CN107698763B - Preparation method of high-stability cationic silicon emulsion - Google Patents
Preparation method of high-stability cationic silicon emulsion Download PDFInfo
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- CN107698763B CN107698763B CN201710697816.8A CN201710697816A CN107698763B CN 107698763 B CN107698763 B CN 107698763B CN 201710697816 A CN201710697816 A CN 201710697816A CN 107698763 B CN107698763 B CN 107698763B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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Abstract
The invention relates to a preparation method of high-stability cationic silicon emulsion, which is characterized by comprising the following steps: adding water and a nonionic surfactant into a beaker A with a stirrer and a thermometer to obtain a uniformly mixed solution A; adding the organosilane and the aminosilane coupling agent into a beaker B, stirring and dissolving uniformly to obtain a mixed solution B, slowly adding the mixed solution B into the beaker A in batches at room temperature to mix with the mixed solution A, and reacting to prepare a pre-emulsion; slowly dripping water into the pre-emulsion, adding an acidic surfactant after dripping water to obtain a reactant, and neutralizing the reactant with alkali to ensure that the pH of the reactant is =7-8 to obtain anionic silicon emulsion; at room temperature, cationic surfactant is added into the anionic silicon milk to convert the anionic silicon milk into cationic silicon milk, and the solid content of the converted cationic silicon milk is 20-50%. Its advantage does: not only greatly shortens the time for preparing the cationic amino alkyl polyorganosiloxane at low temperature, greatly reduces the difficulty degree for preparing the cationic amino alkyl polyorganosiloxane at low temperature, but also increases the stability of the cationic amino alkyl polyorganosiloxane.
Description
Technical Field
The invention relates to a preparation method of high-stability cationic silicon emulsion.
Background
The cationic silicon emulsion is prepared by polymerizing a polysiloxane monomer, an aminosilane coupling agent and a cationic surfactant, and can be well combined with fabric fibers with negative charges due to the positive charges, so that the cationic silicon emulsion can be well adsorbed on the fabric and can be paved into a thin silicon film on the surfaces of the fabric fibers, and the fabric can show a soft and smooth finishing effect and is widely applied to the textile finishing technology.
Generally, a cationic silicone emulsion is usually prepared by emulsion polymerization of a polysiloxane monomer, an aminosilane coupling agent and a cationic surfactant under the condition of heating, but the stability of the cationic silicone emulsion is obviously reduced due to long-time high-temperature heating, emulsion breaking and oil floating phenomena are prone to occurring in the using process, silicon spots are prone to occurring on a fabric, the overall effect and the attractiveness of a textile are affected, the stability of the cationic silicone emulsion is obviously improved due to the fact that the cationic silicone emulsion reacts at low temperature and is not heated, but the reaction speed of the cationic silicone emulsion is slow at low temperature, the polymerization degree of the cationic silicone emulsion is affected due to the low temperature, the conversion rate of oligomers is very low, the reaction difficulty degree is increased, and therefore the cationic silicone oil with high silicon content cannot be produced, and the hand feeling is often lower than that of common cationic silicone oil.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of high-stability cationic silicone emulsion, wherein a polysiloxane monomer and an aminosilane coupling agent are firstly converted into anionic silicone emulsion which can rapidly react at any temperature and then converted into cationic silicone emulsion, so that the time for preparing the cationic aminoalkyl polyorganosiloxane emulsion at low temperature is greatly shortened, the difficulty degree for preparing the cationic aminoalkyl polyorganosiloxane emulsion at low temperature is greatly reduced, and the stability of the cationic aminoalkyl polyorganosiloxane emulsion is improved.
In order to achieve the above object, the technical solution of the present invention is achieved by a high stability
The preparation method of the cationic silicon emulsion is characterized by comprising the following steps:
step one
Adding water and a nonionic surfactant into a beaker A with a stirrer and a thermometer, wherein the mass ratio of the water to the nonionic surfactant is 0.5-2, and stirring and dissolving the mixture uniformly for 15-30 minutes at room temperature to obtain a uniformly mixed solution A;
step two
Adding the organosilane and the aminosilane coupling agent into a beaker B, wherein the mass of the aminosilane coupling agent accounts for 0.1-10% of that of the polyorganosiloxane, uniformly stirring and dissolving to obtain a mixed solution B, slowly adding the mixed solution B into the beaker A in batches at room temperature to mix with the mixed solution A, and reacting to prepare a pre-emulsion;
step three
Slowly dripping water into the pre-emulsion in the second step, wherein the mass of the water accounts for 50% -70% of the mass of the pre-emulsion, adding an acidic surfactant after dripping, the mass of the acidic surfactant accounts for 0.25% -5% of the mass of the pre-emulsion, carrying out catalytic reaction for 25-35 minutes at room temperature, then carrying out static reaction for 1-5 days at room temperature to obtain a reactant, then neutralizing the reactant with alkali to enable the pH of the reactant to be =7-8, thus obtaining the anionic silicon emulsion, and the mass of the alkali used accounts for 0.05-1% of the reactant;
step four
At room temperature, cationic surfactant is added into anionic silicon milk to convert the anionic silicon milk into cationic silicon milk, the solid content of the converted cationic silicon milk is 20-50%, and the molar ratio of the added cationic surfactant to the anionic silicon milk is 1.1-5.
In the technical scheme, the nonionic surfactant is branched fatty alcohol-polyoxyethylene ether series or isomeric tridecanol ether series.
In the technical scheme, the structural formula of the organosilane is as follows:
in the technical scheme, the amino silane coupling agent is aminoethyl aminopropyl methyl dialkyl silane, and the structural formula is as follows:
in the technical scheme, the acidic surfactant is dodecyl benzene sulfonic acid.
In the technical scheme, the cationic emulsifier is hexadecyl trimethyl ammonium chloride.
Compared with the prior art, the invention has the advantages that: the polysiloxane monomer and the aminosilane coupling agent are firstly converted into the anionic silicone emulsion which can quickly react under any temperature condition, and then converted into the cationic silicone emulsion, so that the time for preparing the cationic amino-alkyl polyorganosiloxane emulsion at low temperature is greatly shortened, the difficulty degree for preparing the cationic amino-alkyl polyorganosiloxane emulsion at low temperature is greatly reduced, and the stability of the cationic amino-alkyl polyorganosiloxane emulsion is improved.
Detailed Description
The following examples further illustrate embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example one
The preparation method of the high-stability cationic silicon emulsion comprises the following steps:
step one
Adding 45 parts of isomeric tridecanol ether 12EO and 54 parts of water into a beaker A with a stirrer and a thermometer, and stirring for 15-30 minutes under the condition that the stirring speed is 1300-1500r/min until a uniform mixed solution A is formed;
step two
Adding 315 parts of polysiloxane monomer and 2.2 parts of aminoethyl aminopropyl methyl dialkoxysilane into the other beaker B, and stirring the mixture of the polysiloxane monomer and the aminoethyl aminopropyl methyl dialkoxysilane for 15 minutes to be uniform to form a mixed solution B; adding the mixed solution B into the beaker A obtained in the first step for 5 times at a stirring speed of 1300 plus 1500r/min to be mixed with the mixed solution A, and adding the mixed solution B once every 15 minutes until the mixed solution in the beaker A forms uniform white emulsion, wherein the adding time of the mixed solution is 2-3 hours, so as to obtain pre-emulsion;
step three
Slowly adding 436 parts of water dropwise into the pre-emulsion obtained in the second step, slowly adding 9 parts of dodecylbenzene sulfonic acid after the water is completely added, continuously and rapidly stirring at room temperature for 30-60 minutes, standing at room temperature for 48 hours, obtaining a reactant after the mixture reacts, neutralizing the reactant with 1.7 parts of triethanolamine to enable the pH of the reactant to be =8, and preparing to obtain anionic silicon emulsion;
step four
Adding a mixed solution of 4.9 parts of absolute ethyl alcohol and 12.3 parts of hexadecyl trimethyl ammonium chloride into the prepared anionic silicon milk at room temperature, and uniformly stirring to obtain blue milky cationic silicon milk with the solid content of 40-45%;
the above are parts by weight.
Example two
The preparation method of the high-stability cationic silicon emulsion comprises the following steps:
step one
Adding 50 parts of branched fatty alcohol-polyoxyethylene ether 9EO and
stirring 40 parts of water for 15-30 minutes at the stirring speed of 1300-1500r/min until a uniformly mixed solution A is formed;
step two
Adding 300 parts of polysiloxane monomer and 2.45 parts of aminoethyl aminopropyl methyl dialkoxy silane into the other beaker B, uniformly mixing and stirring for 15 minutes to form a mixed solution B, adding the mixed solution B into the beaker B for 5 times at the stirring speed of 1300-1500r/min, and adding the mixed solution B once every 15 minutes until the mixed solution in the beaker A is milky white, wherein the adding time of the mixed solution is 2-3 hours to obtain a pre-emulsion;
step three
Slowly dripping 540 parts of water into the pre-emulsion, slowly adding 7.5 parts of dodecylbenzene sulfonic acid after the dripping of the water is finished, continuously and rapidly stirring at room temperature for 30-60 minutes, standing at room temperature for 48 hours to obtain a reactant, neutralizing the reactant by using 1.2 parts of triethanolamine to ensure that the pH =8 of the reactant, and preparing to obtain anionic silicon emulsion;
step four
At room temperature, adding a mixed solution of 4.9 parts of absolute ethyl alcohol and 10 parts of hexadecyl trimethyl ammonium chloride into the anionic silicon milk, and uniformly stirring to obtain blue light milky cationic silicon milk with the solid content of 40-45%;
the above are parts by weight.
EXAMPLE III
The preparation method of the high-stability cationic silicon emulsion comprises the following steps:
step one
Adding 40 parts of isomeric tridecanol ether 12EO and 43 parts of water into a beaker A provided with a stirrer and a thermometer, and stirring for 15-30 minutes under the condition that the stirring speed is 100-300r/min until a uniformly mixed solution A is formed;
step two
And adding 350 parts of polysiloxane monomer and 2.45 parts of aminoethyl aminopropyl methyl dialkoxy silane into the other beaker B, uniformly mixing and stirring for 15 minutes to form a mixed solution B, adding the mixed solution B into the beaker at a stirring speed of 100 plus one liter of 300r/min for 5 times, and adding the mixed solution B into the beaker once every 15 minutes until the mixed solution in the beaker forms milky white to obtain a pre-emulsion, wherein the adding time of the mixed solution is 2-3 hours.
Step three
Slowly dropwise adding 423.5 parts of water into the pre-emulsion, slowly adding 102 parts of 2% NAOH aqueous solution after the dropwise adding of the water is finished, continuously and rapidly stirring at room temperature for 30-60 minutes, standing at room temperature for 120 hours to obtain a reactant, neutralizing the reactant with acetic acid to ensure that the pH =7 of the reactant, and preparing to obtain anionic silicon emulsion;
step four
Adding the mixture of 15 parts of absolute ethyl alcohol and 15 parts of hexadecyl trimethyl ammonium chloride into the anionic silicon milk, and stirring for 15-30 minutes. Obtaining blue light opal cationic silicon emulsion with the solid content of 35-40%;
the above are parts by weight.
Example four
The preparation method of the high-stability cationic silicon emulsion comprises the following steps:
step one
Adding 50 parts of isomeric tridecanol ether 12EO and 60 parts of water into a beaker A provided with a stirrer and a thermometer, and stirring for 15-30 minutes under the condition that the stirring speed is 100-300r/min until a uniformly mixed solution A is formed;
step two
Adding 350 parts of polysiloxane monomer and 2.45 parts of aminoethyl aminopropyl methyl dialkoxy silane into the other beaker B, uniformly mixing and stirring for 15 minutes to form a mixed solution B, adding the mixed solution B into the beaker A for 5 times at the stirring speed of 100 plus one tool at 300r/min to mix with the mixed solution A, and adding the mixed solution B once every 15 minutes until the mixed solution in the flask is milky white to obtain a pre-emulsion, wherein the adding time of the mixed solution is 2-3 hours;
step three
Slowly dripping 400 parts of water into the pre-emulsion, slowly adding 102 parts of 2% NAOH aqueous solution after the dripping of the water is finished, then continuously and rapidly stirring for 30-60 minutes at room temperature, standing for 120 hours at room temperature to obtain a reactant, neutralizing the reactant by using 18 parts of 35% hydrochloric acid solution to ensure that the pH =1.85 of the reactant, then heating to 50 ℃, keeping the temperature at 50 ℃ for 120 hours at constant temperature, after the temperature is finished, neutralizing the reactant by using 30 parts of 2% NAOH aqueous solution to ensure that the pH =7 of the reactant, and preparing to obtain the anionic silicon emulsion;
step four
Adding a mixed solution of 15 parts of absolute ethyl alcohol and 15 parts of hexadecyl trimethyl ammonium chloride into the anionic silicon milk, and stirring for 15-30 minutes to form a uniform body, namely the blue light opal cationic silicon milk with the solid content of 35-40%;
the above are parts by weight.
The embodiments of the present invention are described in detail with reference to the examples, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention.
Claims (4)
1. A preparation method of high-stability cationic silicon emulsion is characterized by comprising the following steps: step one
Adding water and a nonionic surfactant into a beaker A with a stirrer and a thermometer, wherein the mass ratio of the water to the nonionic surfactant is 0.5-2, and stirring and dissolving the mixture uniformly for 15-30 minutes at room temperature to obtain a uniformly mixed solution A;
step two
Adding the organosilane and the aminosilane coupling agent into a beaker B, wherein the mass of the aminosilane coupling agent accounts for 0.1-10% of that of the polyorganosiloxane, uniformly stirring and dissolving to obtain a mixed solution B, slowly adding the mixed solution B into the beaker A in batches at room temperature to mix with the mixed solution A, and reacting to prepare a pre-emulsion;
step three
Slowly dripping water into the pre-emulsion in the second step, wherein the mass of the water accounts for 50% -70% of the mass of the pre-emulsion, adding an acidic surfactant after dripping, the mass of the acidic surfactant accounts for 0.25% -5% of the mass of the pre-emulsion, carrying out catalytic reaction for 25-35 minutes at room temperature, then carrying out static reaction for 1-5 days at room temperature to obtain a reactant, then neutralizing the reactant with alkali to enable the pH of the reactant to be =7-8, thus obtaining the anionic silicon emulsion, and the mass of the alkali used accounts for 0.05-1% of the reactant; the acid surfactant is dodecyl benzene sulfonic acid, and the alkali is triethanolamine;
step four
At room temperature, adding a cationic surfactant into anionic silicon milk to convert the anionic silicon milk into cationic silicon milk, wherein the solid content of the converted cationic silicon milk is 20-50%, and the molar ratio of the added cationic surfactant to the anionic silicon milk is 1.1-5; the cationic surfactant is cetyltrimethylammonium chloride.
2. The method for preparing high-stability cationic silicon emulsion according to claim 1, wherein the nonionic surfactant is a branched fatty alcohol-polyoxyethylene ether series or an isomeric tridecanol ether series.
3. The method for preparing high-stability cationic silicon milk according to claim 1, wherein the structural formula of the polyorganosilane is:
4. the method for preparing high-stability cationic silicon emulsion according to claim 1, wherein the aminosilane coupling agent is aminoethyl aminopropyl methyl dialkyl silane, and the structural formula of the aminosilane coupling agent is as follows:
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| CN1670056A (en) * | 2005-03-07 | 2005-09-21 | 华明扬 | Process for preparing anion composite modified organosilicon emulsion |
| CN103497339A (en) * | 2013-09-29 | 2014-01-08 | 淮安凯悦科技开发有限公司 | Hydroxyl polyether-terminated polydimethylsiloxane and blue light emulsion of hydroxyl polyether-terminated polydimethylsiloxane as well as preparation method of blue light emulsion |
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| JP4335145B2 (en) * | 2002-11-04 | 2009-09-30 | ザ プロクター アンド ギャンブル カンパニー | Fabric treatment compositions comprising various silicones, methods of preparing them, and methods of using them |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670056A (en) * | 2005-03-07 | 2005-09-21 | 华明扬 | Process for preparing anion composite modified organosilicon emulsion |
| CN103497339A (en) * | 2013-09-29 | 2014-01-08 | 淮安凯悦科技开发有限公司 | Hydroxyl polyether-terminated polydimethylsiloxane and blue light emulsion of hydroxyl polyether-terminated polydimethylsiloxane as well as preparation method of blue light emulsion |
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| Title |
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| 阴离子型有机硅微乳液的制备及应用;夏建明等;《印染》;20070831(第16期);第27页右栏第1部分、第28页第3.1.1和3.1.4部分、第29页第3.3部分、第30页第3.4.1部分 * |
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