Modified fluorosilicone oil as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic silicone oil, and particularly relates to modified fluorosilicone oil as well as a preparation method and application thereof. The modified fluorosilicone oil provided by the invention has a structure as shown in a formula I, and n is any integer from 1 to 15; the ratio of c to d is (1-7): 1, the value of a / (a + b + c + d + e) is 0-30%, and the value of e / (a + b + c + d + e) is 1-45%. A side chain of the modified fluorosilicone oil provided by the invention simultaneously contains a hydrophilic group trimethylolpropane monopropyl ether group, an oleophylic group alpha-methyl phenethyl group, a long-chain alkyl group and an oleophobic group nonafluorohexyl group, so that the modified fluorosilicone oil has good solvent resistance and low surface energy performance; the low-temperature fluidity and surface energy distribution can be improved, when the defoaming agent is applied to a coating, the coating can have good defoaming property and leveling property, and the defoaming agent has good compatibility with white carbon black matting powder in a matte coating and can enable the white carbon black matting powder to be directionally arranged. Formula I.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon oil technology, specifically relating to a modified fluorosilicone oil, its preparation method, and its application. Background Technology

[0002] Silicone oil is a high-molecular-weight polymer composed of repeating Si-O-Si structural units. Its unique molecular structure offers many advantages, such as strong chemical inertness and low surface tension, making it easy to spread and suitable as a wetting agent and defoamer. Furthermore, silicone oil remains stable at both extremely low and high temperatures, exhibiting wide temperature range performance. In addition, it possesses excellent electrical insulation properties, making it suitable for the electronics and electrical industries. However, organosilicon materials have poor resistance to acids, alkalis, and solvents. The high bond energy of the CF bond allows polymers containing CF bonds to be used in strong acid and alkali environments. Introducing fluorinated functional groups into the polysiloxane segments can effectively improve the acid, alkali, and solvent resistance of silicone oil. Simultaneously, due to its low surface energy, it can be used for leveling and defoaming in the coatings industry.

[0003] Existing fluorinated silicone oils have good leveling and defoaming properties when used as coating additives, but they have poor compatibility with silica matting powder, which affects the surface properties of matte coatings. Summary of the Invention

[0004] In view of this, the present invention provides a modified fluorosilicone oil, its preparation method and application. The modified fluorosilicone oil provided by the present invention has good compatibility with silica matting powder in coatings. When added to coatings, it has good defoaming and leveling properties and can make the matting powder oriented.

[0005] To solve the above-mentioned technical problems, the present invention provides a modified fluorosilicone oil having the structure shown in Formula I: Formula I; Where n is any integer from 1 to 15; The ratio of c:d is 1 to 7:1, the value of a / (a+b+c+d+e) is 0 to 30%, and the value of e / (a+b+c+d+e) is 1 to 45%.

[0006] Preferably, n is any integer from 4 to 10.

[0007] This invention also provides a method for preparing the modified fluorosilicone oil described above, comprising the following steps: Compound 1, compound 2, trimethylolpropane monoallyl ether, and α-methylstyrene were first mixed to obtain a mixed solution; The mixed solution and the second catalyst are mixed and then subjected to an addition reaction to obtain the modified fluorosilicone oil; Compound 1, Compound 2; where m is the sum of b, c, and d.

[0008] Preferably, compound 2 comprises 1-octene or 1-heptene.

[0009] Preferably, the mass ratio of compound 1 to compound 2 is 40:2~12, the mass ratio of compound 1 to trimethylolpropane monoallyl ether is 40:8~10, and the mass ratio of compound 1 to α-methylstyrene is 40:6~20.

[0010] Preferably, the first mixing is carried out under stirring conditions, and the first mixing process is accompanied by a temperature rise, the final temperature of which is 58~62°C.

[0011] Preferably, the catalyst comprises a Karstedt catalyst; the second mixing is carried out under stirring conditions.

[0012] Preferably, the addition reaction is carried out at a temperature of 80~120℃ for a time of 0.5~3 h.

[0013] Preferably, the addition reaction further includes: subjecting the system after the addition reaction to vacuum distillation to obtain the modified fluorosilicone oil.

[0014] The present invention also provides the application of the modified fluorosilicone oil described in the above technical solution or the modified fluorosilicone oil prepared by the preparation method described in the above technical solution as a coating additive.

[0015] This invention provides a modified fluorosilicone oil having the structure shown in Formula I: Formula I; where n is any integer from 1 to 15; c:d is 1 to 7:1, a / (a+b+c+d+e) is 0 to 30%, and e / (a+b+c+d+e) is 1 to 45%. The modified fluorosilicone oil side chain provided by this invention simultaneously contains the hydrophilic trimethylolpropane monopropyl ether group, the lipophilic α-methylphenylethyl group, the long-chain alkyl group, and the oleophobic nonafluorohexyl group, giving it good solvent resistance and low surface energy properties; it can improve low-temperature fluidity and surface energy distribution, and when applied to coatings, it can give the coatings good defoaming and leveling properties, and it has good compatibility with silica matting powder in matte coatings, enabling it to oriented. Attached Figure Description

[0016] Figure 1 The image shows the hydrogen spectrum of the modified fluorosilicone oil prepared in Example 1. Detailed Implementation

[0017] This invention provides a modified fluorosilicone oil having the structure shown in Formula I: Formula I; Where n is any integer from 1 to 15, and can be any integer from 4 to 10, specifically 4, 5, 6, 7, 8 or 9; c:d is 1 to 7:1, specifically 2:1, 4:1 or 5:1; the value of a / (a+b+c+d+e) is 0 to 30%, specifically 10%, 15%, 20% or 25%; the value of e / (a+b+c+d+e) is 1 to 45%, specifically 10%, 20%, 30% or 35%.

[0018] This invention also provides a method for preparing the modified fluorosilicone oil described above, comprising the following steps: Compound 1, compound 2, trimethylolpropane monoallyl ether, and α-methylstyrene were first mixed to obtain a mixed solution; The mixed solution and the second catalyst are mixed and then subjected to an addition reaction to obtain the modified fluorosilicone oil; , Compound 2; where m is the sum of b, c, and d.

[0019] Compound 1, Compound 2, trimethylolpropane monoallyl ether, and α-methylstyrene are first mixed to obtain a mixed solution. In one specific embodiment of the invention, Compound 2 may include 1-octene or 1-heptene; the mass ratio of Compound 1 to Compound 2 may be 40:2~12, or 40:3~10; the mass ratio of Compound 1 to trimethylolpropane monoallyl ether may be 40:8~10, specifically 40:9; the mass ratio of Compound 1 to α-methylstyrene may be 40:6~20, or 40:9~15. The present invention controls the values ​​of b, c, and d in Formula I by controlling the amount of Compound 2, trimethylolpropane monoallyl ether, and α-methylstyrene added.

[0020] As a specific embodiment of the present invention, the first mixing can be carried out under stirring conditions. The present invention does not have any special limitation on the stirring, as long as it can be mixed evenly. The first mixing process is accompanied by heating, and the final temperature of the heating can be 58~62℃, specifically 60℃.

[0021] After obtaining the mixed solution, the present invention further mixes the mixed solution with the catalyst and then performs an addition reaction to obtain the modified fluorosilicone oil. As a specific embodiment of the present invention, the catalyst may include a Karstedt catalyst; the present invention may add the catalyst at the end of the heating process in the first mixing process; the amount of catalyst added may be 12-20 ppm (calculated based on the actual platinum content); the second mixing may be carried out under stirring conditions; the present invention has no special limitations on the stirring, as long as it can achieve uniform mixing.

[0022] In one specific embodiment of the present invention, the temperature of the addition reaction can be 80~120℃ or 90~110℃; the time of the addition reaction can be 0.5~3 h, specifically 1 h, 2 h or 3 h.

[0023] In this invention, the equation for the addition reaction is shown in equation a: Formula a.

[0024] In one specific embodiment of the present invention, the addition reaction may further include: subjecting the system after the addition reaction to vacuum distillation to obtain the modified fluorosilicone oil; the vacuum distillation temperature may be 70~110℃, and the vacuum distillation time may be 1~2 h. In another specific embodiment of the present invention, the vacuum distillation may further include: cooling the system after vacuum distillation to room temperature, where the room temperature may be 20~35℃, or even 25~30℃.

[0025] The preparation method provided by this invention has the advantages of simple operation, mild reaction conditions, no solvent required, and stable and excellent product performance. It can be widely used in coatings, paints and other industries that require matte finish, leveling and defoaming properties.

[0026] This invention also provides the application of the modified fluorosilicone oil described in the above-described technical solutions or the modified fluorosilicone oil prepared by the preparation method described in the above-described technical solutions as a coating additive. As a specific embodiment of this invention, the coating may include an alkyd resin coating; the amount of the modified fluorosilicone oil added to the coating as a coating additive may be 0.08~0.12%, specifically 0.1%.

[0027] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0028] Example 1 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 3:4:3) with a viscosity of 45 cp, 8.6 g of 1-octene, 9.0 g of α-methylstyrene, and 9.0 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 1 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 110 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0029] The prepared liquid was subjected to proton NMR spectroscopy analysis, and the resulting proton NMR spectrum is shown below.Figure 1 As shown, the measurement results are as follows: 1 H-NMR (CDCl3, 400M), delta 7.19-7.16 (m, Ph-H), 3.65~3.55 (m, CH2OH), 3.39 (m, Si-CH2CH2CH2O), 2.06-2.02(m, Si-CH2CH2CF2CF2CF2CF3), 1.58(s, Si-CH2CHPhCH3), 1.29-1.25(m, Si-CH2CH2CH2CH2CH2CH2CH2CH3), 0.86-0.76 (m, Si-CH2CH2CH2CH2CH2CH2CH2CH3 and Si-CH2CH2CF2CF2CF2CF3), 0.50 (m, Si-CH2CH2CH2CH2CH2CH2CH2CH3, Si-CH2CHPhCH3 and Si-CH2CH2CH2O), 0.15-0.08 (s,Si-CH3).

[0030] The proton NMR spectrum results show that the liquid prepared by this invention contains trimethylolpropane monopropyl ether, phenyl and long-chain alkyl groups, which constitutes a nonafluorohexyl silicone oil, indicating that a compound with the structure shown in Formula I has been prepared.

[0031] Example 2 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 3:4:3) with a viscosity of 45 cp, 11.2 g of 1-octene, 11.8 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 1 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 70 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0032] Example 3 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 3:4:3) with a viscosity of 45 cp, 2.24 g of 1-octene, 16.52 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 1 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 70 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0033] Example 4 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 3:4:3) with a viscosity of 45 cp, 3.36 g of 1-octene, 13.4 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 1 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 70 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0034] Example 5 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 1:1:1) with a viscosity of 40 cp, 2.24 g of 1-octene, 16.52 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 0.8 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 70 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0035] Example 6 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, 40.0 g of compound 1 (a:m:e approximately 0:3:1) with a viscosity of 30 cp, 2.0 g of 1-heptene, 16.52 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether were added. The mixture was stirred and heated until the temperature reached 60 °C. At this point, 0.09 g of Karstedt catalyst (platinum content approximately 0.8 wt%) was added. The temperature was raised to 110 °C for an addition reaction for 2 h. After the reaction was completed, the mixture was distilled under reduced pressure at 70 °C for 1 h and then cooled to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0036] Example 7 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 1:1:1) with a viscosity of 36 cp, 2.0 g of 1-heptene, 16.52 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 1 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 70 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0037] Example 8 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 2:4:3) with a viscosity of 41 cp, 10 g of 1-heptene, 11.8 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 1 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 70 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0038] Example 9 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 0:1:1) with a viscosity of 45 cp, 2.0 g of 1-heptene, 16.52 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 0.8 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 110 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0039] Example 10 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, add 40.0 g of compound 1 (a:m:e approximately 1:4:3) with a viscosity of 45 cp, 5.9 g of 1-heptene, 11.4 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether. Stir and heat the mixture until the temperature reaches 60 °C. Then add 0.09 g of Karstedt catalyst (platinum content approximately 1 wt%) and heat to 110 °C for 2 h for the addition reaction. After the reaction is complete, distill under reduced pressure at 70 °C for 1 h and cool to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0040] Example 11 To a 250 mL three-necked flask equipped with a thermometer, mechanical stirrer, and reflux condenser, 40.0 g of compound 1 (a:m:e approximately 0.5:1:1) with a viscosity of 45 cp, 9.5 g of 1-octene, 6.0 g of α-methylstyrene, and 9 g of trimethylolpropane monoallyl ether were added. The mixture was stirred and heated until the temperature reached 60 °C. At this point, 0.09 g of Karstedt catalyst (platinum content approximately 1.2 wt%) was added. The mixture was heated to 110 °C for 2 h to undergo an addition reaction. After the reaction was completed, the mixture was distilled under reduced pressure at 70 °C for 1 h and then cooled to room temperature (25 °C) to obtain modified fluorosilicone oil.

[0041] Test case Modified fluorosilicone oils prepared in Examples 1-11 were added to alkyd resin coatings at a rate of 0.1% of the coating weight. The surface tension of the coatings after adding modified fluorosilicone oils was tested using the maximum bubble pressure method according to GB / T 42415-2023 "Determination of Static Surface Tension of Surfactants". The results are listed in Table 1. The coatings after adding modified fluorosilicone oils were sprayed on a 300×400 paint panel. After curing, the defoaming properties, leveling properties, and matting powder orientation were visually inspected. The results are listed in Table 1.

[0042] Table 1. Performance results of the modified fluorosilicone oils prepared in Examples 1-11

[0043] Note: The alkyd resin (type 3902) is from Jiangsu Sanmu Group; the matting agent is H20 type fumed silica from Wacker Chemie AG, Germany. As can be seen from the results in Table 1, adding the modified fluorosilicone oil provided by the present invention to the coating can significantly reduce the surface tension of the coating, giving it good defoaming and leveling properties; and the modified fluorosilicone oil provided by the present invention has good compatibility with matting powder, enabling the matting powder to be oriented.

[0044] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A modified fluorosilicone oil, characterized in that, It has the structure shown in Equation I: Formula I; Where n is any integer from 1 to 15; The ratio of c:d is 1 to 7:1, the value of a / (a+b+c+d+e) is 0 to 30%, and the value of e / (a+b+c+d+e) is 1 to 45%.

2. The modified fluorosilicone oil according to claim 1, characterized in that, n is any integer from 4 to 10.

3. The method for preparing the modified fluorosilicone oil according to claim 1 or 2, characterized in that, Includes the following steps: Compound 1, compound 2, trimethylolpropane monoallyl ether, and α-methylstyrene were first mixed to obtain a mixed solution; The mixed solution and the second catalyst were mixed and then subjected to a hydrosilylation reaction to obtain the modified fluorosilicone oil; Compound 1, Compound 2; where m is the sum of b, c, and d.

4. The preparation method according to claim 3, characterized in that, Compound 2 includes 1-octene or 1-heptene.

5. The preparation method according to claim 3 or 4, characterized in that, The mass ratio of compound 1 to compound 2 is 40:2~12, the mass ratio of compound 1 to trimethylolpropane monoallyl ether is 40:8~10, and the mass ratio of compound 1 to α-methylstyrene is 40:6~20.

6. The preparation method according to claim 5, characterized in that, The first mixing is carried out under stirring conditions, and the first mixing process is accompanied by a temperature increase, the final temperature of which is 58~62℃.

7. The preparation method according to claim 3, characterized in that, The catalyst includes a Karstedt catalyst; the second mixing is carried out under stirring conditions.

8. The preparation method according to claim 3 or 7, characterized in that, The addition reaction is carried out at a temperature of 80~120℃ for a time of 0.5~3 h.

9. The preparation method according to claim 8, characterized in that, The addition reaction further includes subjecting the system after the addition reaction to vacuum distillation to obtain the modified fluorosilicone oil.

10. The application of the modified fluorosilicone oil according to claim 1 or 2 or the modified fluorosilicone oil prepared by the preparation method according to any one of claims 3 to 9 as a coating additive.

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