CN115044044A - Sulfonic group modified silicone oil and preparation method and application thereof - Google Patents
Sulfonic group modified silicone oil and preparation method and application thereof Download PDFInfo
- Publication number
- CN115044044A CN115044044A CN202210821725.1A CN202210821725A CN115044044A CN 115044044 A CN115044044 A CN 115044044A CN 202210821725 A CN202210821725 A CN 202210821725A CN 115044044 A CN115044044 A CN 115044044A
- Authority
- CN
- China
- Prior art keywords
- silicone oil
- modified silicone
- sulfonic acid
- acid group
- sulfonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000000746 purification Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 43
- 239000000243 solution Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 150000003459 sulfonic acid esters Chemical class 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 239000003599 detergent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000008053 sultones Chemical class 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005363 dialkylsulfonamide group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000008206 lipophilic material Substances 0.000 description 1
- -1 medical treatment Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- 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
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/54—Silicon compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses sulfonic modified silicone oil and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, taking propenyl-1, 3-sultone and hydrogen-containing silicone oil as raw materials in an inert atmosphere, carrying out addition reaction by using a platinum catalyst, and separating and purifying to obtain sulfonate modified silicone oil; s2, adding the sulfonate modified silicone oil into an alkali solution, carrying out hydrolysis reaction, and separating and purifying to obtain the sulfonate modified silicone oil.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to sulfonic modified silicone oil and a preparation method and application thereof.
Background
Compared with a carbon-based surfactant, the hydrogen-containing silicone oil has the advantages that the specific hydrophobic group (Si-C-Si, Si-O-Si or Si-Si) of the hydrogen-containing silicone oil greatly enhances the hydrophobicity, and the silicon oxygen bond in the hydrophobic chain of the silicone oil has bond energy far higher than that of a carbon-carbon bond and a carbon-oxygen bond, so that the performance of the silicone oil surfactant is very stable, but the silicone oil product has poor fuel oil resistance and chemical medium resistance, most of the silicone oil product is insoluble in water and difficult to disperse, so that the use of the silicone oil surfactant is limited, and therefore the silicone oil surfactant needs to be modified.
According to the difference of the substituent groups, the silicone oil can be divided into two main categories of reactive modified silicone oil and non-reactive modified silicone oil. The properties of the modified silicone oil are greatly different due to different properties and numbers of the substituent groups. At present, modified silicone oil mainly comprises amino silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, alcohol-based modified silicone oil, phenol-based modified silicone oil, sulfhydryl modified silicone oil, polyether modified silicone oil, fluorine-containing modified silicone oil and the like, and the modified silicone oil has wide application and wide application in the fields of cosmetics, medical treatment, textiles, foods, machinery and the like.
However, the existing modified silicone oil has the defects of large surface tension and low surface activity.
Disclosure of Invention
In view of the above, the application provides a sulfonic modified silicone oil, and a preparation method and an application thereof, and an obtained product has the advantages of low surface tension, high surface activity, simple preparation process and high yield.
In order to achieve the technical purpose, the following technical scheme is adopted in the application:
in a first aspect, the present application provides a method for preparing a sulfonic acid group modified silicone oil, comprising the following steps:
s1, taking propenyl-1, 3-sultone and hydrogen-containing silicone oil as raw materials in an inert atmosphere, carrying out addition reaction by using a platinum catalyst, and separating and purifying to obtain sulfonate modified silicone oil;
s2, adding the sulfonate modified silicone oil into an alkali solution, carrying out hydrolysis reaction, and separating and purifying to obtain the sulfonic modified silicone oil.
Preferably, the hydrogen content of the hydrogen-containing silicone oil is 0.18% -0.65%.
Preferably, the molar ratio of the hydrogen-containing silicone oil to the propenyl-1, 3-sultone is 1: 1.2.
Preferably, in step S1, the mass of the platinum catalyst is 0.1% of the raw material.
Preferably, in step S2, the alkali solution is a sodium hydroxide solution and/or a potassium hydroxide solution.
Preferably, the mass fraction of the alkali solution is 40%.
Preferably, in step S1, the step of separating and purifying is to add the addition reaction product to activated carbon for decolorization, then filter, and degas the filtrate.
Preferably, in step S2, the step of separating and purifying is to add the hydrolysis reaction product into ethanol, stir at 0-5 ℃, then pump filter, wash the filter cake with ethanol, and dry.
In a second aspect, the present application provides a sulfonic acid group-modified silicone oil.
In a third aspect, the application provides an application of a sulfonic acid group modified silicone oil in a surfactant.
The beneficial effect of this application is as follows: according to the method, the hydrogen-containing silicone oil and propenyl-1, 3-sultone are connected through hydrosilylation, and then the sultone is hydrolyzed under an alkaline condition, so that the lipophilic hydrogen-containing silicone oil and the hydrophilic sulfonic acid group are connected, the hydrophilicity of a hydrophilic end is further enhanced by the hydroxyl group obtained after hydrolysis, and the obtained sulfonic modified silicone oil has low surface tension and high surface activity.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The application provides a preparation method of sulfonic group modified silicone oil, which comprises the following steps:
s1, under an inert atmosphere, taking propenyl-1, 3-sultone and hydrogen-containing silicone oil with the hydrogen content of 0.18% -0.65% as raw materials, carrying out addition reaction by using a platinum catalyst, adding the addition reaction product into active carbon for decoloring, then filtering, and degassing the filtrate to obtain sulfonate modified silicone oil;
s2, adding sulfonate modified silicone oil into a sodium hydroxide solution and/or a potassium hydroxide solution with the mass fraction of 40%, performing hydrolysis reaction, adding a hydrolysis reaction product into ethanol, stirring at 0-5 ℃, performing suction filtration, washing a filter cake with ethanol, and drying to obtain sulfonic modified silicone oil;
the reaction formula is as follows:
a surfactant refers to a substance that is capable of significantly addressing the surface tension of a target solution. The molecular structure of the surfactant contains hydrophilic group and hydrophobic group, when the surfactant contacts with a solution, the hydrophilic group can be dissolved with water, the hydrophobic group can be dissolved with oil phase, the hydrogen-containing silicone oil is a good lipophilic material, and the sulfonic acid group is a good hydrophilic group.
In some embodiments, the molar ratio of hydrogen-containing silicone oil to propenyl-1, 3-sultone is 1: 1.2.
In some embodiments, the mass of the platinum catalyst in step S1 is 0.1% of the feedstock.
In a second aspect, the present application provides a sulfonic acid group-modified silicone oil.
In a third aspect, the present application provides a use of a sulfonic acid group-modified silicone oil in a surfactant, for example, a sulfonic acid group-modified silicone oil is added as a surfactant to a detergent, an emulsifier, a dispersant, or the like.
Example 1
A preparation method of sulfonic group modified silicone oil comprises the following steps:
adding 1.0kg of hydrogen-containing silicone oil with the hydrogen content of 0.18 percent into a reaction bottle with a mechanical stirring device, adding 0.64g of Karstedt catalyst, replacing air in the reaction bottle, filling sufficient argon, heating to 80 ℃ under the argon atmosphere, stirring for 15min, injecting 0.72kg of propenyl-1, 3-sultone with air discharged in advance into the reaction bottle, and then carrying out heat preservation reaction for 6 h; after the reaction is finished, the reaction liquid is cooled to room temperature and filtered to obtain the product oily liquid. Then adding activated carbon for decolorization to remove residual platinum catalyst in the product, and filtering to obtain 1.26kg of sultone-based modified silicone oil.
Adding 1.0kg of sodium hydroxide solution with the mass fraction of 40% into a reaction bottle, distilling at 100 ℃ under reduced pressure to remove 70% of water, adding 1.5kg of ethanol, cooling to 5 ℃, stirring at 5 ℃ for 30min, carrying out suction filtration on the obtained solid-liquid mixture, washing a filter cake with 1.5kg of ethanol, and drying at 80 ℃ to finally obtain 1.20kg of solid product sulfonic modified silicone oil with the yield of 93%.
As determined by Hydrophilic Lipophilic Balance (HLB): dissolving 0.2g of the sample in 20mL of a mixed solution of 1, 4-dioxane and benzene (90:4), titrating the solution with distilled water until the solution is obviously turbid, recording the volume V of the distilled water, and substituting the HLB (hydrophile-lipophile balance) of the formula of 25.7 ligV-11.3 to obtain the solution; the hydrophilic-lipophilic balance (HLB) was found to be 6.2.
The surface tension is measured according to a maximum pressure bubble method, namely the modified silicone oil to be measured is placed in a surface tension meter, the end face of a capillary is tangent to the liquid level, the liquid level rises along the capillary, a piston of an air pumping cylinder is opened to pump air slowly, the liquid level in the capillary is subjected to a pressure higher than that of the liquid level in a bottle A, so that a pressure difference exists at the moment, the pressure difference is an additional pressure P (P is P atmosphere-P system), when the radius of the capillary is equal to the radius of formed bubbles, the additional pressure is the maximum at the moment, a relational expression Pmax is 2/r, r is the radius of the capillary, and is the surface tension, and the surface tension of the modified silicone oil with the thickness of 0.1mol/L measured by the method is 30.9N/m.
Example 2
A preparation method of sulfonic group modified silicone oil comprises the following steps:
adding 1.2kg of hydrogen-containing silicone oil with the hydrogen content of 0.22% into a reaction bottle with a mechanical stirring device, adding 1.0g of Karstedt catalyst, replacing air in the reaction bottle, filling sufficient nitrogen, heating to 80 ℃ in the nitrogen atmosphere, stirring for 15min, injecting 1.0kg of propenyl-1, 3-sultone with air discharged in advance into the reaction bottle, then carrying out heat preservation reaction for 6h, cooling the reaction liquid to room temperature after the reaction is finished, filtering to obtain an oily liquid of a product, adding activated carbon for decoloration to remove the residual platinum catalyst in the product, and filtering to obtain 1.27kg of sulfonic acid ester modified silicone oil.
Adding 1.0kg of sodium hydroxide solution with the mass fraction of 30% into a reaction bottle, distilling at 100 ℃ under reduced pressure to remove 70% of water, adding 1.5kg of ethanol, cooling to 5 ℃, stirring at 5 ℃ for 30min, carrying out suction filtration on the obtained solid-liquid mixture, washing a filter cake with 1.5kg of ethanol, and drying at 80 ℃ to finally obtain 1.22kg of solid product sulfonic modified silicone oil with the yield of 95%.
As determined by Hydrophilic Lipophilic Balance (HLB): dissolving 0.2g of the sample in 20mL of a mixed solution of 1, 4-dioxane and benzene (90:4), titrating the solution with distilled water until the solution is obviously turbid, recording the volume V of the distilled water, and substituting the HLB (hydrophile-lipophile balance) of the formula of 25.7 ligV-11.3 to obtain the solution; the hydrophilic-lipophilic balance (HLB) of the product is 6.0.
The surface tension values of the sulfonic acid group-modified silicone oil in this example were measured by the method in example 1 to be: 29.4N/m.
Example 3
A preparation method of sulfonic group modified silicone oil comprises the following steps:
adding 1.0kg of hydrogen-containing silicone oil with the hydrogen content of 0.65 percent into a reaction bottle with a mechanical stirring device, adding 0.64g of Karstedt catalyst, replacing air in the reaction bottle, filling sufficient nitrogen, heating to 80 ℃ in the nitrogen atmosphere, stirring for 15min, injecting 0.72kg of propenyl-1, 3-sultone with air discharged in advance into the reaction bottle, then carrying out heat preservation reaction for 6h, cooling the reaction liquid to room temperature after the reaction is finished, filtering to obtain an oily liquid of a product, adding activated carbon for decoloration to remove the residual platinum catalyst in the product, and filtering to obtain 1.25kg of sulfonic acid ester modified silicone oil.
Adding 1.0kg of sodium hydroxide solution with the mass fraction of 40% into a reaction bottle, distilling at 100 ℃ under reduced pressure to remove 70% of water, adding 1.5kg of ethanol, cooling to 5 ℃, stirring at 5 ℃ for 30min, carrying out suction filtration on the obtained solid-liquid mixture, washing a filter cake with 1.5kg of ethanol, and drying at 80 ℃ to finally obtain 1.19kg of solid product sulfonic modified silicone oil with the yield of 92%.
As determined by Hydrophilic Lipophilic Balance (HLB): dissolving 0.2g of the sample in 20mL of a mixed solution of 1, 4-dioxane and benzene (90:4), titrating the solution with distilled water until the solution is obviously turbid, recording the volume V of the distilled water, and substituting the HLB (hydrophile-lipophile balance) of the formula of 25.7 ligV-11.3 to obtain the solution; the hydrophilic-lipophilic balance (HLB) of the product is 5.9.
The surface tension values of the sulfonic acid group-modified silicone oil in this example were measured by the method in example 1 to be: 28.7N/m.
Example 4
A preparation method of sulfonic group modified silicone oil comprises the following steps:
adding 1.0kg of hydrogen-containing silicone oil with the hydrogen content of 0.18 percent into a reaction bottle with a mechanical stirring device, adding 0.64g of Karstedt catalyst, replacing air in the reaction bottle, filling sufficient nitrogen, heating to 80 ℃ in the nitrogen atmosphere, stirring for 15min, injecting 0.72kg of propenyl-1, 3-sultone with air discharged in advance into the reaction bottle, then carrying out heat preservation reaction for 6h, cooling the reaction liquid to room temperature after the reaction is finished, filtering to obtain an oily liquid of a product, adding activated carbon for decoloration to remove the residual platinum catalyst in the product, and filtering to obtain 1.23kg of sulfonic acid ester modified silicone oil.
Adding 1.0kg of potassium hydroxide solution with the mass fraction of 40% into a reaction bottle, distilling at 100 ℃ under reduced pressure to remove 70% of water, adding 1.5kg of ethanol, cooling to 5 ℃, stirring at 5 ℃ for 30min, carrying out suction filtration on the obtained solid-liquid mixture, washing a filter cake with 1.5kg of ethanol, and drying at 80 ℃ to finally obtain 1.21kg of solid product sulfonic modified silicone oil with the yield of 92%.
As determined by Hydrophilic Lipophilic Balance (HLB): dissolving 0.2g of the sample in 20mL of a mixed solution of 1, 4-dioxane and benzene (90:4), titrating the solution with distilled water until the solution is obviously turbid, recording the volume V of the distilled water, and substituting the HLB (hydrophile-lipophile balance) of the formula of 25.7 ligV-11.3 to obtain the solution; the hydrophilic-lipophilic balance (HLB) of the product is 5.6.
The surface tension values of the sulfonic acid group-modified silicone oil in this example were measured by the method in example 1 to be: 30.5N/m.
Example 5
A preparation method of sulfonic group modified silicone oil comprises the following steps:
adding 1.0kg of hydrogen-containing silicone oil with the hydrogen content of 0.22% into a reaction bottle with a mechanical stirring device, adding 0.64g of Karstedt catalyst, replacing air in the reaction bottle, filling sufficient nitrogen, heating to 80 ℃ in the nitrogen atmosphere, stirring for 15min, injecting 0.72kg of propenyl-1, 3-sultone with air discharged in advance into the reaction bottle, then carrying out heat preservation reaction for 6h, cooling the reaction liquid to room temperature after the reaction is finished, filtering to obtain an oily liquid of a product, adding activated carbon for decoloration to remove the residual platinum catalyst in the product, and filtering to obtain 1.25kg of sulfonic acid ester modified silicone oil.
Adding 1.0kg of potassium hydroxide solution with the mass fraction of 40% into a reaction bottle, distilling at 100 ℃ under reduced pressure to remove 70% of water, adding 1.5kg of ethanol, cooling to 5 ℃, stirring at 5 ℃ for 30min, carrying out suction filtration on the obtained solid-liquid mixture, washing a filter cake with 1.5kg of ethanol, and drying at 80 ℃ to finally obtain 1.24kg of solid product sulfonic modified silicone oil with the yield of 94%.
As determined by Hydrophilic Lipophilic Balance (HLB): dissolving 0.2g of the sample in 20mL of a mixed solution of 1, 4-dioxane and benzene (90:4), titrating the solution with distilled water until the solution is obviously turbid, recording the volume V of the distilled water, and substituting the HLB (hydrophile-lipophile balance) of the formula of 25.7 ligV-11.3 to obtain the solution; the hydrophilic-lipophilic balance (HLB) of the product is 5.7.
The surface tension values of the sulfonic acid group-modified silicone oil in this example were measured by the method in example 1 to be: 29.7N/m.
Example 6
A preparation method of functional fluorine modified silicone oil comprises the following steps:
adding 1.0kg of hydrogen-containing silicone oil with the hydrogen content of 0.65 percent into a reaction bottle with a mechanical stirring device, adding 0.64g of Karstedt catalyst, replacing air in the reaction bottle, filling sufficient nitrogen, heating to 80 ℃ in the nitrogen atmosphere, stirring for 15min, injecting 0.72kg of propenyl-1, 3-sultone with air discharged in advance into the reaction bottle, then carrying out heat preservation reaction for 6h, cooling the reaction liquid to room temperature after the reaction is finished, filtering to obtain an oily liquid of a product, adding activated carbon for decoloration to remove the residual platinum catalyst in the product, and filtering to obtain 1.26kg of sulfonic acid ester modified silicone oil.
Adding 1.0kg of potassium hydroxide solution with the mass fraction of 40% into a reaction bottle, distilling at 100 ℃ under reduced pressure to remove 70% of water, adding 1.5kg of ethanol, cooling to 5 ℃, stirring at 5 ℃ for 30min, carrying out suction filtration on the obtained solid-liquid mixture, washing a filter cake with 1.5kg of ethanol, and drying at 80 ℃ to obtain 1.27kg of solid product sulfonic modified silicone oil with the yield of 96%.
As determined by Hydrophilic Lipophilic Balance (HLB): dissolving 0.2g of the sample in 20mL of a mixed solution of 1, 4-dioxane and benzene (90:4), titrating the solution with distilled water until the solution is obviously turbid, recording the volume V of the distilled water, and substituting the HLB (hydrophile-lipophile balance) of the formula of 25.7 ligV-11.3 to obtain the solution; the hydrophilic-lipophilic balance (HLB) of the product is 5.5.
The surface tension values of the sulfonic acid group modified silicone oil in this example were measured by the method in example 1 as follows: 28.4N/m.
The HLB value is a quantity that characterizes the relative size between the hydrophilic and lipophilic groups of the surfactant, and ranges from 0 to 20, with closer to 0 indicating greater lipophilicity and closer to 20 indicating greater hydrophilicity. According to the fact that the HLB value of the product is measured for many times, the range of the HLB value of the product is 5.5-6.2, and the modified silicone oil is shown to have a better lipophilic value. The surface tension of the surfactant prepared by the method is 28.4N/m-30.9N/m, and compared with the surface tension of 35.0N/m-45.0N/m of the common hydrophilic modified silicone oil, the surface tension is reduced, and the dispersion is facilitated.
Application example
The application of the sulfonic modified silicone oil in applying the prepared sulfonic modified silicone oil to pet dog detergent comprises the following steps: adding 1kg of water into a reaction bottle with a mechanical stirring device, heating to 55 ℃, sequentially adding 40g of anionic surfactant, 60g of biomass charcoal, 120g of salt lake water concentrated solution and 80g of sodium xylene sulfonate into the reaction bottle, stirring to be completely dissolved, adding 60g of the sulfonic modified silicone oil and 60g of regulator into the reaction bottle after substances in the reaction bottle are completely dissolved, stirring for 20min at 55 ℃, finally adding 100g of dialkyl sulfonamide, 60g of antifungal agent, 40g of protecting agent, 60g of natural source acaricide, 100g of plant essence and 140g of glycerin into the reaction bottle, stirring for 30min at 55 ℃, adjusting the pH to be about 8 by using sodium silicate during stirring, standing and cooling after the reaction is finished, packaging and bottling, thus preparing the pet dog detergent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention.
Claims (10)
1. The preparation method of the sulfonic modified silicone oil is characterized by comprising the following steps:
s1, taking propenyl-1, 3-sultone and hydrogen-containing silicone oil as raw materials in an inert atmosphere, carrying out addition reaction by using a platinum catalyst, and separating and purifying to obtain sulfonate modified silicone oil;
s2, adding the sulfonate modified silicone oil into an alkali solution, carrying out hydrolysis reaction, and separating and purifying to obtain the sulfonic modified silicone oil.
2. The method for preparing a sulfonic acid group-modified silicone oil according to claim 1, wherein the hydrogen content of the hydrogen-containing silicone oil is 0.18% to 0.65%.
3. The method for producing a sulfonic acid group-modified silicone oil according to claim 1, wherein the molar ratio of the hydrogen-containing silicone oil to the propenyl-1, 3-sultone is 1:1.2 to 1: 1.4.
4. The method for producing a sulfonic acid group-modified silicone oil according to claim 1, wherein in step S1, the mass of the platinum catalyst is 0.03% to 0.10% of the raw material.
5. The method for producing a sulfonic acid group-modified silicone oil according to claim 1, wherein in step S2, the alkali solution is a sodium hydroxide solution and/or a potassium hydroxide solution.
6. The method for preparing a sulfonic acid group-modified silicone oil according to claim 1, wherein the mass fraction of the alkali solution is 30% to 40%.
7. The method for producing a sulfonic acid group-modified silicone oil according to claim 1, wherein in step S1, the step of separation and purification is a step of adding the addition reaction product to activated carbon to decolorize, followed by filtration, and degassing the filtrate.
8. The method for preparing sulfonic acid group-modified silicone oil according to claim 1, wherein in step S2, the step of separating and purifying comprises adding the hydrolysis reaction product to ethanol, stirring at 0-5 ℃, then performing suction filtration, washing the filter cake with ethanol, and drying.
9. Sulfonic acid group-modified silicone oil obtained by the production method according to any one of claims 1 to 8.
10. Use of the sulfonic acid group-modified silicone oil according to claim 9 in a surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210821725.1A CN115044044B (en) | 2022-07-13 | 2022-07-13 | Sulfonic group modified silicone oil and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210821725.1A CN115044044B (en) | 2022-07-13 | 2022-07-13 | Sulfonic group modified silicone oil and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115044044A true CN115044044A (en) | 2022-09-13 |
| CN115044044B CN115044044B (en) | 2023-04-14 |
Family
ID=83165255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210821725.1A Active CN115044044B (en) | 2022-07-13 | 2022-07-13 | Sulfonic group modified silicone oil and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115044044B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000319307A (en) * | 1999-05-12 | 2000-11-21 | Dai Ichi Kogyo Seiyaku Co Ltd | New decomposable reactive emulsifier, and modification of polymer using the same |
| CN1439452A (en) * | 2002-08-23 | 2003-09-03 | 上海制皂有限公司 | Organic silicon anionic surfctant and its synthesis |
| WO2013097167A1 (en) * | 2011-12-27 | 2013-07-04 | 广东标美硅氟新材料有限公司 | Silicone surfactant, and preparation method and use thereof |
-
2022
- 2022-07-13 CN CN202210821725.1A patent/CN115044044B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000319307A (en) * | 1999-05-12 | 2000-11-21 | Dai Ichi Kogyo Seiyaku Co Ltd | New decomposable reactive emulsifier, and modification of polymer using the same |
| CN1439452A (en) * | 2002-08-23 | 2003-09-03 | 上海制皂有限公司 | Organic silicon anionic surfctant and its synthesis |
| WO2013097167A1 (en) * | 2011-12-27 | 2013-07-04 | 广东标美硅氟新材料有限公司 | Silicone surfactant, and preparation method and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115044044B (en) | 2023-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Dissolution of highly molecular weight cellulose isolated from wheat straw in deep eutectic solvent of Choline/L-Lysine hydrochloride | |
| Ju et al. | Continuous production of lignin nanoparticles using a microchannel reactor and its application in UV-shielding films | |
| CN106731883B (en) | Polydopamine nano lignocellulose polyvinylidene fluoride composite ultrafiltration membrane and preparation method thereof | |
| JP6439712B2 (en) | Method for producing spherical polymethylphenylsilsesquioxane particles | |
| CN108310984A (en) | A kind of anti-pollution hydrophilic PVDF Modified Membrane and preparation method thereof | |
| CN110041474B (en) | Organic/inorganic hybrid cation reverse demulsifier and preparation method and application thereof | |
| CN104291412B (en) | For the preparation method of the reverse-phase emulsifier containing polymer sewage from oil extraction process | |
| CN115044044B (en) | Sulfonic group modified silicone oil and preparation method and application thereof | |
| WO2022048099A1 (en) | Method for preparing narrow-distribution triethanolamine block polyether, block polyether, and use thereof | |
| CN115677886B (en) | Method for preparing high-acetalization-rate polyvinyl butyral without adding surfactant | |
| CA1244368A (en) | Processing of a heteropolysaccharides solution; heteropolysaccharides powder compositions and their use | |
| CN112877042A (en) | Modified porous green environment-friendly powder defoaming agent and preparation method thereof | |
| CN105061768B (en) | A kind of preparation method of epoxy-capped pendant vinyl yhnethylphenyl silicone oil | |
| CN103877941B (en) | A kind of spherical silica-based hybrid inorganic-organic boron adsorbent and preparation method thereof | |
| CN114367202B (en) | Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis | |
| CN113041849B (en) | Method for preparing hydrogenated nitrile rubber/mesoporous silica composite cation exchange membrane by utilizing semi-interpenetrating network polymerization method and application thereof | |
| CN112898500B (en) | Preparation method of stable cationic pigment dispersant and stable cationic pigment dispersant | |
| CN113444237B (en) | Quaternized polyether reverse demulsifier and preparation method thereof | |
| CN115124720B (en) | Modified gelatin for coating printing and dyeing adhesive as well as preparation method and application thereof | |
| CN108310976A (en) | A kind of preparation method of high throughput nanometer compounding sea water desalination film | |
| CN114907844A (en) | Sodium lignosulfonate-based nitrogen/sulfur double-doped carbon quantum dot and preparation method thereof | |
| CN111330451B (en) | Preparation method of hydrophobic carbon point modified forward osmosis composite membrane | |
| CN115028785A (en) | Temperature-resistant salt-tolerant oil displacement surfactant and preparation method thereof | |
| CN109678725B (en) | Process for preparing p-phenylenediamine | |
| CN102690374A (en) | Method for comprehensively drying liquid rubber and drying device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A sulfonic acid modified silicone oil and its preparation method and application Effective date of registration: 20231220 Granted publication date: 20230414 Pledgee: Bank of China Limited Xiangyang Branch Pledgor: ZAOYANG HUAWEI FLUOSILICIC MATERIAL Co.,Ltd. Registration number: Y2022980029505 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |