Amino modified silicone oil with T-shaped structure as well as preparation method and application of amino modified silicone oil

Abstract

The invention provides amino modified silicone oil with a T-shaped structure as well as a preparation method and application thereof, and belongs to the field of daily chemical products. Octamethylcyclotetrasiloxane, a second catalyst, a silane oligomer and a T-type end-alkyl end-capping reagent are mixed and react to obtain the T-type alkyl modified amino silicon oil. The hair conditioner has the beneficial effects that the hair conditioner can help a hair care product to make straight and silky hair, and the excessive conditioning or greasy feeling caused by deposition is avoided. An organic silicon structure of the compound contains an amino side chain and an alkyl end group, and meanwhile, a hair care product containing the compound can effectively repair dry, damaged or perm-dyed hair, endows thermal protection with smooth and soft performance, enables the hair to be shiny and shiny, is long-acting and smooth, is easy to care, and has a wide market application prospect.

Description

Technical Field

[0001] The present invention relates to the field of daily chemical products, and in particular to a T-shaped alkyl-modified amino silicone oil and a preparation method thereof. The present invention also relates to the application of the silicone oil in the field of daily chemical products. Background Art

[0002] As one of the indispensable raw materials in hair care products, silicone oil can be mixed with other components according to the characteristics of different dosage forms, so that the hair can achieve the purpose of cleansing, refreshing, soft and shiny after using the product. However, the differences in the composition, molecular weight and viscosity of silicone oil or silicone oil combination used in existing products will lead to completely different effects after use: if the components are not properly matched and the viscosity is too high, although the hair will have a short-term smoothness and glossiness after use, the effect will not last long, and instead the smoothness will become greasy and sticky, and the hair will collapse, slippery but not smooth; but when the viscosity of silicone oil or silicone oil combination is insufficient, it cannot repair and fill the minor damage on the hair. Although the product has a better refreshing feeling after use, the hair is extremely hydrophobic, and a certain degree of frizzy split ends will appear, which is refreshing but not slippery.

[0003] Therefore, there is still a need in the prior art to develop a silicone oil or silicone oil composition for use in hair care products, so that the product can truly give the hair a lasting and long-lasting smooth feeling after use. Summary of the invention

[0004] The purpose of the present invention is to provide a T-shaped terminal alkyl modified amino silicone oil. The silicone oil obtained can be used directly or emulsified and prepared in combination with other raw materials to prepare a hair care product, which can effectively repair dry, damaged or dyed hair, and impart heat protection, smoothness and softness, making the hair shiny, long-lasting and smooth, and easy to care for.

[0005] To achieve the above technical objectives, the technical solution of the present invention is as follows:

[0006] The present invention provides a method for preparing an amino-modified silicone oil with a T-shaped structure, comprising the following steps:

[0007] ①, heating and stirring the reaction system containing T-type hydrogen-terminated silicone oil and olefin compounds to reach the initiation temperature of the catalyst;

[0008] ②, under a protective atmosphere, adding the first catalyst, the system undergoes a hydrosilylation reaction, heating to a certain temperature and continuing the reaction for a certain period of time, and then performing a desilylation reaction to obtain the T-type terminal alkyl capping agent;

[0009] ③. Under a protective atmosphere, the aminosilane coupling agent is subjected to a hydrolysis reaction, the temperature is raised to a certain temperature and the reaction is continued for a certain period of time, and then the temperature is raised to a certain temperature for a dehydrogenation reaction to obtain a silane oligomer;

[0010] ④. Under a protective atmosphere, octamethylcyclotetrasiloxane (D4), the second catalyst, the silane oligomer and the T-type terminal alkyl capping agent are mixed, the temperature is raised to a certain temperature and the reaction is continued for a certain time, and then the temperature is raised to a certain temperature for de-low reaction to obtain a T-type alkyl modified amino silicone oil.

[0011] Furthermore, the T-type hydrogen-terminated silicone oil in step ① of the present invention has the structural formula shown in Formula I,

[0012]

[0013]

[0014] Wherein, in formula I, the range of x is 1-700, the range of y is 1-700, and the range of z is 1-700.

[0015] Furthermore, the olefin compound is selected from C2-C22 α-olefins; further, the olefin compound is selected from at least one of hexadecene, heptadecene and octadecene.

[0016] Furthermore, in step ①, the molar ratio of the T-type hydrogen-terminated silicone oil to the olefin compound is 1:3-6, ensuring that the Si-H group in the T-type hydrogen-terminated silicone oil can fully react with the double bond group of the olefin.

[0017] Furthermore, the catalyst initiation temperature in step ① is 40-60°C.

[0018] Furthermore, the T-type terminal alkyl capping agent in step ② is a structural formula shown in formula II,

[0019]

[0020] Wherein, in formula II, the range of x is 1 to 700, the range of y is 1 to 700, and the range of z is 1 to 700;

[0021] The structural formula of R1 is a C2-C22 alkyl group; further, the R 1 Selected from hexadecyl, heptadecyl and octadecyl.

[0022] Furthermore, in step ②, the first catalyst is selected from a noble metal catalyst or a complex of a noble metal and isopropanol / ethanol, the noble metal is selected from at least one of platinum, palladium and rhodium, and further, the first catalyst is selected from at least one of chloroplatinic acid, a Speier catalyst and a Karstedt catalyst.

[0023] Furthermore, the hydrosilylation reaction temperature in step ② is 40-90°C, the reaction time is 2-5h, the concentration of the first catalyst is 5000ppm, and the content of the catalyst is 1-50ppm. Furthermore, the degassing temperature is 90-120°C, the degassing pressure is 10mbar-100mbar, so that the residual low molecular weight of the reaction system is reduced to less than 1000ppm, and the degassing time is preferably 3-5h.

[0024] Furthermore, the aminosilane coupling agent described in step ③ includes at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane.

[0025] Furthermore, the hydrolysis reaction temperature in step ③ is 30-60°C, and the reaction time is 1-4h. Furthermore, the dehydration temperature is 60-100°C, and the dehydration pressure is 10mbar-100mbar, so that the residual low molecular weight of the reaction system is reduced to less than 1000ppm, and the dehydration time is preferably 1-4h.

[0026] Furthermore, step ③ comprises mixing 50 to 100 parts by mass of the aminosilane coupling agent with 4 to 9 parts by mass of the deionized water to carry out a hydrolysis reaction.

[0027] Furthermore, in step ④, the T-type terminal alkyl modified amino silicone oil has the structural formula shown in formula III,

[0028]

[0029] Wherein, in formula III, x ranges from 1 to 700, y ranges from 1 to 700, and z ranges from 1 to 700;

[0030] The structural formula of R1 is a C2-C22 alkyl group; further, the R 1 Selected from hexadecyl, heptadecyl and octadecyl;

[0031] R2 contains at least one of the corresponding silane oligomers of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane.

[0032] Furthermore, in step ④, the second catalyst is tetramethylammonium hydroxide.

[0033] Furthermore, step ④ comprises mixing 40 to 100 parts by mass of the octamethylcyclotetrasiloxane, 1 to 5 parts by mass of the T-type terminal alkyl capping agent, 0.5 to 1.3 parts by mass of the silane oligomer and 0.01 to 0.15 parts by mass of the second catalyst.

[0034] Furthermore, the reaction temperature in step ④ is 90-120°C, and the reaction time is 3-8h; further, the deoxidation temperature is 130-170°C, the deoxidation pressure is 10mbar-100mbar, and the deoxidation time is 3-8h, so that the residual low molecular weight of the reaction system is reduced to below 1000ppm.

[0035] Furthermore, the protective atmosphere of the present invention is at least one of nitrogen, helium and argon.

[0036] The present invention provides a T-shaped terminal alkyl modified amino silicone oil prepared by any one of the above preparation methods.

[0037] Furthermore, the viscosity of the T-type terminal alkyl modified amino silicone oil is 4500-10000 mPa.s, the particle size of the emulsion is within a suitable range, and the application effect is more excellent.

[0038] The present invention also provides an application of the T-shaped terminal alkyl modified amino silicone oil prepared by any one of the above preparation methods in the field of daily chemical products.

[0039] Preferably, the daily chemical product is a hair care product.

[0040] Preferably, the hair care product is at least one of shampoo, conditioner or hair dye.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] The invention selects T-type terminal hydrogen silicone oil with a T-type structure, and the prepared T-type terminal alkyl capping agent can not only increase the length of the organic silicon chain segment and a richer three-dimensional structure, but also has a large adjustable space and can effectively improve the capping rate; and the modified silicone oil is characterized by containing an amino side chain and an alkyl end group. Hair care products containing the compound can effectively repair dry, damaged or dyed hair, and impart heat protection, smoothness and softness, make the hair shiny, long-lasting and smooth, and easy to care for, and can help hair care products create straight and silky hair without excessive conditioning or greasy feeling due to deposition, and has broad market application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a comparison of the electron microscope scanning of the hair scales after using the shampoo without silicone oil JLN-2 and the shampoo with silicone oil JLN-2;

[0044] Figure 2 The sensory evaluation chart is of dry hair after using shampoo without silicone oil JLN-2, shampoo with silicone oil JLN-2, and nothing else. DETAILED DESCRIPTION

[0045] In order to better clarify and understand the purpose, process scheme and advantages of the present invention, the technical scheme and implementation method of the present invention are further described clearly, completely and in detail through specific examples and in combination with the accompanying drawings. It should be noted that the embodiments described in the present invention are implemented on the premise of the technical scheme of the present invention, and detailed implementation methods and specific operating processes are given, but they are only part of the embodiments of the present invention, not all of the embodiments. The specific implementation methods described are limited to explaining and interpreting the present invention, and do not limit the present invention. Based on the embodiments in the present invention, all other implementation methods obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0046] The experimental methods and conditions used in the following examples are conventional methods and conventional conditions unless otherwise specified. The materials, reagents or instruments used in the examples, unless otherwise specified, can be obtained from commercial sources or prepared by conventional methods. The reaction conditions embodied in the content of the invention of the present invention can achieve the reaction and obtain the product with the expected effect. Due to space limitations, some embodiments are listed below to further illustrate the advantages of the technical solution of the present invention.

[0047] Example 1

[0048] In a 500ml four-necked flask equipped with a temperature probe and a reflux condenser, 252g of hexadecene and 100g of T-terminated hydrogenated silicone oil were added, and then the nitrogen was turned on to keep the system under a nitrogen atmosphere. The temperature was raised to 50°C at a stirring speed of 250rpm, and then 0.2g of Karstedt catalyst with a concentration of 5000ppm was added. The system was then heated to 90°C and reacted at this temperature for 5h. The temperature was then raised to 110°C, and the vacuum was turned on for negative pressure degassing. The vacuum value was set to 40mbar. Under this condition, the degassing was performed for 4h, and finally the temperature was cooled to room temperature for discharging to obtain the product T-terminated hexadecylsiloxane, named M-1.

[0049] In a dry four-necked flask equipped with a temperature probe and a reflux condenser, 100 g of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane was added, and then the nitrogen was turned on to keep the system under a nitrogen atmosphere. Then, 8 g of deionized water was slowly added dropwise using a constant pressure dropping funnel at room temperature. The addition was completed within 2 h, and then heated to 50 ° C. and maintained at this temperature for 2 h. Then the temperature was raised to 90 ° C. and distilled under reduced pressure at 40 mbar for 2 h to obtain the product N-(β-aminoethyl)-γ-aminopropylmethyl oligomer, named M-2.

[0050] In a dry four-necked flask equipped with a temperature probe and a reflux condenser, add 230 g of D4, 20 g of M-1, 5 g of M-2 and 0.08 g of tetramethylammonium hydroxide, then turn on the nitrogen to keep the system under a nitrogen atmosphere, heat to 110°C, react at a constant temperature at a stirring speed of 250 rpm for 6 hours, then heat to 140°C, set the vacuum value to 40 mbar and perform reduced pressure distillation for 6 hours to obtain the product, named JLN-1.

[0051] JLN-1: 1H NMR (400 MHz, chloroform-d) 2.71–2.60 (m, 15H), 2.56 (td, J=7.0, 6.0 Hz, 25H), 1.49 (p, J=7.1 Hz, 10H), 1.36–1.19 (m, 90H), 0.96–0.83 (m, 8H), 0.79–0.70 (m, 6H), 0.69–0.57 (m, 8H), 0.12–-0.21 (m, 1105H).

[0052] The viscosity of the T-type terminal alkyl modified amino silicone oil of Example 1 was measured to be 4850 mPa.s.

[0053] Example 2

[0054] In a dry four-necked flask equipped with a temperature probe and a reflux condenser, add 240g of D4, 10g of M-1, 5g of M-2 and 0.08g of tetramethylammonium hydroxide, then turn on the nitrogen to keep the system under a nitrogen atmosphere, raise the temperature to 110°C, maintain a constant temperature reaction at a stirring speed of 250rpm for 6h, then raise the temperature to 140°C, set the vacuum value to 40mbar for reduced pressure distillation to obtain the product, named JLN-2.

[0055] The viscosity of the T-type terminal alkyl modified amino silicone oil of Example 2 was measured to be 6500 mPa.s.

[0056] Example 3

[0057] In a dry four-necked flask equipped with a temperature probe and a reflux condenser, add 245g of D4, 5g of M-1, 5g of M-2 and 0.08g of tetramethylammonium hydroxide, then turn on the nitrogen to keep the system under a nitrogen atmosphere, raise the temperature to 110°C, maintain a constant temperature reaction at a stirring speed of 250rpm for 6h, then raise the temperature to 140°C, set the vacuum value to 40mbar for reduced pressure distillation, and obtain a product named JLN-3.

[0058] The viscosity of the T-type terminal alkyl modified amino silicone oil of Example 3 was measured to be 8584 mPa.s.

[0059] Application Effect Example 1

[0060] 1. The silicone oil JLN-2 prepared in Example 2 was applied to a shampoo formula, and a blank without silicone oil JLN-2 was used as a blank control. A volunteer with damaged hair was randomly selected for a half-head test. Half of the head was washed with a blank shampoo, and the other half was washed with a shampoo containing silicone oil JLN-2. The state of the hair scales was observed under a scanning electron microscope, and the changes in hair quality before and after were evaluated by sensory evaluation;

[0061] The above shampoo formula is as shown in Table 1 below:

[0062] Table 1: Formula of shampoo with added Example 2 and blank shampoo

[0063]

[0064]

[0065] 2. The preparation method of shampoo is as follows: pre-disperse the raw materials of phase A1, phase A2 and phase C; add phase B into a reaction bottle, heat it to 70°C and stir it evenly; cool phase B to 40°C, add phase A1, phase A2 and phase C and stir them evenly; add phase D into the reaction bottle in sequence, adjust the pH value to about 5 to 6.5, and discharge the material after it meets the requirements to obtain shampoo with silicone oil JLN-2 added and blank shampoo without silicone oil JLN-2 added.

[0066] 3. Results

[0067] The hair was observed under a scanning electron microscope. Figure 1 As shown, Figure A and Figure B are the hair scales after using a blank shampoo without adding silicone oil JLN-2; Figure C and Figure D are the hair scales after using a shampoo with added silicone oil JLN-2; by comparison, it is found that the use of the shampoo with added silicone oil JLN-2 has a significant repair and improvement effect on damaged, arched, and rough hair scales, indicating that the T-type terminal alkyl modified amino silicone oil prepared by the present invention can make the hair scales neat when used in shampoo.

[0068] Sensory evaluation: Using shampoo with silicone oil JLN-2 to wash hair can significantly reduce the friction of wet and dry combing of hair. The foam is very rich during the washing process, which is conducive to better acting on the roots of the scalp. After washing, the hair becomes soft, smooth and feels very smooth. After drying, the hair is fluffy and does not fit the scalp.

[0069] The T-shaped terminal alkyl modified amino silicone oil prepared by the present invention has a uniform structure, stable performance and high conversion rate compared with other modified amino silicone oils in terms of structure; and because it also has alkyl end-capping and side chain amino groups, it can be used as a hair conditioner in hair products, can effectively repair dry, damaged or dyed hair, and give heat protection, smoothness and softness, making hair shiny, long-lasting and smooth, and easy to care for.

[0070] The above embodiments are not limitations of the present invention, and the present invention is not limited to the above embodiments. As long as the requirements of the present invention are met, they belong to the protection scope of the present invention.

Claims

1. A method for preparing an amino-modified silicone oil with a T-shaped structure, characterized in that: The following steps are involved: ①, heating and stirring the reaction system containing T-type hydrogen-terminated silicone oil and olefin compounds to reach the initiation temperature of the catalyst; ②, under a protective atmosphere, adding the first catalyst to cause a hydrosilylation reaction, heating to a certain temperature and continuing the reaction for a certain period of time, and then performing a desilylation reaction to obtain a T-type terminal alkyl capping agent; ③. Under a protective atmosphere, the aminosilane coupling agent is subjected to a hydrolysis reaction, the temperature is raised to a certain temperature and the reaction is continued for a certain period of time, and then a dehydrogenation reaction is carried out to obtain a silane oligomer; ④. Under a protective atmosphere, octamethylcyclotetrasiloxane, the second catalyst, silane oligomer and T-type terminal alkyl capping agent are mixed, heated to a certain temperature and continued to react for a certain period of time, and then a de-lowering reaction is carried out to obtain T-type alkyl modified amino silicone oil.

2. The method for preparing T-type terminal alkyl modified amino silicone oil according to claim 1, characterized in that: The structural formula of the T-type hydrogen-terminated silicone oil in step ① is shown in Formula I: Wherein, in Formula I, x ranges from 1 to 700, y ranges from 1 to 700, and z ranges from 1 to 700; And / or, the olefin compound in step ① is selected from C2-C22 α-olefins; And / or, the molar ratio of the T-type hydrogen-terminated silicone oil to the olefin compound in step ① is 1:3-6; And / or, the catalyst initiation temperature in step ① is 40-60°C.

3. The method for preparing a T-shaped amino-modified silicone oil according to claim 2, characterized in that: The olefin compound is selected from at least one of hexadecene, heptadecene and octadecene.

4. The method for preparing a T-shaped amino-modified silicone oil according to claim 1, characterized in that: The structural formula of the T-type terminal alkyl capping agent in step ② is shown in Formula II: Wherein, in formula II, x ranges from 1 to 700, y ranges from 1 to 700, and z ranges from 1 to 700; the structural formula of R1 is a C2 to C22 alkyl group; And / or, in step ②, the first catalyst is selected from a noble metal catalyst or a complex of a noble metal and isopropanol / ethanol, and the noble metal is selected from at least one of platinum, palladium and rhodium; And / or, the hydrosilylation reaction temperature in step ② is 30-90° C., the reaction time is 2-5 h, the concentration of the first catalyst is 5000 ppm, and the content of the added catalyst is 1-50 ppm.

5. The method for preparing a T-shaped amino-modified silicone oil according to claim 4, characterized in that: The first catalyst is selected from at least one of chloroplatinic acid, a Speier catalyst and a Karstedt catalyst.

6. The method for preparing a T-shaped amino-modified silicone oil according to claim 1, characterized in that: The aminosilane coupling agent in step ③ includes at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane; And / or, the hydrolysis reaction temperature in step ③ is 30-60° C., and the reaction time is 1-4 h; And / or, step ③ comprises mixing 50 to 100 parts by mass of an aminosilane coupling agent with 4 to 9 parts by mass of water.

7. The method for preparing a T-shaped amino-modified silicone oil according to claim 1, characterized in that: The structural formula of the T-type alkyl-modified amino silicone oil in step ④ is shown in Formula III: Wherein, in formula III, x ranges from 1 to 700, y ranges from 1 to 700, and z ranges from 1 to 700; The structural formula of R1 is a C2-C22 alkyl group; R2 comprises at least one of the corresponding silane oligomers of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane; And / or, in step ④, the second catalyst is tetramethylammonium hydroxide; And / or, step ④ comprises mixing 40 to 100 parts by mass of octamethylcyclotetrasiloxane, 1 to 5 parts by mass of a T-type terminal alkyl capping agent, 0.5 to 1.3 parts by mass of a silane oligomer and 0.01 to 0.15 parts by mass of a second catalyst; And / or, the reaction temperature in step ④ is 90-120° C., and the reaction time is 3-8 h.

8. An amino-modified silicone oil with a T-shaped structure prepared according to the preparation method according to any one of claims 1 to 7.

9. Use of the amino-modified silicone oil with a T-shaped structure prepared by the preparation method according to any one of claims 1 to 7 in the field of daily chemical products.

10. The use of the amino-modified silicone oil with a T-shaped structure in the field of daily chemical products according to claim 9, characterized in that: The daily chemical product is a hair care product.

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