A phenyl silicone oil and its preparation method

Abstract

The present invention discloses a phenyl silicone oil and its synthesis process. The phenyl silicone oil obtained by this process has a low alkoxy content, better storage stability, and does not release small alcohol molecules such as methanol and ethanol after being added to the formulation and used, making it safer and more reliable in the cosmetic field. Compared with similar products, it has a higher refractive index at the same viscosity.

Description

Technical Field

[0001] The present invention relates to a preparation method of a cosmetic silicone oil, and particularly to a phenyl silicone oil and a preparation method thereof. Technical Background

[0002] Phenyl silicone oil is one of the main varieties of silicone oil. Due to its good chemical stability, high and low temperature resistance, electrical insulation, radiation resistance, high refractive index, and physiological inertness, etc., it is widely used in the fields of daily chemicals, electronics, machinery, etc.

[0003] Traditional phenyl silicone oil is a linear polydimethylsiloxane in which part of the methyl groups are replaced by phenyl groups. Using it as a cosmetic raw material can improve gloss and compatibility. However, it has the following disadvantages: it has poor compatibility with solvents with a certain polarity such as ethanol and isopropanol, and compounds such as paraffin and mineral oil with long carbon chains; when the viscosity is low, the refractive index is low; it is very difficult to achieve completely colorless and odorless; especially the odor of silicone oil with diphenylsiloxane linkages is even more difficult to remove.

[0004] The branched phenyl silicone oil disclosed in CN100396715 can replace the traditional linear phenyl silicone oil to solve the compatibility problem, and it can be made colorless and odorless through adsorption, and is applied in the cosmetic field. However, there will be alkoxy residues in its synthesis method system, and the storage stability is not good, and there is a tendency for the viscosity to increase after long-term placement.

[0005] Therefore, it is necessary to develop a phenyl silicone oil with a low alkoxy content, better storage stability, and that does not release small alcohol molecules such as methanol and ethanol after being added to the formula for use. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides a phenyl silicone oil. This phenyl silicone oil is colorless and odorless. Compared with similar products, it has a higher refractive index at the same viscosity, and has good compatibility with common cosmetic raw materials such as weakly polar alcohols, long-chain paraffin, and mineral oil. It is suitable as a cosmetic raw material and can be applied in skin care, hair care, and high-refractive-index color cosmetic products.

[0007] The present invention adopts the following technical solutions:

[0008] In the first aspect of the present invention, a phenyl silicone oil is provided, and its structural formula is:

[0009]

[0010] R1, R2, and R3 are each independently a monovalent hydrocarbon group or aromatic group having 1 to 6 carbon atoms, preferably methyl, ethyl, or phenyl; m = 0 to 10, n = 0 to 10, and m and n are not both 0 at the same time;

[0011] Its basic properties are:

[0012] Appearance: Colorless transparent liquid

[0013] Odor: Odorless

[0014] Viscosity at 25°C: 10 - 100 cp, preferably 10 - 50 cp

[0015] Refractive index at 25°C: 1.4600 - 1.5100

[0016] Content of residual alkoxy groups (calculated by NMR): ≤0.2 mol / kg

[0017] In the second aspect of the present invention, a preparation method of the above-mentioned phenyl silicone oil is provided, which includes the following steps:

[0018] 1) Put alkoxyphenylsilane, a capping agent and a catalyst into a reaction kettle;

[0019] 2) Heat to 50 - 60°C, dropwise add a calculated amount of water to the system and continue to react for a certain period of time;

[0020] 3) Let it stand for oil-alcohol phase separation to separate out small alcohol molecules;

[0021] 4) Add a strong acid protonic acid to the oil phase for enhanced condensation;

[0022] 5) Separate out the acid layer, neutralize and filter;

[0023] 6) Remove low-volatile substances in the system under negative pressure;

[0024] 7) Add activated carbon for adsorption and then filter to obtain phenyl silicone oil.

[0025] In the said preparation method, in step 1), the alkoxyphenylsilane includes at least one of phenyltrimethoxysilane, phenyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane;

[0026] The capping agent is a disiloxane with the structure of [R1R2R3SiO 1 / 2 2, where R1, R2, and R3 are each independently a monovalent hydrocarbon group or aromatic group with 1 - 6 carbon atoms, preferably methyl, ethyl or phenyl;

[0027] The catalyst is an inorganic acid or an organic acid; the inorganic acid is preferably at least one of hydrochloric acid, sulfuric acid, phosphoric acid; the organic acid is preferably at least one of formic acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid; the catalyst is more preferably trifluoromethanesulfonic acid;

[0028] Preferably, the dosage of the catalyst is 1‰ - 5‰ of the total mass of the raw materials.

[0029] In the preparation method, in step 2), the hydrolysis and condensation reaction temperature is 50-60°C, the reaction time is 1-4 h; the amount of water used is 0.5-1 times the total amount of alkoxy functional groups in the raw materials.

[0030] In the preparation method, in step 4), the strong acid protonic acid used for enhanced condensation is concentrated sulfuric acid, the enhanced condensation temperature is 20-100°C, preferably 50-80°C, and the enhanced condensation time is 1-3 h.

[0031] The amount of the strong acid protonic acid used is 1%-5% of the mass of the oil phase.

[0032] In the preparation method, in step 5), neutralization is carried out using a carbonate, the carbonate is one or more of alkali metal carbonates, and the amount used is 3-5% of the mass of the oil phase; more preferably, the carbonate is sodium bicarbonate.

[0033] In the preparation method, in step 6), the pressure of vacuum devolatilization is 10 mbar-50 mbar, the temperature is 100-150°C, and the time is 1-5 h.

[0034] In the preparation method, in step 7), the amount of activated carbon used is 1%-5% of the mass of the material.

[0035] Compared with the prior art, the present invention has the following technical advantages:

[0036] (1) The present invention develops a phenyl silicone oil and its synthesis process. The phenyl silicone oil obtained by this process has a low alkoxy content, better storage stability, and does not release small alcohol molecules such as methanol and ethanol after being added to the formulation and used, making it safer and more reliable in the cosmetic field.

[0037] (2) Compared with similar products, it has a higher refractive index at the same viscosity. Specific embodiments

[0038] To better understand the present invention, the content of the present invention will be further described below in conjunction with embodiments, but the content of the present invention is not limited to the following embodiments.

[0039] Testing methods:

[0040] Viscosity: GB / T 10247-2008.

[0041] Alkoxy content: 1 1H nuclear magnetic resonance spectrometer.

[0042] Refractive index: GB / T 13531.7-2018.

[0043] Storage stability test: Place at a constant temperature of 50°C for 4 weeks, and test the growth rate of viscosity.

[0044] Example 1 (m = 1, n = 1)

[0045] 198.3 g of phenyltrimethoxysilane, 224.4 g of diphenyldimethoxysilane, 243.4 g of hexamethyldisiloxane, and 0.67 g of trifluoromethanesulfonic acid were put into a reaction kettle equipped with a condensing device and nitrogen protection. The materials in the reaction kettle were heated to 50 °C, and 54 g of water was slowly added. The reaction continued at 60 °C for 2 h. After standing for phase separation of the oil-alcohol (the alcohol contains unreacted water), the mixture of methanol and water was separated. 11.5 g of concentrated sulfuric acid was added to the collected 574 g of oil phase, and it was heated to 60 °C and reacted for 3 h. The acid water layer was separated by phase separation. 24.5 g of sodium bicarbonate was added to the oil phase for neutralization for 1 h and then filtered. The oil phase was subjected to vacuum devolatilization at 50 mbar and 120 °C for 2 h. After cooling to room temperature, 15 g of activated carbon was added for adsorption for 2 h and then filtered through a 1-μm filter membrane. The obtained phenyl silicone oil had a viscosity of 20 cp and a methoxy content of 0.035 mol / kg; the refractive index was 1.4955, and the viscosity growth rate in the storage stability test was 1.1%.

[0046] Example 2 (m = 3, n = 0)

[0047] 594.9 g of phenyltrimethoxysilane, 407.5 g of hexamethyldisiloxane, and 5.01 g of concentrated sulfuric acid were put into a reaction kettle equipped with a condensing device and nitrogen protection. The materials in the reaction kettle were heated to 55 °C, and 97.2 g of water was slowly added. The reaction continued at 60 °C for 4 h. After standing for phase separation of the oil-alcohol (the alcohol contains unreacted water), the mixture of methanol and water was separated. 8.2 g of concentrated sulfuric acid was added to the collected 800.6 g of oil phase, and it was heated to 60 °C and reacted for 3 h. The acid water layer was separated by phase separation. 32 g of sodium bicarbonate was added for neutralization for 1 h and then filtered. The oil phase was subjected to vacuum devolatilization at 50 mbar and 140 °C for 2 h. After cooling to room temperature, 20 g of activated carbon was added for adsorption for 2 h and then filtered through a 1-μm filter membrane. The obtained phenyl silicone oil had a viscosity of 28.7 cp and a methoxy content of 0.13 mol / kg; the refractive index was 1.4680, and the viscosity growth rate in the storage stability test was 1.3%.

[0048] Example 3 (m = 0, n = 1)

[0049] 224.4 g of diphenyldimethoxysilane, 162.3 g of hexamethyldisiloxane, and 0.42 g of trifluoromethanesulfonic acid were added to a reaction kettle equipped with a condensation device and nitrogen protection. The materials in the reaction kettle were heated to 50 °C, and 36 g of water was slowly added. The reaction continued at 60 °C for 2 h. After standing, the oil alcohol (the alcohol contains unconsumed complete water) was phase-separated, and the mixture of methanol and water was separated. 14.6 g of concentrated sulfuric acid was added to 365.5 g of the oil phase, and the mixture was heated to 80 °C and reacted for 3 h. The acid water layer was separated by phase separation. 18.2 g of sodium bicarbonate was added for neutralization for 1 h, and then filtered. The oil phase was subjected to vacuum devolatilization at 10 mbar and 120 °C for 5 h. After cooling to room temperature, 10 g of activated carbon was added for adsorption for 2 h, and then filtered through a 1-μm filter membrane. The obtained phenyl silicone oil had a viscosity of 10.3 cp and a methoxy content of 0.031 mol / kg; the refractive index was 1.5015, and the viscosity growth rate in the storage stability test was 1.05%.

[0050] Example 4 (m = 5, n = 5)

[0051] 240 g of phenyltriethoxysilane, 272 g of diphenyldiethoxysilane, 113.7 g of hexamethyldisiloxane, and 3.04 g of trifluoromethanesulfonic acid were added to a reaction kettle equipped with a condensation device and nitrogen protection. The materials in the reaction kettle were heated to 50 °C, and 72 g of water was slowly added. The reaction continued at 60 °C for 4 h. After standing, the oil alcohol (the alcohol contains unconsumed complete water) was phase-separated, and the mixture of ethanol and water was separated. 21 g of concentrated sulfuric acid was added to 420.5 g of the oil phase, and the mixture was heated to 80 °C and reacted for 3 h. The acid water layer was separated by phase separation. 21 g of sodium bicarbonate was added for neutralization for 1 h, and then filtered. The oil phase was subjected to vacuum devolatilization at 10 mbar and 120 °C for 5 h. After cooling to room temperature, 11 g of activated carbon was added for adsorption for 2 h, and then filtered through a 1-μm filter membrane. The obtained phenyl silicone oil had a viscosity of 95 cp and an ethoxy content of 0.150 mol / kg; the refractive index was 1.5095, and the viscosity growth rate in the storage stability test was 2.4%.

[0052] Comparative Example 1

[0053] Prepare phenyl silicone oil according to Example 3 disclosed in CN100396715C

[0054] Add 222 g of deionized water and 72 g of hydrochloric acid with a mass concentration of 38% to a 1 L four-necked flask and stir. Mix 196 g of phenyltriethoxysilane and 400 g of hexamethyldisiloxane evenly, and slowly add them dropwise to the flask within 2 hours, controlling the reaction temperature at 60 °C. After the addition, raise the temperature to 75 °C and react for another 3 hours. After the reaction, let it stand to separate water. Repeatedly wash the oil phase with alkali and water until it is neutral. Then, perform vacuum distillation at 11.3 KPa and 150 °C for 2 hours. After cooling to room temperature, add 12 g of activated carbon, raise the temperature to 40 °C, stir for 4 hours, and then filter to obtain a colorless and odorless product. The ethoxy content is tested to be 0.89 mol / kg, and the viscosity increases by 25% in the storage stability test.

[0055] Comparative Example 2

[0056] Add 240 g of phenyltriethoxysilane, 272 g of diphenyldiethoxysilane, 113.7 g of hexamethyldisiloxane, and 3.04 g of trifluoromethanesulfonic acid into a reaction kettle equipped with a condensation device and nitrogen protection. Heat the materials in the reaction kettle to 50 °C, slowly add 72 g of water, and continue to react at 60 °C for 4 h. Let it stand for the oil-alcohol (the alcohol contains unconsumed complete water) to phase-separate, and separate the mixture of ethanol and water. Add 23 g of sodium bicarbonate to about 420.5 g of the oil phase, neutralize for 1 h, and then filter. Perform vacuum devolatilization on the oil phase at 10 mbar and 120 °C for 5 h. After cooling to room temperature, add 12 g of activated carbon to adsorb for 2 h, and then filter with a 1 μm filter membrane. The viscosity of the obtained phenyl silicone oil is 94 cp, the ethoxy content is 0.95 mol / kg; the refractive index is 1.5097, and the viscosity increases by 27% in the storage stability test.

Claims

1. A preparation method of phenyl silicone oil, the structural formula of the phenyl silicone oil is: Among them, R1, R2, and R3 are each independently methyl, ethyl or phenyl; m = 0 to 10, n = 0 to 10, and m and n are not both 0 at the same time; its residual alkoxy content ≤ 0.2 mol / kg; The preparation method includes the following steps: a) Put alkoxyphenylsilane, a capping agent and a catalyst into a reaction kettle; Among them, the alkoxyphenylsilane includes at least one of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane, and the capping agent is a disiloxane having a 1 / 2 2 structure, wherein R1, R2, and R3 are each independently methyl, ethyl, or phenyl, and the catalyst is an inorganic acid or an organic acid. Among them, the inorganic acid is selected from at least one of hydrochloric acid, sulfuric acid, and phosphoric acid, and the organic acid is selected from at least one of methanesulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid; b) Heat to 50 - 60 °C, add the calculated amount of water to the system and continue to react for a certain time; c) Let it stand for oil-alcohol phase separation and separate out small alcohol molecules; d) Add a strong acid protonic acid to the oil phase to strengthen condensation; e) Separate out the acid layer, neutralize and filter; f) Remove low-volatile substances in the system; g) Add activated carbon for adsorption and then filter to obtain phenyl silicone oil.

2. The preparation method according to claim 1, wherein The dosage of the catalyst is 1‰ - 5‰ of the total mass of the raw materials.

3. The preparation method according to claim 1, characterized in that, In step b, the dosage of water is 0.5 - 1 times the total amount of alkoxy functional groups in the raw materials.

4. The preparation method according to claim 1, characterized in that, In step d, the strong acid protonic acid is concentrated sulfuric acid.

5. The preparation method according to claim 4, characterized in that, In step d, the dosage of the strong acid protonic acid is 1% - 5% of the mass of the oil phase.

6. The preparation method according to claim 1, characterized in that, In step d, the strengthening condensation temperature is 20 - 100 °C, and the strengthening condensation time is 1 - 3 h.

7. The preparation method according to claim 6, characterized in that, In step d, the strengthening condensation temperature is 50 - 80 °C.

8. The preparation method according to claim 1, characterized in that, In step e, use a carbonate or sodium bicarbonate for neutralization, and the carbonate is one or more of alkali metal carbonates.

9. The preparation method according to claim 8, wherein, In step e, the dosage of the carbonate or sodium bicarbonate is 3 - 5% of the mass of the oil phase.

10. The preparation method according to claim 1, characterized in that, In step f, carry out vacuum devolatilization, the pressure is 10 mbar - 50 mbar, the temperature is 100 - 150 °C, and the time is 1 - 5 h.

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