CN103172811A - Zirconium-modified phenolic resin and preparation method thereof - Google Patents
Zirconium-modified phenolic resin and preparation method thereof Download PDFInfo
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- CN103172811A CN103172811A CN2013100788585A CN201310078858A CN103172811A CN 103172811 A CN103172811 A CN 103172811A CN 2013100788585 A CN2013100788585 A CN 2013100788585A CN 201310078858 A CN201310078858 A CN 201310078858A CN 103172811 A CN103172811 A CN 103172811A
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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
Generally be called resol (PF) by phenols and the aldehyde compound polymkeric substance that polycondensation forms under catalyst action.As one of three large thermosetting resins, that PF has is cheap, heat-resisting, anti-ablation, fire-retardant, be fuming less, the advantage such as manufacturability is good and being widely used, so far still as the main matrix resin of resin base ablation resistant material.But when being used as the matrix of the based composites of anti-the Ablative resin or being converted into the carbon matrix of C/C matrix material, traditional PF exists in solidification process that a large amount of low molecular weight volatile things generate, the thermo-oxidative stability of cured article and the shortcoming such as carbon yield is on the low side, is difficult to satisfy it as the requirements at the higher level of aerospace material to ablation resistance.Therefore the PF of the modification of PF and the addition reaction synthesizing new structure by the thermostability group just becomes the focus of ablation resistant material research.
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 have good thermotolerance, ablation resistance and a 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.
A kind of method for preparing modified zirconia resol claimed in claim 1 is characterized in that step comprises reinforced, as to reflux, stir, add zirconium oxychloride ethanolic soln, regulates pH, discharging, removal solvent process, and 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 ℃, and reaction 1-2h obtains resin reaction liquid;
Step 2: press 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: stir on intensification limit, limit, drips simultaneously the zirconyl chloride solution for preparing, and the pH value of controlling solution is 7-9;
Step 4: after temperature reaches 80-95 ℃, after insulation 2-2.5h, discharging;
Step 5: the product that the upper step obtains is put into vacuum drying oven 30-60 ℃ 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 have good thermotolerance, ablation resistance and a mechanical property, have wide range of applications, possess significant economic and social benefit.
Description of drawings
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 common resol.
Embodiment
Embodiment one:
1) be respectively 24 parts, 10 parts by the mass fraction of phenol and formaldehyde and feed intake, and add massfraction be 40% sodium hydroxide solution 2.5g as catalyzer, warming while stirring to 70 ℃, reaction 1h;
2) by mass fraction be: 40 parts of ethanol, 20 parts of methyl ethyl diketones, 20 parts of zirconium oxychlorides, 1 part of configuration zirconyl chloride solution of hydrogen peroxide;
3) temperature to 95 of regulating thermostatic water-bath ℃ drips the zirconyl chloride solution for preparing, and the pH value of controlling solution is 8-9;
4) after temperature reaches 95 ℃, after insulation 2h, discharging;
5) product that the upper step was obtained is put into 50 ℃ of insulation 5h of vacuum drying oven, namely obtains modified zirconia resol.
Embodiment two:
1) be respectively 24 parts, 10 parts by the mass fraction of phenol and formaldehyde and feed intake, and add massfraction be 40% sodium hydroxide solution 2g as catalyzer, warming while stirring to 70 ℃, reaction 1h;
2) by mass fraction be: 40 parts of ethanol, 20 parts of methyl ethyl diketones, 10 parts of zirconium oxychlorides, 1 part of configuration zirconyl chloride solution of hydrogen peroxide;
3) temperature to 85 of regulating thermostatic water-bath ℃ drips the zirconyl chloride solution for preparing, and the pH value of controlling solution is 8-9;
4) after temperature reaches 85 ℃, after insulation 2h, discharging;
5) product that the upper step was obtained is put into 50 ℃ of insulation 5h of vacuum drying oven, namely obtains modified zirconia resol.
Embodiment three:
1) be respectively 24 parts, 10 parts by the mass fraction of phenol and formaldehyde and feed intake, and add massfraction be 40% sodium hydroxide solution 1.5g as catalyzer, warming while stirring to 70 ℃, reaction 1h;
2) by mass fraction be: 40 parts of ethanol, 20 parts of methyl ethyl diketones, 15 parts of zirconium oxychlorides, 1 part of configuration zirconyl chloride solution of hydrogen peroxide;
3) temperature to 85 of regulating thermostatic water-bath ℃ drips the zirconyl chloride solution for preparing, and the pH value of controlling solution is 8-9;
4) after temperature reaches 85 ℃, after insulation 2.5h, discharging;
5) product that the upper step was obtained is put into 50 ℃ of insulation 5h of vacuum drying oven, namely obtains modified zirconia resol.
The resistance to elevated temperatures of the modified zirconia resol of the present invention's preparation is more better than common resol.The thermal weight loss of modified zirconia resol and common resol 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 common resol; When temperature reached 600 ℃, the carbon yield of modified zirconia resol was 62%, far above common resol (carbon yield of ordinary resin 600 ℃ the time is 48%).The infrared spectra comparison diagram of modified zirconia resol and common resol as shown in Figure 2, in figure, the c curve is the infrared spectra curve of modified zirconia resol, curve d is the infrared spectra curve of common resol.1355cm in curve c
-1, 1527cm
-1, 1694cm
-1Stronger peak appears in the wavelength place, proves absolutely that zirconium introduced in the macromolecular chain of resol; 1160cm in curve c
-1The peak at place obviously weakens by force, illustrates that the ehter bond in prepared modified zirconia resol obviously reduces.
Claims (2)
1. a 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.
2. method for preparing modified zirconia resol claimed in claim 1 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 ℃, and reaction 1-2h obtains resin reaction liquid;
Step 2: press 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: stir on intensification limit, limit, drips simultaneously the zirconyl chloride solution for preparing, and the pH value of controlling solution is 7-9;
Step 4: after temperature reaches 80-95 ℃, after insulation 2-2.5h, discharging;
Step 5: the product that the upper step obtains is put into vacuum drying oven 30-60 ℃ of insulation 3-5h, namely obtain modified zirconia resol.
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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 CN103172811B (en) | 2015-02-25 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435766A (en) * | 2013-08-30 | 2013-12-11 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| CN104341949A (en) * | 2013-08-02 | 2015-02-11 | 中国石油天然气股份有限公司 | Wear-resistant inner anticorrosive paint and preparation and application thereof |
| CN112250464A (en) * | 2020-10-26 | 2021-01-22 | 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 |
Citations (1)
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| CN101439976A (en) * | 2008-12-24 | 2009-05-27 | 本钢板材股份有限公司 | Composition for making submerged nozzle |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439976A (en) * | 2008-12-24 | 2009-05-27 | 本钢板材股份有限公司 | Composition for making submerged nozzle |
Non-Patent Citations (2)
| Title |
|---|
| 王于刚等: "锆改性酚醛树脂的合成与表征", 《化学推进剂与高分子材料》, vol. 7, no. 4, 25 July 2009 (2009-07-25), pages 37 - 39 * |
| 石岳等: "含锆C/C复合材料制备的研究", 《第22届炭-石墨材料学术会议论文集：炭学文集》, 1 October 2010 (2010-10-01), pages 104 - 111 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341949A (en) * | 2013-08-02 | 2015-02-11 | 中国石油天然气股份有限公司 | Wear-resistant inner anticorrosive paint and preparation and application thereof |
| CN104341949B (en) * | 2013-08-02 | 2016-12-28 | 中国石油天然气股份有限公司 | Wear-resistant inner anticorrosive paint and preparation and application thereof |
| CN103435766A (en) * | 2013-08-30 | 2013-12-11 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| 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 |
| CN112250464A (en) * | 2020-10-26 | 2021-01-22 | 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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