CN114316275A - Side chain type amino silicone oil emulsion and preparation method thereof - Google Patents
Side chain type amino silicone oil emulsion and preparation method thereof Download PDFInfo
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- CN114316275A CN114316275A CN202210016854.3A CN202210016854A CN114316275A CN 114316275 A CN114316275 A CN 114316275A CN 202210016854 A CN202210016854 A CN 202210016854A CN 114316275 A CN114316275 A CN 114316275A
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- 229920013822 aminosilicone Polymers 0.000 title claims abstract description 70
- 239000000839 emulsion Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004945 emulsification Methods 0.000 title abstract description 5
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 229920002545 silicone oil Polymers 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- -1 amino hydrocarbon Chemical class 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 25
- 239000002245 particle Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000004530 micro-emulsion Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 241000662429 Fenerbahce Species 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 230000010494 opalescence Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a side chain type amino silicone oil emulsion and a preparation method thereof, wherein the preparation method comprises the following steps: under the protection of inert gas, carrying out reduced pressure reaction on linear body hydroxyl silicone oil and an amino alkyl coupling agent under the catalysis of TMAH, and then carrying out heating treatment under the reduced pressure condition to obtain side chain type amino silicone oil; emulsifying side chain type amino silicone oil to obtain side chain type amino silicone oil emulsion; according to the preparation method disclosed by the invention, through a specific preparation process and a specific emulsification method, the prepared side-chain amino silicone oil emulsion has excellent transmittance and stability, the transmittance can reach 97% at most, and meanwhile, the stability is excellent.
Description
Technical Field
The invention relates to the technical field of amino silicone oil emulsion, in particular to side-chain amino silicone oil emulsion and a preparation method thereof.
Background
The amino silicone oil is amino alkyl polysiloxane obtained by substituting methyl in dimethyl silicone oil with amino. The amino group has the characteristics of strong polarity, high reactivity, adsorbability, thermal stability, low surface tension and the like, and is widely applied to the fields of chemical industry, textile industry, automobile manufacturing industry and the like.
Since the amino silicone oil is a hydrophobic substance, the amino silicone oil can be used only by emulsifying the amino silicone oil into an amino silicone oil emulsion. A large amount of amino contained in the amino silicone oil has polarity, and can generate firmer directional adsorption with hydroxyl in the fiber, and meanwhile, after the amino silicone oil is prepared into microemulsion, the emulsion has smaller grain size and better finishing effect on fabrics. The preparation method of the amino silicone oil microemulsion mainly comprises the following steps: the amino silicone oil is synthesized by bulk polymerization and then emulsified, and the method is characterized in that: the preparation method is simple to operate, convenient to produce and suitable for large-scale production, but for amino silicone oil with high viscosity, stable microemulsion is difficult to prepare; in addition, differences in emulsifiers and emulsification processes lead to poor permeability and stability of the amino silicone oil emulsions prepared.
Disclosure of Invention
The invention aims to provide a side chain type amino silicone oil emulsion and a preparation method thereof, and the side chain type amino silicone oil emulsion prepared by the preparation method has excellent transmittance and stability.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of side chain type amino silicone oil emulsion, which comprises the following steps:
(a) under the protection of inert gas, carrying out reduced pressure reaction on linear body hydroxyl silicone oil and an amino alkyl coupling agent under the catalysis of TMAH, and then carrying out heating treatment under the reduced pressure condition to obtain side chain type amino silicone oil;
(b) and (3) emulsifying the side chain type amino silicone oil to obtain the side chain type amino silicone oil emulsion.
Preferably, in the step (a), the mass ratio of the linear body hydroxyl silicone oil to the ammonia-hydrocarbon-based coupling agent is (92-97): (2-6);
the linear body hydroxyl silicone oil is WS-62M; the amino-hydrocarbon coupling agent is N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane.
Preferably, in the step (a), the final concentration of TMAH added is 500-1000 ppm.
Preferably, in the step (a), the reduced pressure reaction conditions are as follows:
the negative pressure is 0.6-0.8 Mpa; the temperature is 75-85 ℃, and the time is 1-2 h.
Preferably, in the step (a), the heating treatment is heating to 150 ℃, and the heat preservation is carried out for 30-50 min.
Preferably, in the step (b), the emulsifying comprises:
(1) mixing side chain type amino silicone oil, a composite emulsifier and water to obtain a mixed solution;
(2) stirring the mixed solution at 600-900 rpm for 18-22 min;
(3) adding glacial acetic acid into the stirred mixed solution until the pH value is 5-6.5, then continuously stirring for 4-6 min, adding water and stirring for 16-25 min at 550-650 rpm.
Preferably, in the step (1), the content of the side chain type amino silicone oil in the mixed solution is 18-22%; the content of the composite emulsifier is 4-5%;
the composite emulsifier is polyoxyethylene tridecyl ether and ethylene glycol monobutyl ether, wherein the mass ratio of the polyoxyethylene tridecyl ether to the ethylene glycol monobutyl ether is 3: 1.5-2.5.
Preferably, in the step (3), the addition amount of water is 70-78% of the total mass after addition.
The invention provides a side chain type amino silicone oil emulsion prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that at least:
according to the preparation method disclosed by the invention, through a specific preparation process and a specific emulsification method, the prepared side-chain amino silicone oil emulsion has excellent transmittance and stability, the transmittance can reach 97% at most, and meanwhile, the stability is excellent.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a FT-IR analysis chart of side chain type aminosilicone and WS-62M prepared in example 3 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of side chain type amino silicone oil prepared in example 3 of the present invention;
FIG. 3 is a graph showing the transmittance of emulsions prepared at different pH's in Experimental example 3 of the present invention;
FIG. 4 is a graph showing the transmittance of emulsions prepared according to the present invention in example 4 with different amounts of the composite emulsifier;
FIG. 5 transmittance of emulsions prepared at different stirring rates in Experimental example 5 of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail with reference to the following embodiments. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The following examples used the following starting materials:
linear body hydroxy silicone oil: WS-62M; tech, Wake chemical Co., Ltd;
tetramethylammonium hydroxide TMAH, RG, hadamard reagent limited;
amino-hydrocarbon-based coupling agent: n-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane KH-602, RG, Adamas reagent, Inc.;
trideceth, E-1302, technical grade;
ethylene glycol monobutyl ether, BCS, technical grade;
fatty alcohol polyoxyethylene ether AEO-9, technical grade;
cetyl trimethyl ammonium bromide CTAB, technical grade;
glacial acetic acid, AR.
Example 1
This example is a method for preparing a side-chain amino silicone oil emulsion, comprising the steps of:
(a) under the protection of nitrogen, carrying out reduced pressure reaction on the linear body hydroxyl silicone oil and the ammonia alkyl coupling agent for 2 hours at 75 ℃ and-0.8 Mpa under the catalysis of TMAH according to the mass ratio of 97: 6, then heating to 150 ℃ under the reduced pressure condition and preserving heat for 30 minutes to obtain side chain type amino silicone oil, wherein the addition final concentration of TMAH is 1000 ppm;
(b) mixing side chain type amino silicone oil, a composite emulsifier and water to obtain a mixed solution, wherein the content of the side chain type amino silicone oil in the mixed solution is 22%; the content of the composite emulsifier is 5 percent; the composite emulsifier is polyoxyethylene tridecyl ether and ethylene glycol monobutyl ether, and the mass ratio of the polyoxyethylene tridecyl ether to the ethylene glycol monobutyl ether is 3: 1.5;
(c) stirring the mixed solution at 900rpm for 18 min;
(d) adding glacial acetic acid into the stirred mixed solution until the pH value is 5, then continuing stirring for 6min, adding water and stirring at 550rpm for 25min to obtain the side chain type amino silicone oil emulsion, wherein the adding amount of water is 78% of the total mass after the addition.
Example 2
This example is a method for preparing a side-chain amino silicone oil emulsion, comprising the steps of:
(a) under the protection of nitrogen, performing reduced pressure reaction on linear body hydroxyl silicone oil and an amino alkyl coupling agent at 85 ℃ and-0.6 Mpa for 1h under the catalysis of TMAH according to the mass ratio of the linear body hydroxyl silicone oil to the amino alkyl coupling agent of 92: 2, then heating to 150 ℃ under the reduced pressure condition and preserving heat for 50min to obtain side chain type amino silicone oil, wherein the addition final concentration of TMAH is 500 ppm;
(b) mixing side chain type amino silicone oil, a composite emulsifier and water to obtain a mixed solution, wherein the content of the side chain type amino silicone oil in the mixed solution is 18%; the content of the composite emulsifier is 4 percent; the composite emulsifier is polyoxyethylene tridecyl ether and ethylene glycol monobutyl ether, and the mass ratio of the polyoxyethylene tridecyl ether to the ethylene glycol monobutyl ether is 3: 2.5;
(c) stirring the mixed solution at 600rpm for 22 min;
(d) adding glacial acetic acid into the stirred mixed solution until the pH value is 6.5, continuing stirring for 4min, adding water, and stirring at 650rpm for 16min to obtain the side chain type amino silicone oil emulsion, wherein the addition amount of water is 78% of the total mass after the addition.
Example 3
This example is a method for preparing a side-chain amino silicone oil emulsion, comprising the steps of:
(a) under the protection of nitrogen, carrying out reduced pressure reaction on linear body hydroxyl silicone oil and an amino alkyl coupling agent at 80 ℃ and-0.75 Mpa for 2h under the catalysis of TMAH according to the mass ratio of 95: 5, then heating to 150 ℃ under the reduced pressure condition and preserving heat for 40min to obtain side chain type amino silicone oil, wherein the addition final concentration of TMAH is 800 ppm;
(b) mixing side chain type amino silicone oil, a composite emulsifier and water to obtain a mixed solution, wherein the content of the side chain type amino silicone oil in the mixed solution is 20%; the content of the composite emulsifier is 4.5 percent; the composite emulsifier is polyoxyethylene tridecyl ether and ethylene glycol monobutyl ether, and the mass ratio of the polyoxyethylene tridecyl ether to the ethylene glycol monobutyl ether is 3: 2;
(c) stirring the mixed solution at 800rpm for 20 min;
(d) adding glacial acetic acid into the stirred mixed solution until the pH value is 6, then continuing stirring for 5min, adding water and stirring at 600rpm for 20min to obtain the side chain type amino silicone oil emulsion, wherein the adding amount of water is 75% of the total mass after the addition.
Example 4
This example is a method of preparing a side-chain aminosilicone emulsion, which is substantially the same as that of example 3, except that the polyoxyethylenetridecyl ether in the composite emulsifier of example 3 is replaced with an equal amount of AEO-9 and the ethyleneglycol monobutyl ether is replaced with an equal amount of CTAB.
Experimental example 1
1. The side chain type amino silicone oil prepared in example 3 was subjected to infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy, infrared spectroscopy: tabletting with KBr and infrared spectroscopy with Nicolet Nexus 6.0 Fourier transform. Hydrogen nuclear magnetic resonance spectroscopy: using deuterochloroform as solvent, and using BrukeraV400 MHz nuclear magnetic resonance instrument to measure.
FT-IR analysis results of the side chain type amino silicone oil prepared in example 3 and WS-62M are shown in FIG. 1;
the nuclear magnetic resonance hydrogen spectrum result of the side chain type amino silicone oil prepared in the example 3 is shown in figure 2;
as can be seen from FIG. 2, the peak having a chemical shift of δ 0.08 is Si-CH3-proton peak on; the peak at δ 0.54 is the proton peak in Si-CH 2-; peaks at δ 1.2 and δ 1.86 are primary amino-NH2And proton peaks of secondary amino-NH; the peak of delta 1.55 is Si-CH2-CH2-CH2-proton peak of the middle methylene group in NH-; the peak at δ 2.61 is Si-CH2-CH2-CH2-proton peak of methylene group connecting secondary amine group in NH-. Peaks at δ 2.67 and δ 2.81 are HN-CH2-CH2-NH2The proton peak of methylene group connecting primary amine group and secondary amine group.
In conclusion, the analysis of infrared spectrum and nuclear magnetic resonance hydrogen spectrum can confirm that the synthetic substance is side chain type amino silicone oil.
2. The side chain type amino silicone oil emulsion prepared in example 3 was examined for transmittance, average particle diameter, standing stability, centrifugal stability, heat stability and freeze stability, wherein,
transmittance: the transmittance of the product was measured at 25 ℃ using a Cary5000 ultraviolet-visible near-infrared spectrophotometer manufactured by Agilent instruments Ltd of Germany.
Testing the particle size of the emulsion: the particle size of the emulsion particles was determined using a Mastersizer 2000 laser particle size analyzer.
And (3) emulsion stability test:
standing stability: pouring the amino silicone oil emulsion into a standard test tube, standing for 24h, and observing the layering condition of the emulsion.
Centrifugal stability: the emulsion was placed in a 50mL centrifuge tube, centrifuged at 3000r/min for 45min, removed and the appearance observed and recorded.
Heat resistance stability: and (3) placing the microemulsion into a weighing bottle, capping, placing into an oven, drying at 120 ℃ for 30min, cooling and observing.
Freeze-resistant stability: taking a certain amount of amino silicone oil emulsion into a test tube, freezing in a refrigerator at-5 ℃ for 12h, naturally thawing, and observing the layering condition of the emulsion.
The results are shown in table 1:
TABLE 1
As can be seen from the data in table 1, the emulsion prepared in the present application has excellent transmittance, low particle size and excellent stability.
Experimental example 2
Side-chain amino silicone oil emulsions were prepared according to the preparation methods of example 3 and example 4, respectively;
the transmittance and the standing stability of the side-chain amino silicone oil emulsion were examined, wherein,
transmittance: the transmittance of the product was measured at 25 ℃ using a Cary5000 ultraviolet-visible near-infrared spectrophotometer manufactured by Agilent instruments Ltd of Germany.
Standing stability: pouring the amino silicone oil emulsion into a standard test tube, standing for 24h, and observing the layering condition of the emulsion.
The results are shown in table 2:
TABLE 2
| Group of | Transmittance (%) | Stability of standing |
| Example 3 | 97 | Not layering |
| Example 4 | 46 | Not layering |
As can be seen from the data in Table 1: according to the technical scheme, when the composite emulsifier is polyoxyethylene tridecyl ether and ethylene glycol monobutyl ether, the prepared emulsion has better transmittance.
Experimental example 3
This example is the effect of pH on the emulsion
Based on the experimental procedure of example 3, except that glacial acetic acid is used to adjust the pH to 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8 in step (d); then detecting the transmittance of the emulsion prepared under different pH values, and drawing a curve of the detection result as shown in figure 3;
as shown in fig. 3, when the pH is greater than 7, the emulsion is opaque in opalescence, and under the condition of stronger alkalinity, the stability of the emulsion is poor and the transmittance is low; when the pH is less than 7, a transparent amino silicone oil emulsion can be obtained, and the transmittance is good. At pH 6, the amino silicone oil has the best permeability. Under the acidic condition, the amino group in the amino silicone oil and hydrogen ions form quaternary ammonium salt, at the moment, the surface of emulsion particles presents an electric double layer with positive charges, and the repulsion of interaction can be generated among the emulsion particles, so that stable amino silicone oil microemulsion is formed, and the emulsion prepared by the emulsion with the pH value of 5.0-6.5 is the best.
Experimental example 4
The experimental example shows the influence of the dosage of the composite emulsifier on the emulsion
Based on the experimental method of example 2, except that the contents of the complex emulsifier in the mixed solution in the step (b) are adjusted to 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, respectively; then detecting the transmittance of the emulsion prepared under different composite emulsifier contents, and drawing a curve of the detection result as shown in figure 4;
as can be seen from FIG. 4, when the amount of the composite emulsifier is less than 40%, the emulsion is turbid, and the floating oil is even layered due to insufficient amount of the emulsifier; when the dosage of the composite emulsifier is increased to 5.0%, the emulsion system has enough solubilizing micelles, and can dissolve all amino silicone oil to form stable microemulsion, so that the light transmittance is better; when the content of the emulsifier is increased to 5.5%, the emulsion begins to generate turbidity and delamination, the amount of the emulsifier is excessive, and the excessive composite emulsifier cannot be well dissolved in water due to the imbalance of the hydrophilic lipophilic group effect, so that an emulsion system is turbid, and the stability of the emulsion is reduced. Therefore, the dosage of the compound emulsifier is determined to be 4.0-5.0%.
Experimental example 5
The experimental examples show the influence of different stirring rates on the emulsion
Based on the experimental procedure of example 3, except that the mixed solution in step (c) was stirred at 200, 400, 600, 800, 1000rpm for 20min, respectively; then detecting the transmittance of the emulsion prepared at different stirring speeds, and drawing a curve of the detection result as shown in figure 5;
as can be seen from fig. 5, when the stirring speed is slow, the air content in the stirring kettle is high, and the latex particles cannot enter in time, so that the particle size distribution is wide, the particle size is large, and the transmittance is low; when the stirring speed is too high, the collision probability between emulsion particles among products is increased, the particle size is increased due to easy coalescence, and the transmittance is reduced, so that the optimal stirring speed is 600-900 rpm.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (9)
1. A preparation method of a side chain type amino silicone oil emulsion is characterized by comprising the following steps:
(a) under the protection of inert gas, carrying out reduced pressure reaction on linear body hydroxyl silicone oil and an amino alkyl coupling agent under the catalysis of TMAH, and then carrying out heating treatment under the reduced pressure condition to obtain side chain type amino silicone oil;
(b) and (3) emulsifying the side chain type amino silicone oil to obtain the side chain type amino silicone oil emulsion.
2. The method according to claim 1, wherein in the step (a), the mass ratio of the linear hydroxy silicone oil to the amino hydrocarbon-based coupling agent is (92-97) to (2-6);
the linear body hydroxyl silicone oil is WS-62M; the amino-hydrocarbon coupling agent is N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane.
3. The method according to claim 1, wherein TMAH is added to the reaction mixture in a final concentration of 500-1000 ppm in step (a).
4. The method according to claim 1, wherein in the step (a), the reaction conditions under reduced pressure are as follows:
the negative pressure is 0.6-0.8 Mpa; the temperature is 75-85 ℃, and the time is 1-2 h.
5. The preparation method according to claim 1, wherein in the step (a), the heating treatment is heating to 150 ℃ and keeping the temperature for 30-50 min.
6. The method of claim 1, wherein the emulsifying in the step (b) comprises:
(1) mixing side chain type amino silicone oil, a composite emulsifier and water to obtain a mixed solution;
(2) stirring the mixed solution at 600-900 rpm for 18-22 min;
(3) adding glacial acetic acid into the stirred mixed solution until the pH value is 5-6.5, then continuously stirring for 4-6 min, adding water and stirring for 16-25 min at 550-650 rpm.
7. The preparation method according to claim 6, wherein in the step (1), the content of the side-chain type amino silicone oil in the mixed solution is 18% to 22%; the content of the composite emulsifier is 4-5%;
the composite emulsifier is polyoxyethylene tridecyl ether and ethylene glycol monobutyl ether, wherein the mass ratio of the polyoxyethylene tridecyl ether to the ethylene glycol monobutyl ether is 3: 1.5-2.5.
8. The production method according to claim 6, wherein in the step (3), the amount of water added is 70% to 78% of the total mass after addition.
9. The amino silicone oil emulsion of side chain type prepared by the preparation method of any one of claims 1 to 8.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04279667A (en) * | 1990-06-07 | 1992-10-05 | Shin Etsu Chem Co Ltd | Production of oil-in-water type organopolysiloxane emulsion |
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2022
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| JPH04279667A (en) * | 1990-06-07 | 1992-10-05 | Shin Etsu Chem Co Ltd | Production of oil-in-water type organopolysiloxane emulsion |
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| JP2011001419A (en) * | 2009-06-17 | 2011-01-06 | Shin-Etsu Chemical Co Ltd | Composition for preparing amino-modified silicone micro-emulsion, method for producing amino-modified silicone micro-emulsion, and amino-modified silicone micro-emulsion |
| CN102002162A (en) * | 2010-08-10 | 2011-04-06 | 佛山市顺德区德美瓦克有机硅有限公司 | Cation amino silicone oil micro-emulsion and preparation method thereof |
| CN108912333A (en) * | 2018-07-23 | 2018-11-30 | 上海应用技术大学 | A kind of preparation method of high transmittance amido silicon oil |
| CN109280171A (en) * | 2018-08-28 | 2019-01-29 | 上海树脂厂有限公司 | Small particle amido silicone oil microemulsion and its preparation method and application |
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