Phenyl-containing polysiloxane silicone oil for personal care and preparation method thereof

Abstract

The invention provides phenyl-containing polysiloxane silicone oil for personal care and a preparation method of the phenyl-containing polysiloxane silicone oil. The mass of dichlorobenzene in the phenyl-containing polysiloxane silicone oil is 1-20 ppm, the dichlorobenzene has two structures, and the proportion of p-dichlorobenzene in the total content of dichlorobenzene is less than 75 wt%. The phenyl-containing polysiloxane silicone oil has the advantages of being colorless, odorless and low in residue, can be used as an additive of personal care products such as skin care products and hair conditioners, is extremely low in color number, completely odorless and good in compatibility with most personal care product raw materials, and solves the use problem of low-odor and low-color-number additives in the daily chemical industry.

Description

Technical Field

[0001] The present invention belongs to the field of special silicone oils, and particularly relates to a phenyl-containing polysiloxane silicone oil for personal care and a preparation method thereof. Background Art

[0002] Silicone oil is a liquid linear polysiloxane with a molecular structure mainly composed of repeating silicon-oxygen bonds, and organic groups are connected to silicon atoms. It has the advantages of resistance to high and low temperatures, weather resistance, good film-forming property, hydrophobicity, electrical insulation, flame retardancy, physiological inertness, low surface tension, etc., and is widely used in industries such as electronics, construction, ceramics, and textiles.

[0003] Phenyl-containing polysiloxane silicone oil is one of the main varieties of silicone oils. Due to its good chemical stability, resistance to high and low temperatures, electrical insulation, radiation resistance, high refractive index, and physiological inertness, etc., it is widely used in industries such as daily chemicals, electronics, and machinery. Most phenyl-containing polysiloxane silicone oils on the market are linear polydimethylsiloxanes in which some methyl groups are replaced by phenyl groups or some T-shaped polydimethylsiloxanes with branched structures. Using it as a cosmetic raw material can improve glossiness and compatibility, but there are the following deficiencies: the odor is relatively obvious, the color number is relatively high, and its use in the field of daily cosmetics is relatively limited.

[0004] CN100396715C discloses a branched phenyl silicone oil and a preparation method thereof, which has the characteristics of low viscosity and high refractive index. With its branched structure, it has good compatibility with a variety of cosmetic raw materials, high safety, and does not contain heavy metals, but the control of odor and color number in the field of cosmetics is slightly poor.

[0005] CN103408759A discloses a preparation method of a high refractive index methyl phenyl silicone oil. This method has the characteristics of high refractive index, good product uniformity, and high purity, but its process is simple, and the odor and color number cannot meet the standards in the field of cosmetics.

[0006] The above technologies basically meet the requirements of the cosmetics field for high refractive index and good compatibility of silicone oils through structural design, but there are defects in controlling the problems of odor and color number that are particularly sensitive in the cosmetics field. There is no clear requirement for the odor threshold, and at the same time, the content of small molecules is not detected. Therefore, we need a new treatment process, with the help of excellent adsorbents, to make the silicone oil reach an extremely low color number and completely odorless level, meeting the requirements for odor and color number in the cosmetics field and other fields. Summary of the Invention

[0007] One of the objectives of the present invention is to provide a phenyl-containing polysiloxane silicone oil for personal care. This phenyl-containing polysiloxane silicone oil for personal care is colorless, odorless, and has low residue. It can be used as an additive for personal care products such as skin care products and hair conditioners. It has an extremely low color number, is completely odorless, and has good compatibility with most raw materials for personal care products, solving the problem of using additives with low odor and low color number in the daily chemical industry.

[0008] To achieve the above objective, the technical solution adopted by the present invention is as follows:

[0009] A phenyl-containing polysiloxane silicone oil for personal care, and the structural formula of the phenyl-containing polysiloxane silicone oil is:

[0010]

[0011] Wherein, R is one or more of H, a C1-C6 hydrocarbon group, n is an integer greater than 0, preferably n is an integer greater than or equal to 2, and more preferably n is an integer of 3-5;

[0012] The mass of dichlorobenzene in the silicone oil is 1-20 ppm;

[0013] The dichlorobenzene has the structural formula I and / or structural formula II:

[0014]

[0015] Wherein, the proportion of dichlorobenzene with structural formula II in the total content of dichlorobenzene is less than 75 wt%.

[0016] Another objective of the present invention is to provide a method for preparing a phenyl-containing polysiloxane silicone oil.

[0017] A method for preparing the above-mentioned phenyl-containing polysiloxane silicone oil, and the method performs devolatilization treatment and adsorbent addition treatment on the phenyl-containing polysiloxane silicone oil.

[0018] In a large number of studies on the odor source of phenyl-containing polysiloxane silicone oil, the inventors surprisingly found that dichlorobenzene remains in the phenyl-containing polysiloxane silicone oil, and dichlorobenzene is exactly the main source of the product odor. Based on the above discovery, the inventors specifically proposed a combined treatment plan of devolatilization treatment and adsorbent addition treatment. The devolatilization treatment mostly removes small molecules such as end-capping agents, initially removing the product odor brought by small molecules such as end-capping agents, and at the same time achieving the purpose of controlling the product viscosity. Limited by the devolatilization process, devolatilization temperature, yield, product performance, etc., small molecules with a large odor such as dichlorobenzene cannot be removed by devolatilization, and an adsorbent needs to be added for adsorption treatment. After the adsorbent is saturated with adsorption, it can be desorbed and recycled, and the adsorption performance does not decay.

[0019] In one embodiment of the present invention, the devolatilization treatment process is one or more of vacuum distillation, nitrogen stripping, and negative pressure removal by a thin-film evaporator; preferably, the temperature of the vacuum distillation is 120°C ≤ T ≤ 200°C, and the pressure is 5 mbar ≤ p ≤ 200 mbar; preferably, the nitrogen flow rate for nitrogen stripping is 0.02 m 3 / min ≤ Q ≤ 3 m 3 / min, and the stripping time is 5 h ≤ t ≤ 18 h.

[0020] In one embodiment of the present invention, the adsorbent selected for the adsorbent addition treatment is an inorganic porous adsorbent, preferably one or more of silica gel, alumina, calcium silicate, activated carbon, diatomaceous earth, and natural clay; preferably, the specific surface area of the adsorbent is 1200 m² / g ≤ S ≤ 2000 m² / g, the particle size is 2 nm ≤ D ≤ 20 nm, and the iodine adsorption value is 1000 mg / g ≤ IV ≤ 1500 mg / g.

[0021] In one embodiment of the present invention, the temperature of the adsorbent addition treatment is 30 - 80°C, and the time is 1 - 6 h.

[0022] In one embodiment of the present invention, the adsorbent addition amount is 0.1 - 10 wt% of the reaction mother liquor, and preferably the addition amount is 1 - 5 wt% of the reaction mother liquor.

[0023] Another object of the present invention is to provide a use of a phenyl-containing polysiloxane silicone oil.

[0024] A use of a phenyl-containing polysiloxane silicone oil, wherein the silicone oil is the above-mentioned silicone oil or the silicone oil prepared by the above method, and the silicone oil is used as an additive component in personal care products, preferably as a brightening agent for shampoo, a moisturizing agent for skin lotion, and a lubricant for sunscreen.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] The phenyl-containing polysiloxane silicone oil for personal care prepared by the method of the present invention can control the residual dichlorobenzene within 1 - 20 ppm through vacuum distillation, nitrogen stripping, and adsorbent adsorption treatment, wherein the content of p-dichlorobenzene is less than 75%. At the same time, the specific surface area of the adsorbent is greater than 1200 m² / g, the particle size is less than 20 nm, and the iodine adsorption value is greater than 1000 mg / g, which is more easily desorbed while adsorbing. Therefore, the adsorbent can be reused, and the phenyl-containing polysiloxane silicone oil for personal care obtained by this process method has no odor at all and the color number can be reduced to below 5. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a TIC scan diagram before and after the treatment of the target product in Example 1 and a comparison diagram after the treatment with other commercially available adsorbents. Detailed implementation mode

[0028] The present invention will be further described below through specific implementation modes. The embodiments described in the present invention are only for the description of the present invention and do not limit the scope of the present invention.

[0029] Raw material source:

[0030] The silicone oil prepared by this invention has a structure that is a mixture with the repeating unit n value ranging from 1 to 6, and the R group is one or more of H or hydrocarbon groups with C1-C6, such as methyl, vinyl, phenyl, etc.

[0031]

[0032] Characterization method and testing instrument:

[0033] Analysis Project Method and Instrument Model Color Number Test ADF Color Number Tester Model SDP-001 Nuclear Magnetic Test NMR NMReady-60e Chromatography Test TIC Chromatography Scanner KH-3800Plus Viscosity Test Rotary Viscometer Brookfield Purity Test GC Agilent8890 / 7890 Refractive Index Test Refractometer Mettler RM40

[0034] Example 1

[0035] Put 380 g of phenyltrimethoxysilane and 290 g of hexamethyldisiloxane into the reactor, add 30 ml of catalyst, heat up to 40 °C, stir and mix evenly, add water for hydrolysis and condensation reaction for 1 h, then heat up to 100 °C to distill off the light components, cool down to 30 °C and then add 15.5 g of neutralizer calcium carbonate, stir for 2 h and filter to obtain the synthesized special silicone oil intermediate product, whose structure is T-type silicone oil, a mixture with the repeating unit n value ranging from 1 to 6, and the R group is methyl. Add 600 g of the synthesized special silicone oil intermediate product to a 1 L reactor, start stirring, heat up and carry out vacuum distillation. When the temperature reaches 160 °C and the pressure drops to 50 mbar, start nitrogen stripping, with a nitrogen flow rate of 1.8 m 3 / min, stir for 13 hours, cool down to 70 °C, add 25 g of adsorbent diatomaceous earth with a specific surface area of 1600 ㎡ / g, particle size of 2 nm, and iodine adsorption value of 1080 mg / g, stir for 4 hours to obtain the target product I. See the comparison of TIC scans before and after adsorption Figure 1 .

[0036] Judging from the TIC chromatogram scan results, the content of p-dichlorobenzene, which has an obvious impact on the product odor, can be basically removed after devolatilization and adsorption. Before adsorption, it was 200 ppm, and after adsorption, it was 1 ppm. The content of o-dichlorobenzene also dropped to a very low level. Before adsorption, it was 59 ppm, and after adsorption, it was 5 ppm. The product is completely odorless and has a very low color number.

[0037] Example 2

[0038] Put 400 g of phenyltrichlorosilane and 290 g of tetramethyldivinyldisiloxane into a reactor, add 20 ml of catalyst, heat up to 70 °C, stir and mix evenly, add water for hydrolysis and condensation reaction for 3 h, then heat to 70 °C to distill off the light components, cool down to 25 °C and add 20 g of neutralizing agent calcium carbonate, stir for 1 h and filter to obtain the synthesized intermediate product of special silicone oil, whose structure is T-type silicone oil, a mixture with the repeating unit n value of 1 - 6, and the R group is vinyl. Put 600 g of the synthesized intermediate product of special silicone oil into a 1 L reactor, start stirring, heat up and carry out vacuum distillation. After the temperature reaches 190 °C and the pressure drops to 120 mbar, start nitrogen stripping, with the nitrogen flow rate of 0.1 m 3 / min, stir for 8 h and cool down to 50 °C, add 7 g of adsorbent activated carbon with a specific surface area of 1300 m² / g, particle size of 15 nm, and iodine adsorption value of 1020 mg / g, and stir for 2 h to obtain the target product II.

[0039] Example 3

[0040] Put 455 g of phenyltriethoxysilane and 290 g of hexamethyldisiloxane into a reactor, add 25 ml of catalyst, heat up to 50 °C, stir and mix evenly, add water for hydrolysis and condensation reaction for 4 h, then heat to 85 °C to distill off the light components, cool down to 20 °C and add 18 g of neutralizing agent calcium carbonate, stir for 3 h and filter to obtain the synthesized intermediate product of special silicone oil, whose structure is T-type silicone oil, a mixture with the repeating unit n value of 1 - 6, and the R group is methyl. Put 600 g of the synthesized intermediate product of special silicone oil into a 1 L reactor, start stirring, heat up and carry out vacuum distillation. After the temperature reaches 170 °C and the pressure drops to 100 mbar, start nitrogen stripping, with the nitrogen flow rate of 0.9 m 3 / min, stir for 10 h and cool down to 60 °C, add 16 g of adsorbent diatomite with a specific surface area of 1400 m² / g, particle size of 10 nm, and iodine adsorption value of 1050 mg / g, and stir for 3 h to obtain the target product III.

[0041] Example 4

[0042] Put 380 g of phenyltrimethoxysilane and 290 g of tetramethyldivinyldisiloxane into a reactor, add 20 ml of catalyst, heat up to 60 °C, stir and mix evenly, add water for hydrolysis and condensation reaction for 2 h, then heat to 105 °C to distill off the light components, cool down to 40 °C and add 25 g of neutralizing agent calcium carbonate, stir for 2 h and filter to obtain the synthesized intermediate product of special silicone oil, whose structure is T-type silicone oil, a mixture with the repeating unit n value of 1 - 6, and the R group is vinyl. Put 600 g of the synthesized intermediate product of special silicone oil into a 1 L reactor, start stirring, heat up and carry out vacuum distillation. After the temperature reaches 180 °C and the pressure drops to 80 mbar, start nitrogen stripping, with the nitrogen flow rate of 0.6 m 3 / min, stir for 12 hours, cool down to 70 °C, add 14 g of adsorbent alumina with a specific surface area of 1500 m² / g, a particle size of 8 nm, and an iodine adsorption value of 1050 mg / g, and stir for 4 hours to obtain the target product Ⅳ.

[0043] Example 5

[0044] Put 400 g of phenyltrimethoxysilane and 300 g of hexamethyldisiloxane into the reactor, add 40 ml of catalyst, heat up to 70 °C, stir and mix evenly, add water for hydrolysis and condensation reaction for 3 h, then heat up to 120 °C to distill off the light components, cool down to 45 °C, add 28 g of neutralizing agent calcium carbonate, stir for 1 h, and filter to obtain the synthesized special silicone oil intermediate product. Its structure is T-type silicone oil, and the repeating unit n value is a mixture of 1 - 6, and the R group is methyl. Add 600 g of the synthesized special silicone oil intermediate product to a 1 L reactor, start stirring, heat up and carry out vacuum distillation. After the temperature reaches 160 °C and the pressure drops to 70 mbar, start nitrogen stripping, and the nitrogen flow rate is 1.2 m 3 / min, stir for 9 hours, cool down to 60 °C, add 18 g of adsorbent diatomite with a specific surface area of 1500 m² / g, a particle size of 5 nm, and an iodine adsorption value of 1080 mg / g, and stir for 2 hours to obtain the target product Ⅴ.

[0045] Comparative Example 1

[0046] Compared with Example 1, the difference is that the devolatilization method is not vacuum distillation plus nitrogen stripping but scraping short-path devolatilization, and the preparation method and adsorption method are the same as those in Example 1.

[0047] Obtain sample Ⅵ.

[0048] Comparative Example 2

[0049] Compared with Example 1, the difference is that no adsorption treatment is carried out, and the preparation method and devolatilization method are the same as those in Example 1.

[0050] Obtain sample Ⅶ.

[0051] Comparative Example 3

[0052] Compared with Example 1, the difference is that the devolatilization method is not vacuum distillation plus nitrogen stripping but only vacuum distillation, and at the same time, no adsorption treatment is carried out, and the preparation method is the same as that in Example 1.

[0053] Obtain sample Ⅷ.

[0054] Table 1 Performance test of samples in Examples 1 - 5 and Comparative Examples 1 - 3

[0055] Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ Ⅶ Ⅷ p-Dichlorobenzene 1ppm 5ppm 5ppm 3ppm 2ppm 55ppm 71ppm 99ppm o-Dichlorobenzene 5ppm 15ppm 7ppm 1ppm 2ppm 101ppm 129ppm 159ppm Odor 10 points 10 points 10 points 10 points 10 points 8 points 7 points 5 points Color Number 3 4 4 3 3 10 10 12

[0056] It can be seen from the test results in Table 1 that after the devolatilization treatment under certain conditions and the adsorption by the adsorbent, the residues of dichlorobenzene and o-dichlorobenzene in Samples I-V are reduced to below 5 ppm and 15 ppm respectively, and the product can be completely odorless; the residues of dichlorobenzene and o-dichlorobenzene in Samples VI, VII, and VIII are relatively high after different devolatilization conditions and the adsorption by different adsorbents, and the product has an odor.

[0057] It can also be seen from the test results in Table 1 that reducing the residues of dichlorobenzene and o-dichlorobenzene is beneficial to reducing the product color number. By adsorbing to reduce the residues of dichlorobenzene and o-dichlorobenzene, the product color number can be controlled below 5.

[0058] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the method of the present invention, several improvements and supplements can still be made, and these improvements and supplements should also be regarded as the protection scope of the present invention.

Claims

1. A phenyl-containing polysiloxane silicone oil for personal care, characterized in that, The structural formula of the phenyl-containing polysiloxane silicone oil is as follows: Wherein, R is one or more of H and C1-C6 hydrocarbon groups, n is an integer greater than 0, preferably n is an integer greater than or equal to 2, and more preferably n is an integer from 3 to 6; The mass of dichlorobenzene in the silicone oil is 1-20 ppm; The dichlorobenzene has the structure of Structural Formula I and / or Structural Formula II: Among them, the proportion of dichlorobenzene with Structural Formula II in the total dichlorobenzene content is less than 75 wt%.

2. A method for preparing the phenyl-containing polysiloxane silicone oil according to claim 1, characterized in that, The method performs devolatilization treatment and adsorbent addition treatment on the phenyl-containing polysiloxane silicone oil.

3. The method according to claim 2, wherein The process of the devolatilization treatment is one or more of vacuum distillation, nitrogen stripping, and negative pressure removal by a thin-film evaporator; Preferably, the temperature of the vacuum distillation is 120°C ≤ T ≤ 200°C, and the pressure is 5 mbar ≤ p ≤ 200 mbar; Preferably, the nitrogen flow rate of the nitrogen stripping is 0.02 m 3 / min ≤ Q ≤ 3 m 3 / min, and the stripping time is 5 h ≤ t ≤ 18 h.

4. The method according to claim 2, characterized in that, The adsorbent selected for the adsorbent addition treatment is an inorganic porous adsorbent, preferably one or more of silica gel, alumina, calcium silicate, activated carbon, diatomaceous earth, and natural clay; Preferably, the specific surface area of the adsorbent is 1200 m² / g ≤ S ≤ 2000 m² / g, the particle size is 2 nm ≤ D ≤ 20 nm, and the iodine adsorption value is 1000 mg / g ≤ IV ≤ 1500 mg / g; And / or, the temperature of the adsorbent addition treatment is 30-80°C, and the time is 1-6 h; And / or, the addition amount of the adsorbent is 0.1-10 wt% of the reaction mother liquor, and preferably the addition amount is 1-5 wt% of the reaction mother liquor.

5. Use of a phenyl-containing polysiloxane silicone oil, the silicone oil is the silicone oil described in Claim 1, or the silicone oil prepared by the method described in any one of Claims 2-4, and the silicone oil is used as an additive component of personal care products, preferably as a brightening agent for shampoo, a moisturizer for skin lotion, and a lubricant for sunscreen.

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