CN104817821A - SiO2-TiO2 inorganic hybrid thermosetting thermosetting phenolic resin and preparation method thereof - Google Patents
SiO2-TiO2 inorganic hybrid thermosetting thermosetting phenolic resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a SiO2-TiO2 inorganic hybrid thermosetting thermosetting phenolic resin and a preparation method thereof. The phenolic resin comprises the following mass part: 100-200 parts of phenol, 85-175 parts of formaldehyde solution, 0.2-8 parts of ethyl orthosilicate and 0.2-8 parts of tetrabutyl titanate. The method comprises the following steps: taking phenol, a formaldehyde solution, ethyl orthosilicate and tetrabutyl titanate as a reactant, and adding 0.3-2 parts of barium hydroxide octahydrate and 0.5-2.5 parts of phosphoric acid solution to adjust pH value of the reactant. The problem of dispersibility of physically-doped silica and titanium dioxide in phenolic resin can be solved, the phenolic resin material with better and more uniform dispersibility can be obtained, Si-O bond and Ti-O bond with high bond energy can be formed after phenolic resin is solidified, residual carbon rate of phenolic resin can be effectively increased, and anti-ablation performance and mechanical property of the composite materials can be improved.
Description
Technical field
The present invention relates to a kind of SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin and preparation method thereof, for ablative thermal protection polymer matrix composites.
Background technology
Resol realizes industrialized synthetic resins the earliest in the world, because it is cheap, there is excellent ablation resistance, resistance toheat, flame retardant properties 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, resol can not be substituted in ablator field.But the weak link on phenolic resin structure as phenolic hydroxyl group, the easy oxidized decomposition of methylene radical, thus reduces anti-yaw damper performance, mechanical property, the resistance toheat of its composite product to a certain extent.In the face of space flight, military industry field are to the day by day harsh requirement of ablation thermal protection composite material and the resistance toheat of aviation field to phenolic resin-base composite, the demand of flame retardant properties, in recent years to the structurally-modified focus becoming this area research of resol.
The SiO reported at present
2-TiO
2the preparation of inorganic hybridization heat-reactive phenolic resin mainly contains chemical method and physical blending process, chemical method is after forming polytitanosiloxane gel by tetrabutyl titanate and tetraethoxy dehydrating condensation, join copolymerization in resol, but the method because of resol molecular chain and polytitanosiloxane molecular chain comparatively large, SiO in the hybrid phenol-formaldehyde resin formed after causing copolymerization
2-TiO
2there is dispersion problem in inorganic particle.Physical blending process is directly by SiO
2and TiO
2nano particle is added in resol, but easily causes nanoparticle agglomerates, dispersed poor.
Summary of the invention
The object of the invention is to the above-mentioned defect overcoming prior art, a kind of SiO is provided
2-TiO
2inorganic hybridization heat-reactive phenolic resin, solve physical doping silicon-dioxide, the titanium dioxide dispersion problem in resol, obtain dispersed better, more uniform phenolic resin material, improves the resistance toheat of resol and the impact property of composite product thereof and tensile property simultaneously.
Another object of the present invention is to provide a kind of SiO
2-TiO
2the preparation method of inorganic hybridization heat-reactive phenolic resin.
Above-mentioned purpose of the present invention is mainly achieved by following technical solution:
A kind of SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin, according to ratio of quality and the number of copies, by 100 ~ 200 parts of phenol, 85 ~ 175 parts of formaldehyde solutions, 0.2 ~ 8 part of tetraethoxy and 0.2 ~ 8 part of tetrabutyl titanate as reactant, and prepared by the pH value adding 0.3 ~ 2 part of barium hydroxide octahydrate and 0.5 ~ 2.5 part of phosphoric acid solution adjustment reactant.
At above-mentioned SiO
2-TiO
2in inorganic hybridization heat-reactive phenolic resin, reactant comprises 110 ~ 170 parts of phenol, 105 ~ 165 parts of formaldehyde, 1 ~ 6 part of tetraethoxy and 1 ~ 6 part of tetrabutyl titanate, and adds 0.75 ~ 1.5 part of barium hydroxide octahydrate and 1 ~ 2 part of phosphoric acid solution adjustment pH value.
At above-mentioned SiO
2-TiO
2in inorganic hybridization heat-reactive phenolic resin, reactant comprises 120 ~ 140 parts of phenol, 130 ~ 150 parts of formaldehyde, 3 ~ 5 parts of tetraethoxys and 3 ~ 5 parts of tetrabutyl titanates are made, and adds 1 ~ 1.2 part of barium hydroxide octahydrate and 1.2 ~ 1.4 parts of phosphoric acid solutions adjustment pH values.
At above-mentioned SiO
2-TiO
2in inorganic hybridization heat-reactive phenolic resin, in formaldehyde solution, the mass concentration of formaldehyde is 35 ~ 37%.
At above-mentioned SiO
2-TiO
2in inorganic hybridization heat-reactive phenolic resin, in phosphoric acid solution, the mass concentration of phosphoric acid is 10 ~ 50%.
A kind of SiO
2-TiO
2the preparation method of inorganic hybridization heat-reactive phenolic resin, comprises the steps:
(1), by ratio of quality and the number of copies, phenol is dissolved in formaldehyde solution, and adding tetraethoxy, tetrabutyl titanate successively, 40 ~ 50 DEG C of stirring in water bath, the pH value adding barium hydroxide octahydrate regulator solution is afterwards 8 ~ 9, slowly be warming up to 60 ~ 70 DEG C, carry out isothermal reaction;
(2), by the solution obtained in step (1) be slowly warming up to 85 ~ 98 DEG C by 60 ~ 70 DEG C, carry out isothermal reaction;
(3), add phosphoric acid solution, the pH value of the solution that set-up procedure (2) obtains is 5 ~ 6, and after stirring 10 ~ 20min, under vacuum condition, dehydration 1 ~ 3h is stirred in water-bath 85 ~ 98 DEG C, prepares SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin.
At above-mentioned SiO
2-TiO
2in the preparation method of inorganic hybridization heat-reactive phenolic resin, stirring in water bath 10 ~ 30min in step (1); Isothermal reaction 1 ~ 3h.
At above-mentioned SiO
2-TiO
2in the preparation method of inorganic hybridization heat-reactive phenolic resin, isothermal reaction 1 ~ 3h in step (2).
At above-mentioned SiO
2-TiO
2in the preparation method of inorganic hybridization heat-reactive phenolic resin, step (1) and the middle temperature rise rate of step (2) are 0.16 ~ 0.33 DEG C/min.
At above-mentioned SiO
2-TiO
2in the preparation method of inorganic hybridization heat-reactive phenolic resin, in formaldehyde solution, 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 following beneficial effect:
(1), the present invention's four hydroxy functional groups utilizing tetrabutyl titanate and tetraethoxy to generate after hydrolyzing, in the process of novolak resin in position, participate in the dehydration condensation between methylol, thus Siliciumatom, titanium atom are incorporated in resin backbone structure, solve physical doping silicon-dioxide, the titanium dioxide dispersion problem in resol, obtain dispersed better, more uniform phenolic resin material, form the higher Si-O key of bond energy and Ti-O key after phenolic resin curing, effectively improve the Residual carbon of resol;
(2), the present invention adopts situ aggregation method to be introduced into the nano silicon in molecular structure to exist with the form of complex compound, can have an effect with the electronic cloud of unsaturated link(age) in resin, and then be combined with each other into tridimensional network with the macromole in resol, thus increasing substantially the resistance toheat of resol, the vitreous state pottery formed after ablation simultaneously improves phenolic resin-base composite anti-yaw damper performance; Equally, be present in the nano titanium oxide in molecular structure with complex form, the polarity that can effectively weaken between macromolecular chain connects, and improves the mechanical property of its composite product, such as, significantly improves impact property and the tensile property of its matrix material;
(3), a large number of experiments show that, SiO of the present invention
2-TiO
2inorganic hybridization heat-reactive phenolic resin, rotary viscosity 5 ~ 100mPas after 50% ethanolic soln dilution, solids content is greater than 80%, and 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3%; SiO of the present invention
2-TiO
2the more common ba phenolic resin of heat release matrix material tensile strength prepared by inorganic hybridization heat-reactive phenolic resin improves more than 5%, and the more common ba phenolic resin of shock strength improves more than 5%;
(4), SiO of the present invention
2-TiO
2inorganic hybridization heat-reactive phenolic resin preparation method technique is simple, it is simple and easy to operate, equipment requirements performance is low, is easy to apply.
Accompanying drawing explanation
Fig. 1 is tetrabutyl titanate of the present invention and teos hydrolysis reaction schematic diagram;
Fig. 2 is SiO of the present invention
2-TiO
2the building-up reactions schematic diagram of inorganic hybridization heat-reactive phenolic resin;
Fig. 3 is SiO of the present invention
2-TiO
2the curing reaction schematic diagram of inorganic hybridization heat-reactive phenolic resin;
Fig. 4 is common ba phenolic resin and SiO of the present invention
2-TiO
2inorganic hybridization heat-reactive phenolic resin infrared spectra comparison diagram.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
SiO of the present invention
2-TiO
2inorganic hybridization heat-reactive phenolic resin, according to ratio of quality and the number of copies, by 100 ~ 200 parts of phenol, 85 ~ 175 parts of formaldehyde solutions, 0.2 ~ 8 part of tetraethoxy and 0.2 ~ 8 part of tetrabutyl titanate as reactant, and prepared by the pH value adding 0.3 ~ 2 part of barium hydroxide octahydrate and 0.5 ~ 2.5 part of phosphoric acid solution adjustment reactant.
Reactant is preferred: comprise 105 ~ 180 parts of phenol, 100 ~ 170 parts of formaldehyde solutions, 0.5 ~ 7 part of tetraethoxy and 0.5 ~ 7 part of tetrabutyl titanate, and adds 0.5 ~ 1.75 part of barium hydroxide octahydrate and 0.75 ~ 2.25 part of phosphoric acid solution adjustment pH value.
Preferred further: to comprise 110 ~ 170 parts of phenol, 105 ~ 165 parts of formaldehyde solutions, 1 ~ 6 part of tetraethoxy and 1 ~ 6 part of tetrabutyl titanate, and add 0.75 ~ 1.5 part of barium hydroxide octahydrate and 1 ~ 2 part of phosphoric acid solution adjustment pH value.
Further preferred: to comprise 115 ~ 160 parts of phenol, 115 ~ 160 parts of formaldehyde solutions, 2 ~ 5.5 parts of tetraethoxys and 2 ~ 5.5 parts of tetrabutyl titanates, and add 0.9 ~ 1.4 part of barium hydroxide octahydrate and 1.1 ~ 1.8 parts of phosphoric acid solutions adjustment pH values.
Most preferably: comprise 120 ~ 140 parts of phenol, 130 ~ 150 parts of formaldehyde solutions, 3 ~ 5 parts of tetraethoxys and 3 ~ 5 parts of tetrabutyl titanates, and add 1 ~ 1.2 part of barium hydroxide octahydrate and 1.2 ~ 1.4 parts of phosphoric acid solutions regulate pH values.
Wherein in formaldehyde solution, 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 invention
2-TiO
2the preparation method of inorganic hybridization heat-reactive phenolic resin, comprises the steps:
(1), by ratio of quality and the number of copies, 100 ~ 200 parts of phenol are dissolved in 85 ~ 175 parts of formaldehyde solutions, and add 0.2 ~ 8 part of tetraethoxy, 0.2 ~ 8 part of tetrabutyl titanate successively, 40 ~ 50 DEG C of stirring in water bath 10 ~ 30min, the pH value adding barium hydroxide octahydrate regulator solution is afterwards 8 ~ 9, slowly be warming up to 60 ~ 70 DEG C, carry out isothermal reaction 1 ~ 3h; Temperature rise rate is 0.16 ~ 0.33 DEG C/min;
(2), by the solution obtained in step (1) be slowly warming up to 85 ~ 98 DEG C by 60 ~ 70 DEG C, carry out isothermal reaction 1 ~ 3h, temperature rise rate is 0.16 ~ 0.33 DEG C/min;
(3), add 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 dehydration 1 ~ 3h is stirred in water-bath 85 ~ 98 DEG C, leave standstill, precipitate, filter, be cooled to room temperature, take out upper strata virgin resin, namely obtain SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin.
If Fig. 1 is tetrabutyl titanate of the present invention and teos hydrolysis reaction schematic diagram; Fig. 2 is SiO of the present invention
2-TiO
2the building-up reactions schematic diagram of inorganic hybridization heat-reactive phenolic resin; Fig. 3 is SiO of the present invention
2-TiO
2the curing reaction schematic diagram of inorganic hybridization heat-reactive phenolic resin.
As shown in Figure 3, SiO of the present invention
2-TiO
2the higher Si-O key of bond energy and Ti-O key is formed after the solidification of inorganic hybridization heat-reactive phenolic resin, effectively improve the Residual carbon of resol, vitreous state pottery is formed be present in the nano silicon ablation in phenol-formaldehyde resin matrix structure with complex form after, improve the anti-yaw damper performance of its matrix material, the polarity that the nano titanium oxide simultaneously existed with complex form effectively weakens between macromolecular chain connects, and improves the mechanical property of its goods.SiO of the present invention
2-TiO
2inorganic hybridization heat-reactive phenolic resin is tawny thick liquid, and rotary viscosity 5 ~ 100mPas after 50% ethanolic soln dilution, solids content is greater 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 formaldehyde solutions, and add 4 parts of tetraethoxys, 4 parts of tetrabutyl titanates successively, 40 DEG C of stirring in water bath 30min, the pH value adding 1.1 parts of barium hydroxide octahydrate regulator solutions is afterwards 8 ~ 9, slowly be warming up to 60 DEG C, carry out isothermal reaction 1 ~ 3h; Temperature rise rate is 0.25 DEG C/min; Formaldehyde solution mass concentration is 37%.
Above-mentioned solution is slowly warming up to 95 DEG C by 60 DEG C, carries out isothermal reaction 1h, temperature rise rate is 0.25 DEG C/min;
Add 1.3 parts of phosphoric acid solutions, the pH value adjusting above-mentioned solution is 5 ~ 6, after stirring 15min, under vacuum condition, after dehydration 1h is stirred in water-bath 95 DEG C, leaves standstill, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, namely obtain SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 20%.
The SiO that the present embodiment obtains
2-TiO
2inorganic hybridization heat-reactive phenolic resin is tawny thick liquid, and rotary viscosity 35mPas after 50% ethanolic soln dilution, solids content is that 83%, 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin Residual carbon mean value is 63.13%, plastisied dispersion 0.76).
Be illustrated in figure 4 common ba phenolic resin and SiO of the present invention
2-TiO
2inorganic hybridization heat-reactive phenolic resin infrared spectra comparison diagram, as seen from the figure, at 1100cm
-1neighbouring is Si-O-C absorption peak, 1050cm
-1neighbouring is Ti-O-C absorption peak, 645cm
-1neighbouring is Ti-O absorption peak, and demonstrate and be successfully introduced in phenol-formaldehyde resin matrix structure by Si-O key and Ti-O key by in-situ copolymerization is legal, other charateristic avsorption bands of resol are shown in Table 1:
Table 1 SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin Infrared spectroscopy
Embodiment 2
According to mass parts, 100 parts of phenol are dissolved in 85 parts of formaldehyde solutions, and add 0.2 part of tetraethoxy, 0.2 part of tetrabutyl titanate successively, 40 DEG C of stirring in water bath 30min, the pH value adding 0.3 part of barium hydroxide octahydrate regulator solution is afterwards 8 ~ 9, slowly be warming up to 60 DEG C, carry out isothermal reaction 1 ~ 3h; Temperature rise rate is 0.16 DEG C/min; Formaldehyde solution mass concentration is 35%.
Above-mentioned solution is slowly warming up to 95 DEG C by 60 DEG C, carries out isothermal reaction 1h, temperature rise rate is 0.16 DEG C/min;
Add 0.5 part of phosphoric acid solution, the pH value adjusting above-mentioned solution is 5 ~ 6, after stirring 15min, under vacuum condition, after dehydration 3h is stirred in water-bath 95 DEG C, leaves standstill, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, namely obtain SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 15%.
The SiO that the present embodiment obtains
2-TiO
2inorganic hybridization heat-reactive phenolic resin is tawny thick liquid, and rotary viscosity 5mPas after 50% ethanolic soln dilution, solids content is that 80%, 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin Residual carbon mean value is 56.76%, plastisied dispersion 0.91).
Embodiment 3
According to mass parts, 200 parts of phenol are dissolved in 175 parts of formaldehyde solutions, and add 8 parts of tetraethoxys, 8 parts of tetrabutyl titanates successively, 45 DEG C of stirring in water bath 30min, the pH value adding 2 parts of barium hydroxide octahydrate regulator solutions is afterwards 8 ~ 9, is slowly warming up to 65 DEG C, carries out isothermal reaction 3h; Temperature rise rate is 0.33 DEG C/min; Formaldehyde solution mass concentration is 37%.
Above-mentioned solution is slowly warming up to 95 DEG C by 65 DEG C, carries out isothermal reaction 1h, temperature rise rate is 0.33 DEG C/min;
Add 2.5 parts of phosphoric acid solutions, the pH value adjusting above-mentioned solution is 5 ~ 6, after stirring 15min, under vacuum condition, after dehydration 3h is stirred in water-bath 95 DEG C, leaves standstill, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, namely obtain SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 20%.
The SiO that the present embodiment obtains
2-TiO
2inorganic hybridization heat-reactive phenolic resin is tawny thick liquid, and rotary viscosity 97mPas after 50% ethanolic soln dilution, solids content is that 84%, 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin Residual carbon mean value is 61.76%, plastisied dispersion 0.57).
Embodiment 4
According to mass parts, 115 parts of phenol are dissolved in 155 parts of formaldehyde solutions, and add 4 parts of tetraethoxys, 4 parts of tetrabutyl titanates successively, 40 DEG C of stirring in water bath 30min, the pH value adding 1.2 parts of barium hydroxide octahydrate regulator solutions is afterwards 8 ~ 9, slowly be warming up to 60 DEG C, carry out isothermal reaction 3h; Temperature rise rate is 0.2 DEG C/min; Formaldehyde solution mass concentration is 37%.
Above-mentioned solution is slowly warming up to 95 DEG C by 60 DEG C, carries out isothermal reaction 2h, temperature rise rate is 0.2 DEG C/min;
Add 1.5 parts of phosphoric acid solutions, the pH value adjusting above-mentioned solution is 5 ~ 6, after stirring 15min, under vacuum condition, after dehydration 1h is stirred in water-bath 95 DEG C, leaves standstill, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, namely obtain SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 20%.
The SiO that the present embodiment obtains
2-TiO
2inorganic hybridization heat-reactive phenolic resin is yellow viscous liquid, and rotary viscosity 61mPas after 50% ethanolic soln dilution, solids content is that 82%, 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin Residual carbon mean value is 60.41%, plastisied dispersion 0.98).
Embodiment 5
According to mass parts, 135 parts of phenol are dissolved in 145 parts of formaldehyde solutions, and add 4 parts of tetraethoxys, 4 parts of tetrabutyl titanates successively, 40 DEG C of stirring in water bath 30min, the pH value adding 1.1 parts of barium hydroxide octahydrate regulator solutions is afterwards 8 ~ 9, slowly be warming up to 70 DEG C, carry out isothermal reaction 3h; Temperature rise rate is 0.33 DEG C/min; Formaldehyde solution mass concentration is 36%.
Above-mentioned solution is slowly warming up to 85 DEG C by 60 DEG C, carries out isothermal reaction 1h, temperature rise rate is 0.33 DEG C/min;
Add 1.3 parts of phosphoric acid solutions, the pH value adjusting above-mentioned solution is 5 ~ 6, after stirring 15min, under vacuum condition, after dehydration 2h is stirred in water-bath 85 DEG C, leaves standstill, precipitates, filters, be cooled to room temperature, take out upper strata virgin resin, namely obtain SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin.In phosphoric acid solution, the mass concentration of phosphoric acid is 20%.
The SiO that the present embodiment obtains
2-TiO
2inorganic hybridization heat-reactive phenolic resin is yellow viscous liquid, and rotary viscosity 28mPas after 50% ethanolic soln dilution, solids content is that 81%, 800 DEG C of more common ba phenolic resins of Residual carbon improve more than 3% (SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin Residual carbon mean value is 61.16%, plastisied dispersion 0.87).
The above; be only the embodiment of the best of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
The content be not described in detail in specification sheets of the present invention belongs to the known technology of professional and technical personnel in the field.
Claims (10)
1. a SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin, it is characterized in that: according to ratio of quality and the number of copies, by 100 ~ 200 parts of phenol, 85 ~ 175 parts of formaldehyde solutions, 0.2 ~ 8 part of tetraethoxy and 0.2 ~ 8 part of tetrabutyl titanate as reactant, and prepared by the pH value adding 0.3 ~ 2 part of barium hydroxide octahydrate and 0.5 ~ 2.5 part of phosphoric acid solution adjustment reactant.
2. a kind of SiO according to claim 1
2-TiO
2inorganic hybridization heat-reactive phenolic resin, it is characterized in that: described reactant comprises 110 ~ 170 parts of phenol, 105 ~ 165 parts of formaldehyde, 1 ~ 6 part of tetraethoxy and 1 ~ 6 part of tetrabutyl titanate, and add 0.75 ~ 1.5 part of barium hydroxide octahydrate and 1 ~ 2 part of phosphoric acid solution adjustment pH value.
3. a kind of SiO according to claim 2
2-TiO
2inorganic hybridization heat-reactive phenolic resin, it is characterized in that: described reactant comprises 120 ~ 140 parts of phenol, 130 ~ 150 parts of formaldehyde, 3 ~ 5 parts of tetraethoxys and 3 ~ 5 parts of tetrabutyl titanates are made, and add 1 ~ 1.2 part of barium hydroxide octahydrate and 1.2 ~ 1.4 parts of phosphoric acid solutions adjustment pH values.
4. a kind of SiO according to the arbitrary claim of claims 1 to 3
2-TiO
2inorganic hybridization heat-reactive phenolic resin, is characterized in that: in described formaldehyde solution, the mass concentration of formaldehyde is 35 ~ 37%.
5. a kind of SiO according to the arbitrary claim of claims 1 to 3
2-TiO
2inorganic hybridization heat-reactive phenolic resin, is characterized in that: in described phosphoric acid solution, the mass concentration of phosphoric acid is 10 ~ 50%.
6. the SiO described in the arbitrary claim of claims 1 to 3
2-TiO
2the preparation method of inorganic hybridization heat-reactive phenolic resin, is characterized in that: comprise the steps:
(1), by ratio of quality and the number of copies, phenol is dissolved in formaldehyde solution, and adding tetraethoxy, tetrabutyl titanate successively, 40 ~ 50 DEG C of stirring in water bath, the pH value adding barium hydroxide octahydrate regulator solution is afterwards 8 ~ 9, slowly be warming up to 60 ~ 70 DEG C, carry out isothermal reaction;
(2), by the solution obtained in step (1) be slowly warming up to 85 ~ 98 DEG C by 60 ~ 70 DEG C, carry out isothermal reaction;
(3), add phosphoric acid solution, the pH value of the solution that set-up procedure (2) obtains is 5 ~ 6, and after stirring 10 ~ 20min, under vacuum condition, dehydration 1 ~ 3h is stirred in water-bath 85 ~ 98 DEG C, prepares SiO
2-TiO
2inorganic hybridization heat-reactive phenolic resin.
7. SiO according to claim 6
2-TiO
2the preparation method of inorganic hybridization heat-reactive phenolic resin, is characterized in that: stirring in water bath 10 ~ 30min in described step (1); Isothermal reaction 1 ~ 3h.
8. SiO according to claim 6
2-TiO
2the preparation method of inorganic hybridization heat-reactive phenolic resin, is characterized in that: isothermal reaction 1 ~ 3h in described step (2).
9. SiO according to claim 6
2-TiO
2the preparation method of inorganic hybridization heat-reactive phenolic resin, is characterized in that: described step (1) and the middle temperature rise rate of step (2) are 0.16 ~ 0.33 DEG C/min.
10. SiO according to claim 6
2-TiO
2the preparation method of inorganic hybridization heat-reactive phenolic resin, is characterized in that: in described formaldehyde solution, 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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