Ultraviolet curing amphiphilic organic silicon and preparation method thereof

Abstract

The invention discloses ultraviolet curing amphiphilic organic silicon and a preparation method thereof, and relates to organic silicon and a preparation method thereof. The invention aims to solve the problem that a preparation method for ultraviolet curing amphiphilic organic silicon does not exist in China at present. The preparation method comprises the following steps: synthesizing sulfhydrylation hydrophobic organic silicon through a hydrolysis condensation method, then mixing the sulfhydrylation hydrophobic organic silicon with water-based alkenylation organic silicon self-made in a laboratory, and synthesizing the ultraviolet curing amphiphilic organic silicon under the assistance of a photoinitiator and ultraviolet light with a specific wavelength through an ultraviolet curing technology and a sulfydryl-olefin click reaction. The invention belongs to the technical field of organic silicon modification.

Description

Technical Field

[0001] The invention relates to organosilicon and a preparation method thereof, belonging to the technical field of organosilicon modification. Background Art

[0002] Amphiphilic silicone is a special type of silicone compound that has both hydrophilic and lipophilic (hydrophobic) groups. This unique structure gives them many excellent and unique properties, making them widely used in many fields. Typical amphiphilic silicone molecules are composed of three parts: silicone backbone, hydrophilic group and lipophilic group. The backbone is generally composed of repeating units of silicon-oxygen bonds (Si-O). Silicon-oxygen bonds have high bond energy, giving the molecule good stability and flexibility. Common hydrophilic groups include polyether segments, carboxyl groups (-COOH), sulfonic acid groups (-SO3H), hydroxyl groups (-OH), amino groups (-NH2), etc. These groups easily form hydrogen bonds with water molecules, making the molecules hydrophilic. Lipophilic groups are usually alkyl groups, such as methyl, ethyl, long-chain alkyl, etc., or aromatic groups, such as phenyl, etc. These groups have good compatibility with non-polar oil substances and show lipophilic properties. Amphiphilic silicones are usually used as drug carriers, biomaterial surface modification, fabric finishing agents, emulsifiers and leveling agents, but there are currently no patent reports on UV-curable amphiphilic silicones in China. Summary of the invention

[0003] The present invention aims to solve the problem that there is no method for preparing ultraviolet-curing amphiphilic organosilicon in China, and further proposes an ultraviolet-curing amphiphilic organosilicon and a method for preparing the same.

[0004] The technical solution adopted by the present invention to solve the above problems is: the UV-curable amphiphilic organosilicon described in the present invention is composed of a mercapto-containing silane coupling agent, a fluorinated siloxane, a solvent, a catalyst, a capping agent, an alkaline substance, a photoinitiator, and a self-made water-based olefinic organosilicon; wherein the mass fraction of the mercapto-containing silane coupling agent is 25-100 parts, the mass fraction of the fluorinated siloxane is 0-75 parts, the mass fraction of the solvent is 10-50 parts, the mass fraction of the catalyst is 1-20 parts, the mass fraction of the capping agent is 1-20 parts, the mass fraction of the alkaline substance is 100-2000 parts, the mass fraction of the photoinitiator is 1-10 parts, and the mass fraction of the self-made water-based olefinic organosilicon is 100-200 parts.

[0005] Furthermore, the mercapto-containing silane coupling agent is composed of one or more of γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane.

[0006] Furthermore, the fluorine-containing siloxane is composed of one or more of (3,3,3-trifluoropropyl)methyldichlorosilane, (3,3,3-trifluoropropyl)methyldimethoxysilane, (3,3,3-trifluoropropyl)methyldiethoxysilane, 1,3,5-trimethyl-1,3,5-tri(3,3,3-trifluoropropyl)-cyclotrisiloxane, (3,3,3-trifluoropropyl)trichlorosilane, (3,3,3-trifluoropropyl)trimethoxysilane, (3,3,3-trifluoropropyl)triethoxysilane, perfluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, and trifluoromethyltrimethylsilane.

[0007] Furthermore, the solvent is composed of one or more of water, methanol, anhydrous ethanol, ethyl acetate, acetone, benzene, toluene, xylene, n-hexane, isopropanol, or chloroform.

[0008] Furthermore, the catalyst is composed of one or more of a platinum catalyst, a palladium catalyst, a rhodium catalyst, a ruthenium catalyst, an iron catalyst, a cobalt catalyst, a nickel catalyst, a copper catalyst, a zinc catalyst, a manganese catalyst, a titanium catalyst, trifluoromethanesulfonic acid, sulfuric acid, or a cation exchange resin.

[0009] Furthermore, the end-capping agent is composed of one or more of hexamethyldisiloxane, tetramethyldihydrogendisiloxane, 1,3-divinyltetramethyldisiloxane, 1,1,1,3,3,3-hexaethyldisiloxane, 1,3-dimethyltetravinyldisiloxane, 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane, or tetramethyldihydroxydisiloxane.

[0010] Furthermore, the alkaline substance is composed of one or more of sodium hydroxide, anhydrous sodium carbonate, magnesium oxide, sodium bicarbonate, potassium hydroxide, or ammonia water.

[0011] Further, the photoinitiator is composed of one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphosphonic acid ethyl ester, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, isopropylthioxanthone, 4-isobutylphenyl-4'-methylphenyliodine hexafluorophosphate, or isopropylferrocenium hexafluorophosphate.

[0012] The steps of the method for preparing a UV-curable amphiphilic silicone according to the present invention include:

[0013] Step 1, adding a mercapto-containing silane coupling agent, a fluorinated siloxane, a solvent and a capping agent into a reaction container in sequence, stirring and heating to a set temperature;

[0014] Step 2, adding a catalyst into the reaction vessel, stirring evenly and then starting the reaction;

[0015] Step 3: After the reaction, the vacuum device is connected, and the heating and stirring reaction is continued under vacuum conditions;

[0016] Step 4: After the reaction is completed, the temperature is raised and unreacted small molecular low-boiling substances and solvents are removed under vacuum conditions;

[0017] Step 5, after cooling to room temperature, add alkaline substances, stir for several hours and then let stand;

[0018] Step 6: vacuum filtration to obtain a hydrophobic organosilicon functionalized material, and taking a small amount of the product for molecular weight testing;

[0019] Step 7: Mix the hydrophobic organosilicon functional material with the water-based olefinic organosilicon prepared in the laboratory, add the photoinitiator and stir evenly;

[0020] Step 8: Use a doctor blade to evenly coat the mixture on the substrate, and then cross-link and cure it with the assistance of ultraviolet light to obtain ultraviolet-cured amphiphilic silicone.

[0021] Furthermore, the stirring rate is 100-200 r / min, the temperature of the reaction container in step 1 is raised to 60-120° C., the temperature of the reaction container in step 4 is raised to 150-200° C., and the reaction time in steps 2 and 3 is 1-12 h.

[0022] The beneficial effects of the present invention are as follows: a method for preparing a UV-curable amphiphilic silicone provided by the present invention comprises synthesizing a thiol-modified hydrophobic silicone by a hydrolysis-condensation method, and then mixing the synthesized thiol-modified hydrophobic silicone with a laboratory-made water-based olefinic silicone, and synthesizing the UV-curable amphiphilic silicone by a UV-curing technology and a thiol-olefin click reaction with the assistance of a photoinitiator and UV light of a specific wavelength; the UV-curable amphiphilic silicone prepared by the present invention has the advantages of both hydrophilicity and lipophilicity, and has important application value and broad market prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is the infrared spectrum of the hydrophobic silicone functional material;

[0024] Figure 2 Schematic diagram of contact angle and surface energy of hydrophobic silicone functionalized materials. Example

[0025] Embodiment 1:

[0026] This embodiment discloses a method for preparing a UV-curable amphiphilic silicone, comprising the following steps:

[0027] Step 1: Add 9.02 g of mercapto-containing silane coupling agent, 23.43 g of fluorinated siloxane, 1.8 g of distilled water, 10 mL of anhydrous ethanol and 0.33 g of a capping agent into a reaction vessel in sequence, stir and heat to 70°C;

[0028] Step 2: Add 40 μL of trifluoromethanesulfonic acid as catalyst into the reaction container, stir evenly and start the reaction;

[0029] Step 3: After reacting for 1 hour, connect the vacuum device and continue heating and stirring the reaction for 2 hours under vacuum conditions;

[0030] Step 4: After the reaction is completed, the temperature is raised to 180°C, and unreacted small molecular low-boiling substances and solvents are removed under vacuum conditions;

[0031] Step 5: After cooling to room temperature, add 6.8 g of anhydrous sodium carbonate, stir for 3 hours and then let stand for 12 hours;

[0032] Step 6: vacuum filtration to obtain a hydrophobic organosilicon functionalized material, and take a small amount of the product for molecular weight testing;

[0033] Step 7: Take a certain amount of hydrophobic organosilicon functional material and mix it with the water-based olefinic organosilicon made in the laboratory in a ratio of 1:1, add a certain amount of photoinitiator and stir evenly;

[0034] Step 8: After the film is scraped, cross-linking and curing is performed under the assistance of ultraviolet light to obtain ultraviolet light-cured amphiphilic silicone.

[0035] Embodiment 2:

[0036] This embodiment discloses a method for preparing a UV-curable amphiphilic silicone, comprising the following steps:

[0037] Step 1: 13.53 g of mercapto-containing silane coupling agent, 11.72 g of fluorinated siloxane, 2.7 g of distilled water, 10 mL of anhydrous ethanol and 0.28 g of end-capping agent were added to a reaction vessel in sequence, stirred and heated to 70°C;

[0038] Step 2: Add 33 μL of trifluoromethanesulfonic acid catalyst into the reaction container, stir evenly and start the reaction;

[0039] Step 3: After reacting for 1 hour, connect the vacuum device and continue heating and stirring the reaction for 2 hours under vacuum conditions;

[0040] Step 4: After the reaction is completed, the temperature is raised to 180°C, and unreacted small molecular low-boiling substances and solvents are removed under vacuum conditions;

[0041] Step 5: After cooling to room temperature, add 5.6 g of anhydrous sodium carbonate, stir for 3 hours and then let stand for 12 hours;

[0042] Step 6: vacuum filtration to obtain a hydrophobic organosilicon functionalized material, and take a small amount of the product for molecular weight testing;

[0043] Step 7: Take a certain amount of hydrophobic organosilicon functional material and mix it with the water-based olefinic organosilicon made in the laboratory in a ratio of 1:1, add a certain amount of photoinitiator and stir evenly;

[0044] Step 8: After the film is scraped, cross-linking and curing is performed under the assistance of ultraviolet light to obtain ultraviolet light-cured amphiphilic silicone.

[0045] Embodiment three:

[0046] This embodiment discloses a method for preparing a UV-curable amphiphilic silicone, comprising the following steps:

[0047] Step 1: 16.23 g of mercapto-containing silane coupling agent, 9.39 g of fluorinated siloxane, 3.25 g of distilled water, 10 mL of anhydrous ethanol and 0.29 g of a capping agent were sequentially added into a reaction vessel, stirred and heated to 70°C;

[0048] Step 2: Add 34 μL of trifluoromethanesulfonic acid catalyst into the reaction container, stir evenly and start the reaction;

[0049] Step 3: After reacting for 1 hour, connect the vacuum device and continue heating and stirring the reaction for 2 hours under vacuum conditions;

[0050] Step 4: After the reaction is completed, the temperature is raised to 180°C, and unreacted small molecular low-boiling substances and solvents are removed under vacuum conditions;

[0051] Step 5: After cooling to room temperature, add 5.8 g of anhydrous sodium carbonate, stir for 3 hours and then let stand for 12 hours;

[0052] Step 6: vacuum filtration to obtain a hydrophobic organosilicon functionalized material, and take a small amount of the product for molecular weight testing;

[0053] Step 7: Take a certain amount of hydrophobic organosilicon functional material and mix it with the water-based olefinic organosilicon made in the laboratory in a ratio of 1:1, add a certain amount of photoinitiator and stir evenly;

[0054] Step 8: After the film is scraped, cross-linking and curing is performed under the assistance of ultraviolet light to obtain ultraviolet light-cured amphiphilic silicone.

[0055] Embodiment 4:

[0056] This embodiment discloses a method for preparing a UV-curable amphiphilic silicone, comprising the following steps:

[0057] Step 1: 16.23 g of mercapto-containing silane coupling agent, 4.69 g of fluorinated siloxane, 3.24 g of distilled water, 10 mL of anhydrous ethanol and 0.24 g of a capping agent were sequentially added into a reaction vessel, stirred and heated to 70°C;

[0058] Step 2: Add 29 μL of trifluoromethanesulfonic acid catalyst into the reaction container, stir evenly and start the reaction;

[0059] Step 3: After reacting for 1 hour, connect the vacuum device and continue heating and stirring the reaction for 2 hours under vacuum conditions;

[0060] Step 4: After the reaction is completed, the temperature is raised to 180°C, and unreacted small molecular low-boiling substances and solvents are removed under vacuum conditions;

[0061] Step 5: After cooling to room temperature, add 4.9 g of anhydrous sodium carbonate, stir for 3 hours and then let stand for 12 hours;

[0062] Step 6: vacuum filtration to obtain a hydrophobic organosilicon functionalized material, and take a small amount of the product for molecular weight testing;

[0063] Step 7: Take a certain amount of hydrophobic organosilicon functional material and mix it with the water-based olefinic organosilicon made in the laboratory in a ratio of 1:1, add a certain amount of photoinitiator and stir evenly;

[0064] Step 8: After the film is scraped, cross-linking and curing is performed under the assistance of ultraviolet light to obtain ultraviolet light-cured amphiphilic silicone.

[0065] The performance tests were performed on the hydrophobic organosilicon functionalized materials and the UV-curable amphiphilic organosilicon obtained in Examples 1 to 4.

[0066] Molecular weight test: Weigh 3-5 mg of hydrophobic organosilicon functional material sample and dissolve it in tetrahydrofuran as solvent, and use gel permeation chromatography to test the molecular weight. The test temperature is 25°C, the solution concentration is 3 mg / L, and the flow rate is 1 mL / min.

[0067] Infrared test: Set the number of scans to 32 times and the scanning range to 4000-600cm -1 , perform background scanning to eliminate instrument errors. Take a small amount of hydrophobic silicone functional material sample and drop it into the infrared sample pool, perform sample scanning, and generate the corresponding infrared spectrum. Subtract the background to perform baseline correction to eliminate baseline drift in the spectrum.

[0068] Static contact angle test: Water and diiodomethane were selected as the test liquids. During the test, the volume of water was 3 μL, the volume of diiodomethane was 1.5 μL, and the test temperature was 20°C. The static contact angle θ of the UV-cured amphiphilic silicone surface was measured by a contact angle meter. 水 ,θ 二碘甲烷. , while using θ 水 and θ 二碘甲烷 Calculation of the surface energy of UV-cured amphiphilic silicones.

[0069] Name, thiol content and properties of hydrophobic organosilicon functional materials

[0070]

[0071] GPC results of hydrophobic silicone functionalized materials

[0072]

[0073] The above is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent replacement and improvement made to the above embodiments without departing from the content of the technical solution of the present invention, based on the technical essence of the present invention, within the spirit and principles of the present invention, still fall within the protection scope of the technical solution of the present invention.

Claims

1. A UV-curable amphiphilic silicone, characterized in that: The ultraviolet light-cured amphiphilic silicone consists of a mercapto-containing silane coupling agent, a fluorinated siloxane, a solvent, a catalyst, a capping agent, an alkaline substance, a photoinitiator, and a self-made water-based olefinic silicone; wherein the mass fraction of the mercapto-containing silane coupling agent is 25-100 parts, the mass fraction of the fluorinated siloxane is 0-75 parts, the mass fraction of the solvent is 10-50 parts, the mass fraction of the catalyst is 1-20 parts, the mass fraction of the capping agent is 1-20 parts, the mass fraction of the alkaline substance is 100-2000 parts, the mass fraction of the photoinitiator is 1-10 parts, and the mass fraction of the self-made water-based olefinic silicone is 100-200 parts.

2. The UV-curable amphiphilic silicone according to claim 1, characterized in that: The mercapto-containing silane coupling agent is composed of one or more of gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane.

3. The UV-curable amphiphilic silicone according to claim 1, characterized in that: The fluorine-containing siloxane is composed of one or more of (3,3,3-trifluoropropyl)methyldichlorosilane, (3,3,3-trifluoropropyl)methyldimethoxysilane, (3,3,3-trifluoropropyl)methyldiethoxysilane, 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)-cyclotrisiloxane, (3,3,3-trifluoropropyl)trichlorosilane, (3,3,3-trifluoropropyl)trimethoxysilane, (3,3,3-trifluoropropyl)triethoxysilane, perfluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, and trifluoromethyltrimethylsilane.

4. The UV-curable amphiphilic silicone according to claim 1, characterized in that: The solvent is composed of one or more of water, methanol, anhydrous ethanol, ethyl acetate, acetone, benzene, toluene, xylene, n-hexane, isopropanol, or chloroform.

5. The UV-curable amphiphilic silicone according to claim 1, characterized in that: The catalyst is composed of one or more of platinum catalyst, palladium catalyst, rhodium catalyst, ruthenium catalyst, iron catalyst, cobalt catalyst, nickel catalyst, copper catalyst, zinc catalyst, manganese catalyst, titanium catalyst, trifluoromethanesulfonic acid, sulfuric acid, or cation exchange resin.

6. The UV-curable amphiphilic silicone according to claim 1, characterized in that: The end-capping agent is composed of one or more of hexamethyldisiloxane, tetramethyldihydrogendisiloxane, 1,3-divinyltetramethyldisiloxane, 1,1,1,3,3,3-hexaethyldisiloxane, 1,3-dimethyltetravinyldisiloxane, 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane, or tetramethyldihydroxydisiloxane.

7. The UV-curable amphiphilic silicone according to claim 1, characterized in that: The alkaline substance is composed of one or more of sodium hydroxide, anhydrous sodium carbonate, magnesium oxide, sodium bicarbonate, potassium hydroxide, or ammonia water.

8. The UV-curable amphiphilic silicone according to claim 1, characterized in that: The photoinitiator is composed of one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphosphonic acid ethyl ester, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, isopropylthioxanthone, 4-isobutylphenyl-4'-methylphenyliodine hexafluorophosphate, or isopropylferrocenium hexafluorophosphate.

9. A method for preparing ultraviolet light-cured amphiphilic silicone, characterized in that: The specific steps include: Step 1, adding a mercapto-containing silane coupling agent, a fluorinated siloxane, a solvent and a capping agent into a reaction container in sequence, stirring and heating to a set temperature; Step 2, adding a catalyst into the reaction vessel, stirring evenly and then starting the reaction; Step 3: After the reaction, the vacuum device is connected, and the heating and stirring reaction is continued under vacuum conditions; Step 4: After the reaction is completed, the temperature is raised and unreacted small molecular low-boiling substances and solvents are removed under vacuum conditions; Step 5: After cooling to room temperature, add alkaline substances, stir for several hours and then let stand; Step 6: vacuum filtration to obtain a hydrophobic organosilicon functionalized material, and taking a small amount of the product for molecular weight testing; Step 7: Mix the hydrophobic organosilicon functional material with the water-based olefinic organosilicon prepared in the laboratory, add the photoinitiator and stir evenly; Step 8: Use a doctor blade to evenly coat the mixture on the substrate, and then cross-link and cure it with the assistance of ultraviolet light to obtain ultraviolet-cured amphiphilic silicone.

10. The method for preparing ultraviolet light-cured amphiphilic silicone according to claim 9, characterized in that: The stirring rate is 100-200 r / min, the temperature of the reaction container in step 1 is raised to 60-120° C., the temperature of the reaction container in step 4 is raised to 150-200° C., and the reaction time in steps 2 and 3 is 1-12 h.

Images