CN112057905A - Polyether modified organic silicon defoaming agent safe to strains and preparation method thereof - Google Patents
Polyether modified organic silicon defoaming agent safe to strains and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of defoaming agents, and particularly discloses a polyether modified organic silicon defoaming agent safe to strains and a preparation method thereof, wherein the preparation method comprises the following steps: sequentially adding the silicon dioxide nano-microspheres, the dimethyl silicone oil, the DMF and the deionized water into a reaction bottle, adding ammonia water while stirring, heating to 50-70 ℃, reacting for 1-2 hours, cooling to room temperature, centrifuging, washing a precipitate with ethanol, and drying to obtain the silicon dioxide nano-microspheres grafted and modified by the dimethyl silicone oil; adding 30-60 parts of silicon dioxide nano microspheres grafted and modified by dimethyl silicone oil, 30-50 parts of polyether modified silicone oil, 1-10 parts of thickening agent, 2-10 parts of emulsifier and 10-50 parts of water into a dispersion tank, heating to 180 ℃ and 200 ℃, stirring for 2-3 hours, then reducing the temperature to 50-60 ℃ in a gradient manner under the stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent. The defoaming agent has the advantages of low surface tension, high defoaming speed, long foam inhibition time, small using amount, no toxicity or harm to strains, wide application range and the like.
Description
Technical Field
The invention relates to the technical field of defoaming agents, in particular to a polyether modified organic silicon defoaming agent safe to strains and a preparation method thereof.
Background
The defoaming agent is one of the indispensable auxiliaries in many production at present. Has been widely applied to various fields such as chemical industry, food, textile, coating, petroleum, paper making, printing and dyeing and the like. The defoaming agents are various in kind and different in performance, and can be classified into mineral oil defoaming agents, polyether defoaming agents, silicone defoaming agents, polyether modified silicone defoaming agents and the like according to the composition. The polyether defoamer is non-toxic, odorless, good in water dispersion and strong in foam inhibition capacity, but is low in foam breaking rate, and cannot effectively extinguish a large amount of foam. The organic silicon defoamer has high defoaming capability, good chemical stability and wide application, but has poor foam inhibition capability, poor dispersion effect in a water phase system, difficult emulsification, influence on the growth of strains, difficult removal of silicon spots and certain limitation in the fermentation, textile and printing and dyeing industries. In recent years, polyether modified organosilicon defoaming agents are the focus of research, and polyether chains are introduced on polysiloxane chains through grafting by a condensation technology to obtain a hydrophilic and lipophilic silicon ether copolymer. The advantages of both the polyether defoamer and the organic silicon defoamer are integrated, the organic silicon defoamer has the excellent characteristics of high defoaming efficiency, stability and the like of the organic silicon defoamer, has the characteristics of strong foam inhibition capability, no toxicity, good dispersibility and the like of the polyether defoamer, and is more widely applied.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a polyether modified organic silicon defoaming agent which is safe to strains and a preparation method thereof, and the defoaming agent has the characteristics of low surface tension, high defoaming speed, long foam inhibition time, small using amount, no toxicity, no harm, wide application range and the like.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a polyether modified silicone defoamer safe to bacterial species, comprising the steps of:
(1) sequentially adding the silicon dioxide nano-microspheres, the simethicone, the N, N-methyl formamide (DMF) and deionized water into a reaction bottle, adding ammonia water while stirring, heating to 50-70 ℃, reacting for 1-2 hours, naturally cooling to room temperature, centrifuging, washing precipitates with ethanol, and drying to obtain the simethicone grafted and modified silicon dioxide nano-microspheres;
(2) and (2) adding 30-60 parts of the silicon dioxide nano microspheres grafted and modified by the dimethyl silicone oil, 30-50 parts of the polyether modified silicone oil, 1-10 parts of the thickening agent, 2-10 parts of the emulsifier and 10-50 parts of water which are prepared in the step (1) into a dispersion tank, heating to 180 ℃ for 200 ℃, stirring for 2-3 hours, then reducing the temperature to 50-60 ℃ in a gradient manner under the stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent.
Optionally, in the step (1), the ratio of the silicon dioxide nano-microspheres, the dimethyl silicone oil, the N, N-methyl formamide (DMF), and the ammonia water is 1-2: 0.5-1.0: 20-30:1-2 (w/v/v/v).
Optionally, in the step (1), the drying temperature is 50-60 ℃.
Further, in the step (1), the preparation method of the silica nanospheres comprises: adding ammonia water into absolute ethyl alcohol, dropwise adding Tetraethoxysilane (TEOS) under vigorous stirring, then stirring for 20-24 hours at 20-30 ℃, and then washing, centrifuging and vacuum-freezing to obtain the silicon dioxide nano-microspheres.
Optionally, in the preparation method of the silica nanosphere, the volume usage ratio of ammonia water, absolute ethyl alcohol and tetraethoxysilane is 5-6: 100:3-4.
Optionally, in the preparation method of the silica nanosphere, washing is performed with absolute ethyl alcohol.
Further, in the step (2), the preparation method of the polyether modified silicone oil comprises the following steps: adding chloroplatinic acid catalyst dissolved by isopropanol into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, and continuing stirring for reaction for 6-8 hours after the hydrogen-containing silicone oil is added to obtain the polyether modified silicone oil.
Optionally, in the preparation method of the polyether modified silicone oil, the molar ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1-1.5: 1.
Optionally, in the preparation method of the polyether modified silicone oil, the amount of the chloroplatinic acid catalyst is 0.03-0.05% of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil.
Optionally, in the step (2), the thickener is at least one selected from hydroxyethyl cellulose, sodium carboxymethyl cellulose, xanthan gum, sodium alginate and glyceryl monostearate.
Optionally, in the step (2), the emulsifier is selected from at least one of span 20, tween 20, span 60, tween 60, span 80 and tween 80.
The invention also provides the polyether modified organic silicon defoaming agent prepared by the method.
As mentioned above, the polyether modified organic silicon defoamer safe to strains and the preparation method thereof have the following beneficial effects:
the polyether modified silicone oil and the silicon dioxide nano microspheres modified by the dimethyl silicone oil are added into the polyether modified organic defoaming agent, so that the polyether modified organic defoaming agent has the advantages of low surface tension, high defoaming speed, long foam inhibition time, small using amount, no toxicity or harm to strains, wide application range and the like. Due to the nanometer SiO2The nano silicon dioxide and the organic silicon are compounded, so that the problems of poor dispersibility, difficulty in emulsification and the like of the organic silicon can be effectively solved, and the defoaming performance of the defoaming agent is improved through the synergistic effect of the nano silicon dioxide and the organic silicon. However, the nano-silica particles have a large amount of hydrophilic hydroxyl groups on the surface, have large surface polarity, and have hydrophilicity and lipophobicity, are easy to agglomerate under the action of a large amount of hydrogen bonds in an organic medium, particularly in a silicone oil system, and have poor dispersion effect, so that the nano-silica particles are difficult to effectively exert the action when being directly added into an organic silicon system. According to the invention, the silicon dioxide nano-microspheres are adopted and subjected to graft modification, and the simethicone is loaded on the silicon dioxide nano-microspheres, so that the problem that the simethicone is easy to agglomerate in organic silicon is effectively solved, the stability of the defoaming agent is ensured, and the dispersibility and the foam inhibition capability of the simethicone in a water phase system are improved.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The invention provides a polyether modified organic silicon defoaming agent safe to strains, which comprises the following components in parts by weight: 30-60 parts of modified silicon dioxide nano microspheres, 30-50 parts of polyether modified silicone oil, 1-10 parts of thickening agent, 2-10 parts of emulsifier and 10-50 parts of water, wherein the preparation method comprises the following steps:
(1) adding ammonia water into absolute ethyl alcohol, dropwise adding Tetraethoxysilane (TEOS) under vigorous stirring, then stirring for 20-24 hours at 20-30 ℃, centrifuging after the reaction is finished, washing the precipitate with absolute ethyl alcohol, centrifuging again, repeating for multiple times, and finally performing vacuum freezing to obtain the silicon dioxide nano microspheres.
(2) And (2) sequentially adding the silicon dioxide nano-microspheres obtained in the step (1), dimethyl silicon oil, N-methyl formamide (DMF) and deionized water into a reaction bottle, adding ammonia water under stirring, heating to 50-70 ℃, reacting for 1-2 hours, naturally cooling to room temperature, centrifuging, washing precipitates with ethanol, and drying in an oven at 50-60 ℃ to obtain the silicon dioxide nano-microspheres grafted and modified by the dimethyl silicon oil.
(3) Dissolving a chloroplatinic acid catalyst by using isopropanol, then adding the solution into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, and continuing stirring for reaction for 6-8 hours after the hydrogen-containing silicone oil is added to obtain the polyether modified silicone oil.
(4) And (3) adding the silicon dioxide nano microspheres grafted and modified by the dimethyl silicone oil prepared in the step (2), the polyether modified silicone oil prepared in the step (3), the thickening agent, the emulsifier and water into a dispersion tank, heating to 180 ℃ and 200 ℃, stirring for 2-3 hours, then reducing the temperature to 50-60 ℃ in a gradient manner under the stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent.
In the step (1), in the preparation method of the silica nanospheres, the volume usage ratio of ammonia water, absolute ethyl alcohol and tetraethoxysilane is 5-6: 100:3-4.
In the step (2), the dosage ratio of the silicon dioxide nano-microspheres, the dimethyl silicone oil, the N, N-methyl formamide (DMF) and the ammonia water is 1-2: 0.5-1.0: 20-30:1-2 (w/v/v/v).
In the step (3), in the preparation method of the polyether modified silicone oil, the molar usage ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1-1.5: 1.
In the step (3), in the preparation method of the polyether modified silicone oil, the dosage of the chloroplatinic acid catalyst is 0.03-0.05% of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil.
Wherein in the step (4), in the step (2), the thickener is at least one selected from hydroxyethyl cellulose, sodium carboxymethyl cellulose, xanthan gum, sodium alginate and glyceryl monostearate.
Wherein in the step (4), the emulsifier is at least one selected from span 20, tween 20, span 60, tween 60, span 80 and tween 80.
Specific examples are given below to further illustrate the preparation of the present invention. The reagents used in the following examples are all commercially available.
Example 1
The preparation method of the polyether modified organic silicon defoaming agent safe to the strains in the embodiment is as follows:
(1) adding 3mL of ammonia water into 100mL of absolute ethyl alcohol, dropwise adding 5mL of Tetraethoxysilane (TEOS) under vigorous stirring, then stirring for 24 hours at 20 ℃, centrifuging after the reaction is finished, washing the precipitate with absolute ethyl alcohol, centrifuging again, repeating for multiple times, and finally performing vacuum freezing to obtain the silicon dioxide nano microspheres.
(2) And (2) sequentially adding 1g of the silicon dioxide nano-microspheres obtained in the step (1), 0.5mL of simethicone, 20mL of N, N-methyl formamide (DMF) and 10mL of deionized water into a reaction bottle, adding 1mL of ammonia water under stirring, heating to 70 ℃, reacting for 2 hours, naturally cooling to room temperature, centrifuging, washing precipitates with ethanol, and drying in an oven at 60 ℃ to obtain the simethicone graft modified silicon dioxide nano-microspheres.
(3) Dissolving a chloroplatinic acid catalyst (solid) by using a small amount of isopropanol, then adding the solution into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, wherein the molar ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1:1, the dosage of the chloroplatinic acid catalyst is 0.03 percent of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil, and after the hydrogen-containing silicone oil is added, continuously stirring for reaction for 8 hours to obtain the polyether modified silicone oil.
(4) And (3) adding 30 parts of the silicon dioxide nano-microspheres grafted and modified by the dimethyl silicone oil prepared in the step (2), 30 parts of the polyether modified silicone oil prepared in the step (3), 1 part of hydroxyethyl cellulose, 202 parts of tween and 10 parts of water into a dispersion tank, heating to 180 ℃, stirring for 2 hours, then reducing the temperature to 50 ℃ in a gradient manner under a stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent.
Example 2
The preparation method of the polyether modified organic silicon defoaming agent safe to the strains in the embodiment is as follows:
(1) adding 4mL of ammonia water into 100mL of absolute ethyl alcohol, dropwise adding 6mL of Tetraethoxysilane (TEOS) under vigorous stirring, then stirring for 20 hours at 30 ℃, centrifuging after the reaction is finished, washing the precipitate with absolute ethyl alcohol, centrifuging again, repeating for multiple times, and finally performing vacuum freezing to obtain the silicon dioxide nano microspheres.
(2) And (2) sequentially adding 2g of the silicon dioxide nano-microspheres obtained in the step (1), 1.0mL of simethicone, 30mL of N, N-methyl formamide (DMF) and 10mL of deionized water into a reaction bottle, adding 2mL of ammonia water under stirring, heating to 60 ℃, reacting for 1.5 hours, naturally cooling to room temperature, centrifuging, washing precipitates with ethanol, and drying in an oven at 50 ℃ to obtain the simethicone grafted and modified silicon dioxide nano-microspheres.
(3) Dissolving a chloroplatinic acid catalyst (solid) by using a small amount of isopropanol, then adding the solution into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, wherein the molar ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1.5:1, the dosage of the chloroplatinic acid catalyst is 0.04 percent of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil, and after the hydrogen-containing silicone oil is added, continuously stirring for reaction for 6 hours to obtain the polyether modified silicone oil.
(4) And (3) adding 60 parts of the silicon dioxide nano-microspheres grafted and modified by the dimethyl silicone oil prepared in the step (2), 50 parts of the polyether modified silicone oil prepared in the step (3), 10 parts of sodium carboxymethylcellulose, 2010 parts of tween and 50 parts of water into a dispersion tank, heating to 200 ℃, stirring for 3 hours, then reducing the temperature to 60 ℃ in a gradient manner under a stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent.
Example 3
The preparation method of the polyether modified organic silicon defoaming agent safe to the strains in the embodiment is as follows:
(1) adding 3mL of ammonia water into 100mL of absolute ethyl alcohol, dropwise adding 5mL of Tetraethoxysilane (TEOS) under vigorous stirring, then stirring for 24 hours at 20 ℃, centrifuging after the reaction is finished, washing the precipitate with absolute ethyl alcohol, centrifuging again, repeating for multiple times, and finally performing vacuum freezing to obtain the silicon dioxide nano microspheres.
(2) And (2) sequentially adding 1.5g of the silicon dioxide nano microspheres obtained in the step (1), 0.6mL of simethicone, 25mL of N, N-methyl formamide (DMF) and 10mL of deionized water into a reaction bottle, adding 1.5mL of ammonia water under stirring, heating to 60 ℃, reacting for 2 hours, naturally cooling to room temperature, centrifuging, washing precipitates with ethanol, and drying in an oven at 55 ℃ to obtain the simethicone graft modified silicon dioxide nano microspheres.
(3) Dissolving a chloroplatinic acid catalyst (solid) by using a small amount of isopropanol, then adding the solution into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, wherein the molar ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1.2:1, the dosage of the chloroplatinic acid catalyst is 0.05 percent of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil, and after the hydrogen-containing silicone oil is added, continuously stirring for reaction for 7 hours to obtain the polyether modified silicone oil.
(4) And (3) adding 40 parts of the silicon dioxide nano microspheres grafted and modified by the dimethyl silicone oil prepared in the step (2), 50 parts of the polyether modified silicone oil prepared in the step (3), 5 parts of hydroxyethyl cellulose, 805 parts of span and 30 parts of water into a dispersion tank, heating to 190 ℃, stirring for 3 hours, then reducing the temperature to 55 ℃ in a gradient manner under a stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent.
Example 4
The preparation method of the polyether modified organic silicon defoaming agent safe to the strains in the embodiment is as follows:
(1) adding 3mL of ammonia water into 100mL of absolute ethyl alcohol, dropwise adding 5mL of Tetraethoxysilane (TEOS) under vigorous stirring, then stirring for 24 hours at 20 ℃, centrifuging after the reaction is finished, washing the precipitate with absolute ethyl alcohol, centrifuging again, repeating for multiple times, and finally performing vacuum freezing to obtain the silicon dioxide nano microspheres.
(2) And (2) sequentially adding 1.5g of the silicon dioxide nano microspheres obtained in the step (1), 0.6mL of simethicone, 25mL of N, N-methyl formamide (DMF) and 10mL of deionized water into a reaction bottle, adding 1.5mL of ammonia water under stirring, heating to 60 ℃, reacting for 2 hours, naturally cooling to room temperature, centrifuging, washing precipitates with ethanol, and drying in an oven at 55 ℃ to obtain the simethicone graft modified silicon dioxide nano microspheres.
(3) Dissolving a chloroplatinic acid catalyst (solid) by using a small amount of isopropanol, then adding the solution into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, wherein the molar ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1.2:1, the dosage of the chloroplatinic acid catalyst is 0.05 percent of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil, and after the hydrogen-containing silicone oil is added, continuously stirring for reaction for 7 hours to obtain the polyether modified silicone oil.
(4) And (3) adding 50 parts of the silicon dioxide nano-microspheres grafted and modified by the dimethyl silicone oil prepared in the step (2), 40 parts of the polyether modified silicone oil prepared in the step (3), 6 parts of hydroxyethyl cellulose, 208 parts of tween and 40 parts of water into a dispersion tank, heating to 200 ℃, stirring for 3 hours, then reducing the temperature to 55 ℃ in a gradient manner under a stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent.
Comparative example 1
The preparation method of the defoaming agent in this comparative example is as follows:
(1) dissolving a chloroplatinic acid catalyst (solid) by using a small amount of isopropanol, then adding the solution into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, wherein the molar ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1.2:1, the dosage of the chloroplatinic acid catalyst is 0.05 percent of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil, and after the hydrogen-containing silicone oil is added, continuously stirring for reaction for 7 hours to obtain the polyether modified silicone oil.
(2) And (2) adding 40 parts of polyether modified silicone oil prepared in the step (1), 50 parts of dimethyl silicone oil, 50 parts of nano silicon dioxide, 6 parts of hydroxyethyl cellulose, 208 parts of tween and 40 parts of water into a dispersion tank, heating to 200 ℃, stirring for 3 hours, then reducing the temperature to 55 ℃ in a gradient manner under a stirring state, and finally naturally cooling to obtain the defoaming agent.
Comparative example 2
The preparation method of the defoaming agent in this comparative example is as follows:
(1) dissolving a chloroplatinic acid catalyst (solid) by using a small amount of isopropanol, then adding the solution into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, wherein the molar ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1.2:1, the dosage of the chloroplatinic acid catalyst is 0.05 percent of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil, and after the hydrogen-containing silicone oil is added, continuously stirring for reaction for 7 hours to obtain the polyether modified silicone oil.
(2) And (2) adding 40 parts of polyether modified silicone oil prepared in the step (1), 50 parts of dimethyl silicone oil, 6 parts of hydroxyethyl cellulose, 208 parts of tween and 40 parts of water into a dispersion tank, heating to 200 ℃, stirring for 3 hours, then reducing the temperature to 55 ℃ in a gradient manner under a stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent.
Testing of defoaming agent Performance
The polyether-modified silicone defoaming agents prepared in examples 1 to 4, the defoaming agents in comparative examples 1 to 2, and two commercially available defoaming agents (1, Henxin chemical THI-X-299 polyether-modified silicon defoaming agent; 2, Defeng polyether-modified silicon defoaming agent) were subjected to performance tests according to the following test methods.
(1) Defoaming and foam suppressing properties: a Roche foam tester is adopted to test defoaming performance and foam inhibition performance, and the specific method comprises the following steps:
adding 200mL of 2 mass percent sodium dodecyl sulfate foaming liquid into a 1000mL measuring cylinder, keeping the temperature to 25 ℃, then inserting a blowing pipe into the bottom of the measuring cylinder, introducing nitrogen at the speed of 3L/min until the foam height reaches 800mL, stopping bubbling, immediately adding 1mL of defoaming agent diluted by 30 times, and recording the time when the foam falls to 50mL by using a stopwatch, wherein the time is the defoaming time. The shorter the time, the better the defoaming performance of the defoaming agent.
After the defoaming performance test is finished, a switch is turned on, nitrogen is introduced at the speed of 3L/min, the time is recorded by a stopwatch, and the time when the foam height rises to 800mL is the foam inhibition time. The longer the time, the better the foam suppressing performance of the defoamer.
(2) Dilution stability: dropping a drop of defoamer emulsion into a beaker filled with deionized water, slightly oscillating, observing whether the defoamer emulsion is layered or demulsified, and sequentially marking as excellent (the emulsion is rapidly dispersed, and the liquid surface has no oily substance), good (the emulsion is rapidly dispersed, and the liquid surface has no oily substance), medium (the emulsion is slowly dispersed, and a little floccule is on the liquid surface), and poor (the emulsion is not easily dispersed, and the floccule is difficult to disappear) according to the dispersion condition in water.
(3) Centrifugal stability: diluting the defoaming agent emulsion by 5 times with deionized water, placing in a centrifuge tube, centrifuging at 3000r/min with a high-speed centrifuge, stopping the centrifuge for observation once every 5min, and recording the layering time.
The natural storage stability time of the defoaming agent as a commodity is more than 6 months, and the emulsion is not layered after being centrifuged at 3000r/min for 30 min.
The test results were as follows:
TABLE 1 Performance test results for polyether modified Silicone defoamers in examples 1-4
As can be seen from the test results in Table 1, the mineral oil defoamers prepared in examples 1 to 6 of the present invention all had superior defoaming performance, foam suppressing performance, dilution stability and centrifugal stability to the defoamers of comparative examples 1 to 2 and the two commercially available polyether-modified silicon defoamers.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a polyether modified organic silicon defoaming agent safe to strains is characterized by comprising the following steps:
(1) sequentially adding the silicon dioxide nano microspheres, the dimethyl silicon oil, the N, N-methyl formamide and the deionized water into a reaction bottle, adding ammonia water under stirring, heating to 50-70 ℃, reacting for 1-2 hours, naturally cooling to room temperature, centrifuging, washing precipitates with ethanol, and drying to obtain the silicon dioxide nano microspheres grafted and modified by the dimethyl silicon oil;
(2) and (2) adding 30-60 parts of the silicon dioxide nano microspheres grafted and modified by the dimethyl silicone oil, 30-50 parts of the polyether modified silicone oil, 1-10 parts of the thickening agent, 2-10 parts of the emulsifier and 10-50 parts of water which are prepared in the step (1) into a dispersion tank, heating to 180 ℃ for 200 ℃, stirring for 2-3 hours, then reducing the temperature to 50-60 ℃ in a gradient manner under the stirring state, and finally naturally cooling to obtain the polyether modified organic silicon defoaming agent.
2. The method of claim 1, wherein: in the step (1), the dosage ratio of the silicon dioxide nano-microspheres, the dimethyl silicone oil, the N, N-methyl formamide (DMF) and the ammonia water is 1-2: 0.5-1.0: 20-30:1-2 (w/v/v/v).
3. The method of claim 1, wherein: in the step (1), the drying temperature is 50-60 ℃.
4. The method of claim 1, wherein: in the step (1), the preparation method of the silica nano-microsphere comprises the following steps: adding ammonia water into absolute ethyl alcohol, dropwise adding Tetraethoxysilane (TEOS) under vigorous stirring, then stirring for 20-24 hours at 20-30 ℃, and then washing, centrifuging and vacuum-freezing to obtain the silicon dioxide nano-microspheres.
5. The method of claim 4, wherein: in the preparation method of the silicon dioxide nano microspheres, the volume dosage ratio of ammonia water, absolute ethyl alcohol and ethyl orthosilicate is 5-6: 100:3-4.
6. The method of claim 4, wherein: in the preparation method of the silicon dioxide nano-microsphere, absolute ethyl alcohol is used for washing.
7. The method of claim 1, wherein: in the step (2), the preparation method of the polyether modified silicone oil comprises the following steps: adding chloroplatinic acid catalyst dissolved by isopropanol into allyl alcohol polyether, heating to 110 ℃ under stirring, then dropwise adding hydrogen-containing silicone oil, and continuing stirring for reaction for 6-8 hours after the hydrogen-containing silicone oil is added to obtain the polyether modified silicone oil.
8. The method of claim 7, wherein: in the preparation method of the polyether modified silicone oil, the molar usage ratio of the allyl alcohol polyether to the hydrogen-containing silicone oil is 1-1.5: 1;
and/or in the preparation method of the polyether modified silicone oil, the dosage of the chloroplatinic acid catalyst is 0.03-0.05 percent of the total weight of the allyl alcohol polyether and the hydrogen-containing silicone oil.
9. The method of claim 1, wherein: in the step (2), the thickener is at least one selected from hydroxyethyl cellulose, sodium carboxymethyl cellulose, xanthan gum, sodium alginate and glyceryl monostearate;
and/or, in the step (2), the emulsifier is selected from at least one of span 20, tween 20, span 60, tween 60, span 80 and tween 80.
10. The polyether modified silicone defoaming agent prepared by the preparation method according to any one of claims 1 to 9.
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| CN114949941A (en) * | 2022-08-01 | 2022-08-30 | 广州嘉德乐生化科技有限公司 | Defoaming agent containing glyceryl monostearate and application of defoaming agent in medical industry |
| CN115317961A (en) * | 2022-08-24 | 2022-11-11 | 哈药集团技术中心 | Preparation method of dimethyl silicone oil defoaming agent |
| CN116554943A (en) * | 2023-03-29 | 2023-08-08 | 安徽沸点新材料有限公司 | High-temperature-resistant silicone oil composite lubricating ester and preparation method thereof |
| CN119118565A (en) * | 2024-09-13 | 2024-12-13 | 江苏赛欧信越消泡剂有限公司 | A defoaming agent for cementing and preparation method thereof |
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| CN113798734A (en) * | 2021-10-15 | 2021-12-17 | 浙江亚通焊材有限公司 | Soldering flux for tin-based soldering paste and laser soft soldering paste for electronic packaging |
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| CN114949941A (en) * | 2022-08-01 | 2022-08-30 | 广州嘉德乐生化科技有限公司 | Defoaming agent containing glyceryl monostearate and application of defoaming agent in medical industry |
| CN115317961A (en) * | 2022-08-24 | 2022-11-11 | 哈药集团技术中心 | Preparation method of dimethyl silicone oil defoaming agent |
| CN116554943A (en) * | 2023-03-29 | 2023-08-08 | 安徽沸点新材料有限公司 | High-temperature-resistant silicone oil composite lubricating ester and preparation method thereof |
| CN119118565A (en) * | 2024-09-13 | 2024-12-13 | 江苏赛欧信越消泡剂有限公司 | A defoaming agent for cementing and preparation method thereof |
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