CN103172811B - Zirconium-modified phenolic resin and preparation method thereof - Google Patents
Zirconium-modified phenolic resin and preparation method thereof Download PDFInfo
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- CN103172811B CN103172811B CN201310078858.5A CN201310078858A CN103172811B CN 103172811 B CN103172811 B CN 103172811B CN 201310078858 A CN201310078858 A CN 201310078858A CN 103172811 B CN103172811 B CN 103172811B
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Abstract
The invention relates to a zirconium-modified phenolic resin and a preparation method thereof. The zirconium-modified phenolic resin is technically characterized by being prepared from the following raw materials in parts by weight: 20-50 parts of phenol, 9-20 parts of formaldehyde, 2-10 parts of sodium hydroxide, 20-40 parts of ethanol, 10-20 parts of acetylacetone, 5-20 parts of zirconium oxychloride, and 0.5-2 parts of hydrogen peroxide. The preparation method comprises the following steps of: charging raw materials, refluxing, stirring, dropwise adding zirconium oxychloride ethanol solution, adjusting the pH value, discharging, and removing the solvent to obtain the zirconium-modified phenolic resin. The preparation method is simple, the cost is low, the content of zirconium is controllable, the prepared zirconium-modified phenolic resin has higher carbon yield, as well as good heat resistance, ablation resistance and mechanical property, is wide in application range, and has obvious economic and social benefits.
Description
Technical field
The invention belongs to polymer-modified field, be specifically related to a kind of modified zirconia resol and preparation method thereof.
Background technology
The polymkeric substance of the general polycondensation under catalyst action by phenols and aldehyde compound is called resol (PF).As one of three large thermosetting resins, PF have cheap, heat-resisting, resistance to ablation, fire-retardant, be fuming less, the advantage such as manufacturability is good and being widely used, be still used as the main base resin of resin base ablation resistant material so far.But when the matrix being used as the based composites of resistance to Ablative resin or the carbon matrix being converted into C/C matrix material, traditional PF deposits that a large amount of low molecular weight volatile thing generates in the curing process, the thermo-oxidative stability of cured article and the shortcoming such as carbon yield is on the low side, is difficult to meet it as the requirements at the higher level of aerospace material to ablation resistance.Therefore PF modification and by the PF of the addition reaction synthesizing new structure of thermostability group just become ablation resistant material research focus.
Summary of the invention
The object of the present invention is to provide a kind of modified zirconia resol and preparation method thereof, preparation method of the present invention is simple, cost is low, the content of zirconium is controlled, the modified zirconia resol carbon yield of preparation is higher, and there is good thermotolerance, ablation resistance and mechanical property, have wide range of applications, possess significant economic and social benefit.
For achieving the above object, the present invention adopts following technical scheme:
A kind of modified zirconia resol, is characterized in that the mass fraction of each raw material is: phenol 20-50 part, formaldehyde 9-20 part, sodium hydroxide 2-10 part, ethanol 20-40 part, methyl ethyl diketone 10-20 part, zirconium oxychloride 5-20 part, hydrogen peroxide 0.5-2 part.
Prepare a method for modified zirconia resol according to claim 1, it is characterized in that step comprise reinforced, the zirconium oxychloride that refluxes, stirs, adds ethanolic soln, regulate pH, discharging, removal solvent process, concrete step is as follows:
Step 1: add phenol, formaldehyde and sodium hydroxide solution in the there-necked flask that agitator, condensation reflux unit are housed, warming while stirring is to 60-75 DEG C, and reaction 1-2h, obtains resin reaction liquid;
Step 2: by mass fraction ethanol 20-40 part, methyl ethyl diketone 10-20 part, zirconium oxychloride 5-20 part, hydrogen peroxide 0.5-2 part configuration zirconyl chloride solution;
Step 3: intensification limit, limit is stirred, and drips the zirconyl chloride solution prepared simultaneously, the pH value controlling solution is 7-9;
Step 4: after temperature reaches 80-95 DEG C, after insulation 2-2.5h, discharging;
Step 5: the product that upper step obtains is put into vacuum drying oven 30-60 DEG C of insulation 3-5h, namely obtain modified zirconia resol.
Remarkable advantage of the present invention is: preparation method of the present invention is simple, cost is low, the content of zirconium is controlled, the modified zirconia resol carbon yield of preparation is higher, and there is good thermotolerance, ablation resistance and mechanical property, have wide range of applications, possess significant economic and social benefit.
Accompanying drawing explanation
Fig. 1 is the hot weightless picture of modified zirconia resol and common resol;
Fig. 2 is the infrared spectrogram of modified zirconia resol and phenolic resin.
Embodiment
Embodiment one:
1) be respectively 24 parts, 10 parts by the mass fraction of phenol and formaldehyde to feed intake, and add massfraction be 40% sodium hydroxide solution 2.5g as catalyzer, warming while stirring to 70 DEG C, reaction 1h;
2) by mass fraction be: ethanol 40 parts, methyl ethyl diketone 20 parts, zirconium oxychloride 20 parts, 1 part, hydrogen peroxide configuration zirconyl chloride solution;
3) temperature to 95 DEG C of regulating thermostatic water-bath, drips the zirconyl chloride solution prepared, and the pH value controlling solution is 8-9;
4) after temperature reaches 95 DEG C, after insulation 2h, discharging;
5) product that upper step obtains is put into vacuum drying oven 50 DEG C insulation 5h, namely obtain modified zirconia resol.
Embodiment two:
1) be respectively 24 parts, 10 parts by the mass fraction of phenol and formaldehyde to feed intake, and add massfraction be 40% sodium hydroxide solution 2g as catalyzer, warming while stirring to 70 DEG C, reaction 1h;
2) by mass fraction be: ethanol 40 parts, methyl ethyl diketone 20 parts, zirconium oxychloride 10 parts, 1 part, hydrogen peroxide configuration zirconyl chloride solution;
3) temperature to 85 DEG C of regulating thermostatic water-bath, drips the zirconyl chloride solution prepared, and the pH value controlling solution is 8-9;
4) after temperature reaches 85 DEG C, after insulation 2h, discharging;
5) product that upper step obtains is put into vacuum drying oven 50 DEG C insulation 5h, namely obtain modified zirconia resol.
Embodiment three:
1) be respectively 24 parts, 10 parts by the mass fraction of phenol and formaldehyde to feed intake, and add massfraction be 40% sodium hydroxide solution 1.5g as catalyzer, warming while stirring to 70 DEG C, reaction 1h;
2) by mass fraction be: ethanol 40 parts, methyl ethyl diketone 20 parts, zirconium oxychloride 15 parts, 1 part, hydrogen peroxide configuration zirconyl chloride solution;
3) temperature to 85 DEG C of regulating thermostatic water-bath, drips the zirconyl chloride solution prepared, and the pH value controlling solution is 8-9;
4) after temperature reaches 85 DEG C, after insulation 2.5h, discharging;
5) product that upper step obtains is put into vacuum drying oven 50 DEG C insulation 5h, namely obtain modified zirconia resol.
The resistance to elevated temperatures of modified zirconia resol prepared by the present invention is more more excellent than phenolic resin.The thermal weight loss of modified zirconia resol and phenolic resin contrasts as shown in Figure 1, and in figure, a curve is the thermogravimetric curve of modified zirconia resol, and curve b is the thermogravimetric curve of phenolic resin; When temperature reaches 600 DEG C, the carbon yield of modified zirconia resol is 62%, far above phenolic resin (carbon yield of ordinary resin 600 DEG C time is 48%).As shown in Figure 2, in figure, c curve is the infrared spectra curve of modified zirconia resol to the infrared spectra comparison diagram of modified zirconia resol and phenolic resin, and curve d is the infrared spectra curve of phenolic resin.1355cm in curve c
-1, 1527cm
-1, 1694cm
-1there is stronger peak in wavelength place, absolutely proves that zirconium has been introduced in the macromolecular chain of resol; 1160cm in curve c
-1the peak at place obviously weakens by force, and the ehter bond in the modified zirconia resol prepared by explanation obviously reduces.
Claims (1)
1. prepare a method for modified zirconia resol, the mass fraction of the described each raw material of modified zirconia resol is: phenol 20-50 part, formaldehyde 9-20 part, sodium hydroxide 2-10 part, ethanol 20-40 part, methyl ethyl diketone 10-20 part, zirconium oxychloride 5-20 part, hydrogen peroxide 0.5-2 part; It is characterized in that step is as follows:
Step 1: add phenol, formaldehyde and sodium hydroxide solution in the there-necked flask that agitator, condensation reflux unit are housed, warming while stirring is to 60-75 DEG C, and reaction 1-2h, obtains resin reaction liquid;
Step 2: by mass fraction ethanol 20-40 part, methyl ethyl diketone 10-20 part, zirconium oxychloride 5-20 part, hydrogen peroxide 0.5-2 part configuration zirconyl chloride solution;
Step 3: intensification limit, limit is stirred, and drips the zirconyl chloride solution prepared simultaneously, the pH value controlling solution is 7-9;
Step 4: after temperature reaches 80-95 DEG C, after insulation 2-2.5h, discharging;
Step 5: the product that upper step obtains is put into vacuum drying oven 30-60 DEG C of insulation 3-5h, namely obtain modified zirconia resol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310078858.5A CN103172811B (en) | 2013-03-13 | 2013-03-13 | Zirconium-modified phenolic resin and preparation method thereof |
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| CN103172811B true CN103172811B (en) | 2015-02-25 |
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| CN104341949B (en) * | 2013-08-02 | 2016-12-28 | 中国石油天然气股份有限公司 | A kind of wear-resisting inner side anticorrosion coating and preparation thereof and application |
| CN103435766B (en) * | 2013-08-30 | 2015-06-24 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| CN112250464B (en) * | 2020-10-26 | 2022-07-15 | 西安工程大学 | Foam carbon composite material for electromagnetic shielding and preparation method thereof |
| CN112794990A (en) * | 2021-02-01 | 2021-05-14 | 北京化工大学 | Inorganic hybrid modified novolac epoxy resin and preparation method thereof |
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