenolic resin;Fig. 3 is SiO of the present invention2-TiO2The curing reaction schematic diagram of inorganic hybridization thermosetting phenolic resin.
As it is shown on figure 3, SiO of the present invention2-TiO2The higher Si-O key of bond energy and Ti-O key is formed after the solidification of inorganic hybridization thermosetting phenolic resin, it is effectively improved the Residual carbon of phenolic resin, to form glassy state pottery after the nano silicon ablation that complex form is present in phenol-formaldehyde resin matrix structure, improve the anti-yaw damper performance of its composite, the nano titanium oxide simultaneously existed with complex form effectively weakens the polarity between macromolecular chain and connects, and improves the mechanical property of its goods.The SiO of the present invention2-TiO2Inorganic hybridization thermosetting phenolic resin is yellowish-brown thick liquid, and rotary viscosity 5~100mPa s after 50% ethanol solution dilution, solids content is more than 80%, and 800 DEG C of more common ba phenolic resins of Residual carbon improve 3%.
Embodiment 1
According to mass parts, 130 parts of phenol are dissolved in 140 parts of formalins, and it is sequentially added into 4 parts of tetraethyl orthosilicates, 4 parts of butyl titanates, 40 DEG C of stirring in water bath 30min, the pH value adding 1.1 parts of barium hydroxide octahydrate regulation solution afterwards is 8~9, it is to slowly warm up to 60 DEG C, carries out isothermal reaction 1~3h;Heating rate is 0.25 DEG C/min;Formalin mass concentration is 37%.
By 60 DEG C, above-mentioned solution being to slowly warm up to 95 DEG C, carries out isothermal reaction 1h, heating rate is 0.25 DEG C/min;
Adding 1.3 parts of phosphoric acid solutions, the pH value adjusting above-mentioned solution is 5~6, after stirring 15min, under vacuum condition, after water-bath 95 DEG C stirring dehydration 1h, stands, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, i.e. obtain SiO2-TiO2Inorganic hybridization thermosetting phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 20%.
The SiO that the present embodiment obtains2-TiO2Inorganic hybridization thermosetting phenolic resin is yellowish-brown thick liquid, and rotary viscosity 35mPa s after 50% ethanol solution dilution, solids content is 83%, and 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO2-TiO2Inorganic hybridization thermosetting phenolic resin Residual carbon meansigma methods is 63.13%, dispersion 0.76).
It is illustrated in figure 4 common ba phenolic resin and SiO of the present invention2-TiO2Inorganic hybridization thermosetting phenolic resin infrared spectrum comparison diagram, as seen from the figure, at 1100cm-1Neighbouring is Si-O-C absworption peak, 1050cm-1Neighbouring is Ti-O-C absworption peak, 645cm-1Near is Ti-O absworption peak, it was demonstrated that successfully Si-O key and Ti-O key being introduced in phenol-formaldehyde resin matrix structure by in-situ copolymerization is legal, other characteristic absorption peaks of phenolic resin are shown in Table 1:
Table 1 SiO2-TiO2Inorganic hybridization thermosetting phenolic resin infrared spectrum analysis
Embodiment 2
According to mass parts, 100 parts of phenol are dissolved in 85 parts of formalins, and it is sequentially added into 0.2 part of tetraethyl orthosilicate, 0.2 part of butyl titanate, 40 DEG C of stirring in water bath 30min, the pH value adding 0.3 part of barium hydroxide octahydrate regulation solution afterwards is 8~9, it is to slowly warm up to 60 DEG C, carries out isothermal reaction 1~3h;Heating rate is 0.16 DEG C/min;Formalin mass concentration is 35%.
By 60 DEG C, above-mentioned solution being to slowly warm up to 95 DEG C, carries out isothermal reaction 1h, heating rate is 0.16 DEG C/min;
Adding 0.5 part of phosphoric acid solution, the pH value adjusting above-mentioned solution is 5~6, after stirring 15min, under vacuum condition, after water-bath 95 DEG C stirring dehydration 3h, stands, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, i.e. obtain SiO2-TiO2Inorganic hybridization thermosetting phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 15%.
The SiO that the present embodiment obtains2-TiO2Inorganic hybridization thermosetting phenolic resin is yellowish-brown thick liquid, and rotary viscosity 5mPa s after 50% ethanol solution dilution, solids content is 80%, and 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO2-TiO2Inorganic hybridization thermosetting phenolic resin Residual carbon meansigma methods is 56.76%, dispersion 0.91).
Embodiment 3
According to mass parts, 200 parts of phenol are dissolved in 175 parts of formalins, and are sequentially added into 8 parts of tetraethyl orthosilicates, 8 parts of butyl titanates, 45 DEG C of stirring in water bath 30min, the pH value adding 2 parts of barium hydroxide octahydrate regulation solution afterwards is 8~9, is to slowly warm up to 65 DEG C, carries out isothermal reaction 3h;Heating rate is 0.33 DEG C/min;Formalin mass concentration is 37%.
By 65 DEG C, above-mentioned solution being to slowly warm up to 95 DEG C, carries out isothermal reaction 1h, heating rate is 0.33 DEG C/min;
Adding 2.5 parts of phosphoric acid solutions, the pH value adjusting above-mentioned solution is 5~6, after stirring 15min, under vacuum condition, after water-bath 95 DEG C stirring dehydration 3h, stands, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, i.e. obtain SiO2-TiO2Inorganic hybridization thermosetting phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 20%.
The SiO that the present embodiment obtains2-TiO2Inorganic hybridization thermosetting phenolic resin is yellowish-brown thick liquid, and rotary viscosity 97mPa s after 50% ethanol solution dilution, solids content is 84%, and 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO2-TiO2Inorganic hybridization thermosetting phenolic resin Residual carbon meansigma methods is 61.76%, dispersion 0.57).
Embodiment 4
According to mass parts, 115 parts of phenol are dissolved in 155 parts of formalins, and are sequentially added into 4 parts of tetraethyl orthosilicates, 4 parts of butyl titanates, 40 DEG C of stirring in water bath 30min, the pH value adding 1.2 parts of barium hydroxide octahydrate regulation solution afterwards is 8~9, is to slowly warm up to 60 DEG C, carries out isothermal reaction 3h;Heating rate is 0.2 DEG C/min;Formalin mass concentration is 37%.
By 60 DEG C, above-mentioned solution being to slowly warm up to 95 DEG C, carries out isothermal reaction 2h, heating rate is 0.2 DEG C/min;
Adding 1.5 parts of phosphoric acid solutions, the pH value adjusting above-mentioned solution is 5~6, after stirring 15min, under vacuum condition, after water-bath 95 DEG C stirring dehydration 1h, stands, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, i.e. obtain SiO2-TiO2Inorganic hybridization thermosetting phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 20%.
The SiO that the present embodiment obtains2-TiO2Inorganic hybridization thermosetting phenolic resin is yellow viscous liquid, and rotary viscosity 61mPa s after 50% ethanol solution dilution, solids content is 82%, and 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO2-TiO2Inorganic hybridization thermosetting phenolic resin Residual carbon meansigma methods is 60.41%, dispersion 0.98).
Embodiment 5
According to mass parts, 135 parts of phenol are dissolved in 145 parts of formalins, and are sequentially added into 4 parts of tetraethyl orthosilicates, 4 parts of butyl titanates, 40 DEG C of stirring in water bath 30min, the pH value adding 1.1 parts of barium hydroxide octahydrate regulation solution afterwards is 8~9, is to slowly warm up to 70 DEG C, carries out isothermal reaction 3h;Heating rate is 0.33 DEG C/min;Formalin mass concentration is 36%.
By 60 DEG C, above-mentioned solution being to slowly warm up to 85 DEG C, carries out isothermal reaction 1h, heating rate is 0.33 DEG C/min;
Adding 1.3 parts of phosphoric acid solutions, the pH value adjusting above-mentioned solution is 5~6, after stirring 15min, under vacuum condition, after water-bath 85 DEG C stirring dehydration 2h, stands, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, i.e. obtain SiO2-TiO2Inorganic hybridization thermosetting phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 20%.
The SiO that the present embodiment obtains2-TiO2Inorganic hybridization thermosetting phenolic resin is yellow viscous liquid, and rotary viscosity 28mPa s after 50% ethanol solution dilution, solids content is 81%, and 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO2-TiO2Inorganic hybridization thermosetting phenolic resin Residual carbon meansigma methods is 61.16%, dispersion 0.87).
The above; being only the detailed description of the invention that the present invention is optimal, but protection scope of the present invention is not limited thereto, any those familiar with the art is in the technical scope that the invention discloses; the change that can readily occur in or replacement, all should contain within protection scope of the present invention.
The content not being described in detail in description of the invention belongs to the known technology of professional and technical personnel in the field.
Claims (10)
1. a SiO2-TiO2Inorganic hybridization thermosetting phenolic resin, it is characterized in that: according to mass fraction ratio, by 100~200 parts of phenol, 85~175 parts of formalins, 0.2~8 part of tetraethyl orthosilicate and 0.2~8 part of butyl titanate as reactant, and by adding 0.3~2 part of barium hydroxide octahydrate and the pH of 0.5~2.5 part of phosphoric acid solution regulation reactant
Value prepares.
A kind of SiO the most according to claim 12-TiO2Inorganic hybridization thermosetting phenolic resin, it is characterized in that: described reactant includes 110~170 parts of phenol, 105~165 parts of formaldehyde, 1~6 part of tetraethyl orthosilicate and 1~6 part of butyl titanate, and adds 0.75~1.5 part of barium hydroxide octahydrate and 1~2 part of phosphoric acid solution regulation pH
Value.
A kind of SiO the most according to claim 22-TiO2Inorganic hybridization thermosetting phenolic resin, it is characterized in that: described reactant includes that 120~140 parts of phenol, 130~150 parts of formaldehyde, 3~5 parts of tetraethyl orthosilicates and 3~5 parts of butyl titanates are made, and add 1~1.2 part of barium hydroxide octahydrate and 1.2~1.4 parts of phosphoric acid solution regulation pH
Value.
4. according to a kind of SiO described in claims 1 to 3 any claim2-TiO2Inorganic hybridization thermosetting phenolic resin, it is characterised in that: in described formalin, the mass concentration of formaldehyde is 35~37%.
5. according to a kind of SiO described in claims 1 to 3 any claim2-TiO2Inorganic hybridization thermosetting phenolic resin, it is characterised in that: in described phosphoric acid solution, the mass concentration of phosphoric acid is 10~50%.
6. the SiO described in claims 1 to 3 any claim2-TiO2The preparation method of inorganic hybridization thermosetting phenolic resin, it is characterised in that: comprise the steps:
(1), it is dissolved in formalin than by phenol by mass fraction, and is sequentially added into tetraethyl orthosilicate, butyl titanate, 40~50 DEG C of stirring in water bath, add the pH of barium hydroxide octahydrate regulation solution afterwards
Value is 8~9, is to slowly warm up to 60~70 DEG C, carries out isothermal reaction;
(2), the solution obtained in step (1) is to slowly warm up to 85~98 DEG C by 60~70 DEG C, carries out isothermal reaction;
(3), adding phosphoric acid solution, the pH value of the solution that set-up procedure (2) obtains is 5~6, after stirring 10~20min, under vacuum condition, and water-bath 85~98 DEG C of stirring dehydrations 1~3h, prepare SiO2-TiO2Inorganic hybridization thermosetting phenolic resin.
SiO the most according to claim 62-TiO2The preparation method of inorganic hybridization thermosetting phenolic resin, it is characterised in that: stirring in water bath 10~30min in described step (1);Isothermal reaction 1~3h.
SiO the most according to claim 62-TiO2The preparation method of inorganic hybridization thermosetting phenolic resin, it is characterised in that: isothermal reaction 1~3h in described step (2).
SiO the most according to claim 62-TiO2The preparation method of inorganic hybridization thermosetting phenolic resin, it is characterised in that: in described step (1) and step (2), heating rate is 0.16~0.33 DEG C/min.
SiO the most according to claim 62-TiO2The preparation method of inorganic hybridization thermosetting phenolic resin, it is characterised in that: in described formalin, the mass concentration of formaldehyde is 35~37%;In phosphoric acid solution, the mass concentration of phosphoric acid is 10~50%.
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