CN101481446B - Preparation of spherical phenolic resin type polymer - Google Patents
Preparation of spherical phenolic resin type polymer Download PDFInfo
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- CN101481446B CN101481446B CN2008100021708A CN200810002170A CN101481446B CN 101481446 B CN101481446 B CN 101481446B CN 2008100021708 A CN2008100021708 A CN 2008100021708A CN 200810002170 A CN200810002170 A CN 200810002170A CN 101481446 B CN101481446 B CN 101481446B
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Abstract
The invention discloses a preparation method of a spherical phenolic resin polymer; the method overcomes the disadvantages that granularity distribution is hard to control, the degree of sphericity is low or a great number of reaction steps are included, and the process is complex in the original preparation method; and the method realizes that spherical metlbond polymer is prepared by a one-step method, thus greatly simplifying synthetic process and obtaining spherical polymer with smooth surface and uniform granularity distribution. After ethyleneglycol monophenylether, formic acid, formaldehyde and droxyethylcellulose used as a stabilizing agent are evenly mixed, concentrated sulfuric acid is slowly dropwise added; after the dropwise addition, the reaction mixture is reacted by heating at a certain temperature and a certain rotating speed; the product is dried after separation, aqueous slkali soaking and water washing. After the one-step method, the spherical phenolic resin polymer with high sphericity degree and 0.5-1.2mm of particle size range is obtained; the spherical phenolic resin polymer can be used as base material of a macromolecule adsorbing agent and is applied to the fields of biological medicine, chromatographic resolution, and environmental improvement, etc.
Description
(1) technical field: the present invention relates to a kind of preparation method of spherical phenolic resin polymer, especially prepare the method for spherical phenolic resin polymer through single step reaction.
(2) background technology: resol is the high molecular polymer that is formed through the polycondensation polyreaction under the katalysis of acid or alkali by phenol and formaldehyde, is to succeed in developing the also representative of business-like thermosetting polymer in the world the earliest.Resol has two kinds of polycondensation methods usually, promptly adopts the excessive method of phenol under the excessive and acid catalysis of formaldehyde to prepare the resol of Resol and Novolac type respectively under base catalysis.In recent years, spherical resol because have the physical strength height, spheroid has a series of premium propertiess such as good rollability, good sphericity, smooth surface, be used widely at aspects such as environmental protection, biomedicine, military affairs, chemical industry, analysis, energy storage materials.At present, the preparation method of spherical resol mainly contains following two kinds of methods: mix phenol and formaldehyde (1) by certain molar ratio after, under the katalysis of acid or alkali, obtain insoluble, infusible resol, be broken into the particle of certain particle size again through mechanical workout.(2) publication number is that the Chinese invention patent of CN 98115717.3 discloses with thermoplastic resol to be raw material, to prepare the method for spherical resol.This method is dissolved in novolac resin and solidifying agent in the solvent with certain proportion earlier and mixes, and then mixed solution is gone down to desolventize in reduced pressure, obtains containing the solid phenolic resin of solidifying agent.Above-mentioned solid mixt is broken into the particle of predetermined particle size,, it is dispersed in is heated to 110～150 degrees centigrade in the dispersion medium and changes into spherical resol as the raw material of balling-up.More than two kinds of methods that prepare spherical resol, the former particle diameter be difficult to control, labour intensity is big, sphericity is relatively poor.The latter need pass through polystep reaction, and reaction time is long, and the balling-up process is loaded down with trivial details.
(3) summary of the invention: the objective of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of single stage method to prepare the method for spherical phenolic resin polymer.
Purpose of the present invention can reach by following measure: ethyleneglycol monophenylether, formaldehyde, formic acid and stablizer are pressed 15～20% of reactant gross weight respectively, 25～40%, 35～44%, after 0.38～1.0% mixed is even, slowly drip 7～12% the vitriol oil account for the reactant gross weight again, after dropwising, with reaction mixture heated and stirred reaction 6～8 hours.With reaction mixture cooling, filter out sphere polymers, with 5% sodium hydroxide solution immersion, deionized water wash, obtain spherical phenolic resin polymer after the oven dry again.
Purpose of the present invention can also reach by following measure: ethyleneglycol monophenylether, formaldehyde, formic acid and stablizer are pressed 17～19% of reactant gross weight respectively, 30～35%, 37～39%, after 0.4～1.0% mixed is even, slowly drip 8～12% the vitriol oil account for the reactant gross weight again, after dropwising, with reaction mixture heated and stirred reaction 6～8 hours.With reaction mixture cooling, filter out sphere polymers, with 5% sodium hydroxide solution immersion, deionized water wash, obtain spherical phenolic resin polymer after the oven dry again.Formaldehyde content in the used formaldehyde of the present invention is 34～37%, and the employing Natvosol is a stablizer, and employing formic acid is solvent, and the content of formic acid is more than or equal to 88%.The present invention is heated to 60-70 degree centigrade with reaction mixture and reacts in water-bath, churned mechanically speed is that per minute 500～800 changes.
Compared with the prior art the present invention has following advantage: preparation method provided by the invention is simple and easy to do, only need just to obtain spherical phenolic resin polymer through single step reaction, preparation process is greatly simplified, and the size distribution of resultant spherical phenolic resin polymer is even, smooth surface, and sphericity is good.
(4) description of drawings:
Fig. 1 is the electron scanning micrograph of the spherical phenolic resin polymer of embodiment 1.
Fig. 2 is the electron scanning micrograph of the spherical phenolic resin polymer of embodiment 2.
Fig. 3 is the electron scanning micrograph of the spherical phenolic resin polymer of embodiment 3.
Fig. 4 is the size distribution figure of the spherical phenolic resin polymer of embodiment 4.
Fig. 5 is the size distribution figure of the spherical phenolic resin polymer of embodiment 5.
Fig. 6 is the size distribution figure of the spherical phenolic resin polymer of embodiment 6.
(5) embodiment: following detailed description the present invention also provides several embodiment:
Embodiment 1: ethyleneglycol monophenylether 27.74 grams, and formic acid 61.00 grams, formaldehyde 70.42 grams, Natvosol 1.29 grams after mixing, at room temperature slowly drip the 14.67 gram vitriol oils.After dropwising, regulate stir speed (S.S.) per minute 700 and change, be heated to 70 degrees centigrade, reacted 6 hours.The sphere polymers that generates is filtered,, be washed with water to neutrality again, dry with 5% soaking with sodium hydroxide solution 5 hours.
The electron scanning micrograph of the spherical phenolic resin polymer of gained as shown in Figure 1.
Embodiment 2: ethyleneglycol monophenylether 27.74 grams, and formic acid 61.00 grams, formaldehyde 35.55 grams, Natvosol 0.99 gram after mixing, at room temperature slowly drips the 14.67 gram vitriol oils.After dropwising, regulate stir speed (S.S.) per minute 600 and change, be heated to 65 degrees centigrade, reacted 7 hours.The sphere polymers that generates is filtered, soaked 5 hours, be washed with water to neutrality again, oven dry with 5% sodium hydroxide solution.
The electron scanning micrograph of the spherical phenolic resin polymer of gained as shown in Figure 2.
Embodiment 3: ethyleneglycol monophenylether 27.74 grams, and formic acid 61.00 grams, formaldehyde 53.33 grams, Natvosol 0.68 gram after mixing, at room temperature slowly drips the 14.67 gram vitriol oils.After dropwising, regulate stir speed (S.S.) per minute 500 and change, be heated to 70 degrees centigrade, reacted 8 hours.The sphere polymers that generates is filtered, soaked 5 hours, be washed with water to neutrality again, oven dry with 5% sodium hydroxide solution.
The electron scanning micrograph of the spherical phenolic resin polymer of gained as shown in Figure 3.
Embodiment 4: ethyleneglycol monophenylether 27.74 grams, and formic acid 61.00 grams, formaldehyde 53.33 grams, Natvosol 1.60 grams after mixing, at room temperature slowly drip the 14.67 gram vitriol oils.After dropwising, regulate stir speed (S.S.) per minute 800 and change, be heated to 60 degrees centigrade, reacted 8 hours.The sphere polymers that generates is filtered, soaked 5 hours, be washed with water to neutrality again, oven dry with 5% sodium hydroxide solution.
The median size of the spherical phenolic resin polymer of gained is 926.6 microns, as shown in Figure 4.
Embodiment 5: ethyleneglycol monophenylether 27.74 grams, and formic acid 61.00 grams, formaldehyde 44.82 grams, Natvosol 0.72 gram after mixing, at room temperature slowly drips the 18.34 gram vitriol oils.After dropwising, regulate stir speed (S.S.) per minute 700 and change, be heated to 70 degrees centigrade, reacted 6 hours.The sphere polymers that generates is filtered, soaked 5 hours, be washed with water to neutrality again, oven dry with 5% sodium hydroxide solution.
The median size of the spherical phenolic resin polymer of gained is 756.7 microns, as shown in Figure 5.
Embodiment 6: ethyleneglycol monophenylether 27.74 grams, and formic acid 61.00 grams, formaldehyde 53.33 grams, Natvosol 1.01 grams after mixing, at room temperature slowly drip the 14.67 gram vitriol oils.After dropwising, regulate stir speed (S.S.) per minute 800 and change, be heated to 65 degrees centigrade, reacted 8 hours.The sphere polymers that generates is filtered, soaked 5 hours, be washed with water to neutrality again, oven dry with 5% sodium hydroxide solution.
The median size of the spherical phenolic resin polymer of gained is 736 microns, as shown in Figure 6.
Claims (6)
1. the preparation method of a spherical phenolic resin polymer, it is characterized in that: with ethyleneglycol monophenylether, formaldehyde, formic acid and Natvosol are pressed 15～20% of reactant gross weight respectively, 25～40%, 35～44%, after 0.38～1.0% mixed is even, slowly drip 7～12% the vitriol oil account for the reactant gross weight again, after dropwising, with reaction mixture heated and stirred reaction 6～8 hours, reaction mixture is cooled off, filter out sphere polymers, soak with 5% sodium hydroxide solution again, deionized water wash obtains spherical phenolic resin polymer after the oven dry.
2. the preparation method of a kind of spherical phenolic resin polymer according to claim 1, it is characterized in that: with ethyleneglycol monophenylether, formaldehyde, formic acid and Natvosol are pressed 17～19% of reactant gross weight respectively, 30～35%, 37～39%, after 0.4～1.0% mixed is even, slowly drip 8～12% the vitriol oil account for the reactant gross weight again, after dropwising, with reaction mixture heated and stirred reaction 6～8 hours, reaction mixture is cooled off, filter out sphere polymers, soak with 5% sodium hydroxide solution again, deionized water wash obtains spherical phenolic resin polymer after the oven dry.
3. the preparation method of a kind of spherical phenolic resin polymer according to claim 1 and 2, it is characterized in that: the formaldehyde content in the formaldehyde is 37～40%.
4. the preparation method of a kind of spherical phenolic resin polymer according to claim 1 and 2 is characterized in that: the formic acid content in the formic acid is for more than or equal to 88%.
5. the preparation method of a kind of spherical phenolic resin polymer according to claim 1 and 2 is characterized in that: reaction mixture is heated to 60～70 degrees centigrade reacts in water-bath.
6. the preparation method of a kind of spherical phenolic resin polymer according to claim 1 and 2 is characterized in that: churned mechanically speed is that per minute 500～800 changes.
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| CN2008100021708A CN101481446B (en) | 2008-01-11 | 2008-01-11 | Preparation of spherical phenolic resin type polymer |
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| CN2008100021708A CN101481446B (en) | 2008-01-11 | 2008-01-11 | Preparation of spherical phenolic resin type polymer |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3823103A (en) * | 1971-07-21 | 1974-07-09 | Union Carbide Corp | Aqueous dispersions based on heathardenable phenolic resins containing a gum mixture stabilizing agent |
| CN1443792A (en) * | 2003-03-21 | 2003-09-24 | 莱州市恒力达化工有限公司 | Microsphere thermosetting phenolic resin and its preparation process |
| CN1583837A (en) * | 2004-06-11 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | Preparation of phenolic resin based micro-balls |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3823103A (en) * | 1971-07-21 | 1974-07-09 | Union Carbide Corp | Aqueous dispersions based on heathardenable phenolic resins containing a gum mixture stabilizing agent |
| CN1443792A (en) * | 2003-03-21 | 2003-09-24 | 莱州市恒力达化工有限公司 | Microsphere thermosetting phenolic resin and its preparation process |
| CN1583837A (en) * | 2004-06-11 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | Preparation of phenolic resin based micro-balls |
Non-Patent Citations (1)
| Title |
|---|
| 孙言志, 纪春暖, 刘春萍, 曲荣君.悬挂双羰基功能基的酚醛树脂的合成及表征.《烟台师范学院学报(自然科学版)》.2002,第18卷(第2期),88-91. * |
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