Quaternization modified comb-shaped water-soluble block polysiloxane and application thereof in preparation of daily chemicals

Abstract

The quaternization modified comb-shaped water-soluble block polysiloxane is synthesized, and the structure of the quaternization modified comb-shaped water-soluble block polysiloxane meets the structural general formula (1); the invention further discloses a preparation method of the quaternization modified comb-shaped water-soluble block polysiloxane and application of the quaternization modified comb-shaped water-soluble block polysiloxane in daily chemicals. When the prepared quaternization modified comb-shaped water-soluble block polysiloxane is applied to a shampoo product, an excellent conditioning effect can be brought to the product, and the deposition amount on hair and the long-term use cumulant of the quaternization modified comb-shaped water-soluble block polysiloxane are lower than those of traditional polydimethylsiloxane and amino silicon oil.

Description

Technical Field

[0001] The invention relates to a silicone oil with a new structure and its preparation and application, belonging to the technical field of daily chemicals, and in particular to a quaternary ammonium modified comb-shaped water-soluble block silicone oil and its application in the preparation of daily chemicals. Background Art

[0002] Polydimethicone is often used in personal care products to improve the smoothness of wet and dry hair. However, due to the hydrophobic physical properties of polydimethicone, the residual amount in undamaged parts of the hair is greater than in damaged parts, which makes polydimethicone have limited improvement in the smoothness of dry and wet hair of damaged hair ends. In addition, the accumulation in healthy hair parts will cause the hair to become flat and greasy after repeated use.

[0003] Chinese invention patent CN107141481A published a quaternary ammonium salt-modified diamino-terminated silicone oil. This type of amino-terminated silicone oil can improve the smoothness of wet hair ends and dry hair, but in actual use it is found that this type of silicone oil is not easy to be washed off a second time, and its accumulation is more obvious than that of polydimethylsiloxane. Long-term use will cause the hair to feel flat and sticky, which is stronger than polydimethylsiloxane.

[0004] Chinese invention patent CN102585251A and international patent WO2006103075A1 respectively disclose the preparation of a bis-amino polyether / polydimethylsiloxane block silicone oil and a comb-shaped p-amino block silicone oil. This type of block-modified silicone oil can improve the problem that the quaternary ammonium salt-modified bis-amino terminal silicone oil is not easy to be washed twice and easily accumulates, causing flat and greasy hair. However, in the case of wet hair, the clear water ends tend to be arranged on the outermost side of the hair, which also leads to the limited ability of the block-type silicone oil to improve the smoothness of wet hair.

[0005] In order to achieve the goal of improving the smoothness of dry and wet hair without causing greasy and flat hair, the present invention provides a new type of comb-shaped quaternary ammonium modified water-soluble silicone oil with a structure different from that of international patent WO2006103075A1. The silicone oil of the present invention is applied to shampoo products and has excellent performance in wet hair smoothness, dry hair smoothness and long-term use cumulative performance. Summary of the invention

[0006] In order to overcome the deficiencies of the prior art, the present invention aims to provide a structure of a quaternary ammonium modified comb-shaped water-soluble block polysiloxane, a preparation method and application thereof in daily chemical products.

[0007] The present invention provides a quaternary ammonium modified comb-shaped water-soluble block polysiloxane, the structure of which satisfies the general structural formula (1):

[0008]

[0009] wherein a is independently an integer selected from 20 to 200; b is independently an integer selected from 1 to 10; c is independently an integer selected from 1 to 10; d is independently an integer selected from 1 to 20; e is an integer from 1 to 20; and R is a C1 to C20 alkyl group.

[0010] Preferably, a is independently selected from integers of 20 to 100; b is independently selected from integers of 1 to 5; c is independently selected from integers of 1 to 5; d is independently selected from integers of 8 to 20; e is an integer of 8 to 20; and R is a C1 to C20 alkyl group.

[0011] More preferably, a is independently an integer selected from 30 to 100; b is independently an integer selected from 1 to 5; c is independently an integer selected from 1 to 5; d is independently an integer selected from 5 to 15; e is an integer of 5 to 15; and R is a C3 to C20 alkyl group.

[0012] More preferably, a is independently an integer selected from 60 to 100; b is independently an integer selected from 1 to 5; c is independently an integer selected from 1 to 5; d is independently an integer selected from 5 to 10; e is an integer selected from 10 to 15; and R is a C3 to C18 alkyl group.

[0013] The present invention provides a method for preparing the quaternary ammonium modified comb-shaped water-soluble block polysiloxane, which specifically comprises the following steps:

[0014] Step 1: Preparation of epoxy-modified polysiloxane prepolymer A;

[0015] Add hydrogen-terminated silicone with hydrogen groups on the side chain and a double-bonded epoxy compound into a reaction vessel, stir and preheat at 40-60° C. for 10-30 min under nitrogen protection, add chloroplatinic acid-isopropanol catalyst, heat to 70-90° C., stir and react for 5-7 hours, remove the solvent isopropanol by rotary evaporation, and obtain epoxy group-modified silicone prepolymer A.

[0016] Step 2: Preparation of alkyl tertiary amine modified polysiloxane prepolymer B;

[0017] The epoxy-modified silicone oil reacts with the long alkyl tertiary amine under the action of isopropanol and glacial acetic acid, the reaction temperature is 60-120°C, the reaction time is 1-7 hours, after the reaction is completed, the solvent is removed by extraction and concentration to obtain the silicone oil prepolymer B whose side chain is modified by the polyether alkyl tertiary amine.

[0018] Step 3: Preparation of polyether-modified block polysiloxane prepolymer C;

[0019] The hydrogen-terminated polydimethylsiloxane and the alkenyl-terminated polyether are subjected to addition reaction at 80-160° C. to obtain a polyether-modified block silicone oil prepolymer C, wherein the mass fraction of the hydrogen-terminated polydimethylsiloxane is 1-5 times that of the alkenyl-terminated polyether.

[0020] Step 4: Preparation of quaternary ammonium modified comb-shaped water-soluble block polysiloxane;

[0021] The prepolymer B and prepolymer C prepared in step 2 and step 3 are reacted with the side chain amino silicone polymer at 60-90° C. for 5-10 hours to obtain the final quaternary ammonium modified comb-shaped water-soluble block silicone oil. The added mass fraction ratio of prepolymer B, prepolymer C, and amino silicone oil is: (0.5-3): (0.5-3): (1-4).

[0022] Furthermore, in step 1), the stirring preheating temperature is 45° C. and the time is 30 min; the chloroplatinic acid-isopropanol catalyst is added, the temperature is raised to 80° C., and the stirring reaction is for 7 hours.

[0023] Furthermore, in step 2), the reaction temperature is 80° C. and the reaction time is 4 to 6 hours.

[0024] Furthermore, in step 3), the addition reaction temperature is 120°C.

[0025] Furthermore, in step 4), the reaction temperature is 80° C. and the reaction time is 6 hours.

[0026] Furthermore, the hydrogen-terminated organosilicon having a hydrogen group in the side chain satisfies the general structural formula (2):

[0027]

[0028] wherein x is an integer from 1 to 5, and y is an integer from 5 to 20; preferably, x is an integer from 1 to 2, and y is an integer from 5 to 16; more preferably, y is an integer from 10 to 16.

[0029] Furthermore, the double-bonded epoxy compound satisfies the general structural formula (3):

[0030]

[0031] wherein e is an integer from 2 to 15; preferably e is an integer from 5 to 15; more preferably e is an integer from 10 to 15.

[0032] Furthermore, the long alkyl tertiary amine satisfies the general structural formula (4):

[0033]

[0034] wherein f is an integer from 2 to 22; preferably, f is an integer from 2 to 19; and more preferably, f is an integer from 2 to 17.

[0035] Furthermore, the hydrogen-terminated polydimethylsiloxane satisfies the general structural formula (5):

[0036]

[0037] wherein g is an integer from 5 to 20; preferably g is an integer from 10 to 20.

[0038] Furthermore, the alkenyl-terminated polyether satisfies the general structural formula (6):

[0039]

[0040] Wherein d is an integer from 2 to 20; preferably d is an integer from 5 to 15.

[0041] Furthermore, the side chain amino silicone polymer satisfies the general structural formula (7):

[0042]

[0043] wherein b is an integer from 1 to 5, and h is an integer from 5 to 20; preferably, b is an integer from 1 to 2, and h is an integer from 5 to 15.

[0044] The invention provides application of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane in daily chemicals.

[0045] The prepared quaternary ammonium modified comb-shaped water-soluble block silicone oil can be used in daily chemicals such as shampoo, conditioner, hair care lotion, hair care essential oil, etc. The application of the prepared quaternary ammonium modified comb-shaped water-soluble block silicone oil in daily chemicals is also very simple, and it can be directly added to the product and stirred and dispersed evenly. The addition amount is 0.3% to 30% according to the product type and performance requirements.

[0046] Furthermore, the daily chemical product is shampoo;

[0047] The formula of the shampoo is the following components in percentage by weight:

[0048] Phase A: balance water, cationic guar gum 0.2%;

[0049] Phase B: Lauryl Hydroxysultaine 30%, Sodium Cocoyl Isethionate 5%;

[0050] Phase C: citric acid 0.08%, phenoxyethanol 0.5%, sodium benzoate 0.4%, fragrance 0.6%;

[0051] Phase D: 0.5-0.8% of quaternary ammonium modified comb-shaped water-soluble block polysiloxane;

[0052] The preparation method of the shampoo comprises the following steps:

[0053] S1. Add the water and cationic guar gum of phase A into the emulsifier, homogenize until completely dispersed, start stirring, heat to 75-85°C, and keep warm for 10-30 minutes;

[0054] S2. Add lauryl hydroxysultaine and sodium cocoyl isethionate of phase B into the emulsifier in sequence, and stir at 75°C for 20-30 minutes;

[0055] S3, cool the material prepared in step S2 to below 40°C, add the raw materials of phase C in sequence, and stir and disperse for 10-20 minutes;

[0056] S4. Add phase D to the material prepared in step S3, and stir for 5-20 minutes until the material is evenly dispersed to obtain a finished shampoo.

[0057] Compared with the prior art, the present invention has the following beneficial effects:

[0058] 1) The quaternary ammonium modified comb-shaped water-soluble block polysiloxane provided by the present invention has excellent combing smoothness for dry and wet hair when used in daily chemicals.

[0059] 2) The quaternized modified comb-shaped water-soluble block polysiloxane provided by the present invention is used in daily chemicals and will not cause excessive deposition and flat and greasy hair after long-term use.

[0060] 3) The quaternary ammonium modified comb-shaped water-soluble block polysiloxane provided by the present invention is easy to use. No matter the product type is shampoo, hair care lotion, or hair care essential oil, and no matter the product appearance requires transparency or opacity, the quaternary ammonium modified comb-shaped water-soluble block silicone oil provided can be directly added. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 IR spectrum of quaternary ammonium modified comb-shaped water-soluble block polysiloxane (WBD-1);

[0062] Figure 2 IR spectrum of quaternary ammonium modified comb-shaped water-soluble block polysiloxane (WBD-2);

[0063] Figure 3 IR spectrum of quaternary ammonium modified comb-shaped water-soluble block polysiloxane (WBD-3);

[0064] Figure 4 IR spectrum of quaternary ammonium modified comb-shaped water-soluble block polysiloxane (WBD-4). DETAILED DESCRIPTION

[0065] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below.

[0066] As used herein, the term "prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0067] When amount, concentration or other value or parameter is expressed as range, preferred range or a series of upper preferred value and lower preferred value limit range, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value and any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when disclosing range "1 to 5", described range should be interpreted as including range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5" etc. When numerical range is described in this article, unless otherwise stated, the range is intended to include its end value and all integers and fractions within the range.

[0068] Many specific details are set forth in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited to the specific embodiments disclosed below.

[0069] The invention synthesizes a quaternary ammonium modified comb-shaped water-soluble segmented polysiloxane. The prepared quaternary ammonium modified comb-shaped water-soluble segmented polysiloxane is applied to shampoo products, which can not only bring excellent conditioning effects to the products, but also has lower deposition amount on hair and lower cumulative amount after long-term use than traditional polydimethylsiloxane and amino silicone oil.

[0070] The present invention provides a structure of a quaternary ammonium modified comb-shaped water-soluble block silicone oil, a preparation method and its application in daily chemical products. The polymer is characterized in that its structure satisfies the general structural formula (1):

[0071]

[0072] wherein a is independently an integer selected from 20 to 200; b is independently an integer selected from 1 to 10; c is independently an integer selected from 1 to 10; d is independently an integer selected from 1 to 20; e is an integer from 1 to 20; and R is a C1 to C20 alkyl group.

[0073] The preparation method of the quaternized modified comb-shaped water-soluble block polysiloxane specifically comprises the following steps:

[0074] Step 1: Preparation of epoxy-modified polysiloxane prepolymer A, the reaction equation is as follows:

[0075]

[0076] Add hydrogen-terminated silicone with hydrogen groups on the side chain and a double-bonded epoxy compound into a reaction vessel, stir and preheat at 40-60° C. for 10-30 min under nitrogen protection, add chloroplatinic acid-isopropanol catalyst, heat to 70-90° C., stir and react for 5-7 hours, remove the solvent isopropanol by rotary evaporation, and obtain epoxy group-modified silicone prepolymer A.

[0077] Step 2: Preparation of alkyl tertiary amine modified polysiloxane prepolymer B, the reaction equation is as follows:

[0078]

[0079] The epoxy-modified silicone oil reacts with the long alkyl tertiary amine under the action of isopropanol and glacial acetic acid, the reaction temperature is 60-120°C, the reaction time is 1-7 hours, after the reaction is completed, the solvent is removed by extraction and concentration to obtain the silicone oil prepolymer B whose side chain is modified by the polyether alkyl tertiary amine.

[0080] Step 3: Preparation of polyether modified block polysiloxane prepolymer C, the reaction equation is as follows:

[0081]

[0082] The hydrogen-terminated polydimethylsiloxane and the alkenyl-terminated polyether are subjected to addition reaction at 80-160° C. to obtain a polyether-modified block silicone oil prepolymer C, wherein the mass fraction of the hydrogen-terminated polydimethylsiloxane is 1-5 times that of the alkenyl-terminated polyether.

[0083] Step 4: Preparation of quaternary ammonium modified comb-shaped water-soluble block polysiloxane, the reaction equation is as follows:

[0084]

[0085] The prepolymer B and prepolymer C prepared in step 2 and step 3 are reacted with the side chain amino silicone polymer at 60-90° C. for 5-10 hours to obtain the final quaternary ammonium modified comb-shaped water-soluble block silicone oil. The added mass fraction ratio of prepolymer B, prepolymer C, and amino silicone oil is: (0.5-3): (0.5-3): (1-4).

[0086] The following are respectively the synthesis examples of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane:

[0087] Synthesis Example 1

[0088] The preparation of the quaternized modified comb-shaped water-soluble block polysiloxane (WBD-1) comprises the following steps:

[0089] Step 1: Preparation of epoxy-modified polysiloxane prepolymer A;

[0090] Compound 1 (x=2, y=10) and compound 2 (e=10) were added to a reaction vessel, stirred and preheated at 45°C for 30 minutes under nitrogen protection, chloroplatinic acid-isopropanol catalyst was added, the temperature was raised to 80°C, stirred and reacted for 7 hours, and the solvent isopropanol was removed by rotary evaporation to obtain epoxy group modified silicone prepolymer A. The mass ratio of compound 1, compound 2, isopropanol and chloroplatinic acid was 1:1.5:3:0.1.

[0091] Step 2: Preparation of alkyl tertiary amine modified polysiloxane prepolymer B;

[0092] Prepolymer A and compound 3 (f=11) were added to an isopropanol solution containing glacial acetic acid, and reacted at 80°C for 6 hours. After the reaction was completed, the solvent was removed by extraction and concentration to obtain a silicone oil prepolymer B with a side chain modified by a polyether alkyl tertiary amine. The mass ratio of prepolymer A, compound 3, isopropanol, and glacial acetic acid was 2.6:1:3:0.2.

[0093] Step 3: Preparation of polyether-modified block polysiloxane prepolymer C;

[0094] Compound 4 (g=15) and compound 5 (d=10) were subjected to addition reaction at 120° C. to obtain polyether-modified block polysiloxane prepolymer C, wherein the mass ratio of compound 4 to compound 5 was 2.6:1.

[0095] Step 4: Preparation of quaternary ammonium modified comb-shaped water-soluble block polysiloxane, the reaction equation is as follows: Figure 4 As shown;

[0096] The prepolymer B and prepolymer C prepared in step 2 and step 3 were reacted with compound 6 (b=2, h=15) at 80°C for 6 hours to obtain the final quaternary ammonium modified comb-shaped water-soluble block polysiloxane. The added mass ratio of prepolymer B, prepolymer C, and amino silicone oil was 2.4:1.7:1.

[0097] The infrared spectrum of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane (WBD-1) is as follows: Figure 1WBD-1 satisfies the general structural formula (1), wherein a=80, b=2, c=5, d=10, e=10, and R=C12.

[0098] Synthesis Example 2

[0099] The preparation of the quaternized modified comb-shaped water-soluble block polysiloxane (WBD-2) comprises the following steps:

[0100] Step 1: Preparation of epoxy-modified polysiloxane prepolymer A;

[0101] Compound 1 (x=2, y=16) and compound 2 (e=10) were added to a reaction vessel, stirred and preheated at 45°C for 30 minutes under nitrogen protection, chloroplatinic acid-isopropanol catalyst was added, the temperature was raised to 80°C, stirred and reacted for 7 hours, and the solvent isopropanol was removed by rotary evaporation to obtain epoxy group modified silicone prepolymer A. The mass fraction ratio of compound 1, compound 2, isopropanol and chloroplatinic acid was 1.2:1.5:4:0.1.

[0102] Step 2: Preparation of alkyl tertiary amine modified polysiloxane prepolymer B;

[0103] Prepolymer A and compound 3 (f=2) were added to an isopropanol solution containing glacial acetic acid, and reacted at 80°C for 4 hours. After the reaction was completed, the solvent was removed by extraction and concentration to obtain a silicone oil prepolymer B with a side chain modified by a polyether alkyl tertiary amine. The mass ratio of prepolymer A, compound 3, isopropanol, and glacial acetic acid was 3:1:4:0.2.

[0104] Step 3: Preparation of polyether-modified block polysiloxane prepolymer C;

[0105] Compound 4 (g=10) and compound 5 (d=10) were subjected to addition reaction at 120° C. to obtain polyether-modified block polysiloxane prepolymer C, wherein the mass ratio of compound 4 to compound 5 was 2.1:1.

[0106] Step 4: Preparation of quaternary ammonium modified comb-shaped water-soluble block polysiloxane;

[0107] The prepolymer B and prepolymer C prepared in step 2 and step 3 were reacted with compound 6 (b=2, h=10) at 80°C for 6 hours to obtain the final quaternary ammonium modified comb-shaped water-soluble block polysiloxane. The added mass ratio of prepolymer B, prepolymer C, and amino silicone oil was 2:1:2.

[0108] The infrared spectrum of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane (WBD-2) is as follows: Figure 2WBD-2 satisfies the general structural formula (1), wherein a=64, b=4, c=4, d=10, e=10, and R=C3.

[0109] Synthesis Example 3

[0110] The preparation of the quaternized modified comb-shaped water-soluble block polysiloxane (WBD-3) comprises the following steps:

[0111] Step 1: Preparation of epoxy-modified polysiloxane prepolymer A;

[0112] Compound 1 (x=1, y=10) and compound 2 (e=10) were added to a reaction vessel, stirred and preheated at 45°C for 30 minutes under nitrogen protection, chloroplatinic acid-isopropanol catalyst was added, the temperature was raised to 80°C, stirred and reacted for 7 hours, and the solvent isopropanol was removed by rotary evaporation to obtain epoxy group modified silicone prepolymer A. The mass ratio of compound 1, compound 2, isopropanol and chloroplatinic acid was 1.2:1:3:0.1.

[0113] Step 2: Preparation of alkyl tertiary amine modified polysiloxane prepolymer B;

[0114] Prepolymer A and compound 3 (f=17) were added to an isopropanol solution containing glacial acetic acid, and reacted at 80°C for 4 hours. After the reaction, the solvent was removed by extraction and concentration to obtain a silicone oil prepolymer B with a side chain modified by a polyether alkyl tertiary amine. The mass ratio of prepolymer A, compound 3, isopropanol, and glacial acetic acid was 1:1:3:0.2.

[0115] Step 3: Preparation of polyether-modified block polysiloxane prepolymer C;

[0116] Compound 4 (g=20) and compound 5 (d=10) were subjected to addition reaction at 120° C. to obtain polyether-modified block polysiloxane prepolymer C, wherein the mass ratio of compound 4 to compound 5 was 3:1.

[0117] Step 4: Preparation of quaternary ammonium modified comb-shaped water-soluble block polysiloxane;

[0118] The prepolymer B and prepolymer C prepared in step 2 and step 3 were reacted with compound 6 (b=2, h=5) at 80°C for 6 hours to obtain the final quaternary ammonium modified comb-shaped water-soluble block polysiloxane. The added mass ratio of prepolymer B, prepolymer C, and amino silicone oil was 1:2:1.

[0119] The infrared spectrum of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane (WBD-3) is shown in Figure 3WBD-3 satisfies the general structural formula (1), wherein a=63, b=2, c=1, d=10, e=10, and R=C18.

[0120] Synthesis Example 4

[0121] The preparation of the quaternized modified comb-shaped water-soluble block polysiloxane (WBD-4) comprises the following steps:

[0122] Step 1: Preparation of epoxy-modified polysiloxane prepolymer A;

[0123] Compound 1 (x=1, y=10) and compound 2 (e=15) were added to a reaction vessel, stirred and preheated at 45°C for 30 minutes under nitrogen protection, chloroplatinic acid-isopropanol catalyst was added, the temperature was raised to 80°C, stirred and reacted for 7 hours, and the solvent isopropanol was removed by rotary evaporation to obtain epoxy group modified silicone prepolymer A. The mass ratio of compound 1, compound 2, isopropanol and chloroplatinic acid was 1:1:3:0.1.

[0124] Step 2: Preparation of alkyl tertiary amine modified polysiloxane prepolymer B;

[0125] Prepolymer A and compound 3 (f=12) were added to an isopropanol solution containing glacial acetic acid, and reacted at 80°C for 4 hours. After the reaction was completed, the solvent was removed by extraction and concentration to obtain a silicone oil prepolymer B with a side chain modified by a polyether alkyl tertiary amine. The mass ratio of prepolymer A, compound 3, isopropanol, and glacial acetic acid was 1:1.5:4:0.2.

[0126] Step 3: Preparation of polyether-modified block polysiloxane prepolymer C;

[0127] Compound 4 (g=20) and compound 5 (d=5) were subjected to addition reaction at 120° C. to obtain polyether-modified block polysiloxane prepolymer C, wherein the mass ratio of compound 4 to compound 5 was 2:1.

[0128] Step 4: Preparation of quaternary ammonium modified comb-shaped water-soluble block polysiloxane;

[0129] The prepolymer B and prepolymer C prepared in step 2 and step 3 were reacted with compound 6 (b=1, h=10) at 80°C for 6 hours to obtain the final quaternary ammonium modified comb-shaped water-soluble block polysiloxane. The added mass ratio of prepolymer B, prepolymer C, and amino silicone oil was 1.5:2:1.

[0130] The infrared spectrum of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane (WBD-4) is as follows: Figure 4WBD-4 satisfies the general structural formula (1), wherein a=99, b=1, c=2, d=5, e=15, and R=C13.

[0131] The prepared quaternary ammonium modified comb-shaped water-soluble block silicone oil can be used in daily chemicals such as shampoo, conditioner, hair care lotion, hair care essential oil, etc. The application of the prepared quaternary ammonium modified comb-shaped water-soluble block silicone oil in daily chemicals is also very simple, and it can be directly added to the product and stirred and dispersed evenly. The addition amount is 0.3% to 30% according to the product type and performance requirements.

[0132] The following is an example of the application of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane in a formulation:

[0133] Table 1 is an example of the application of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane in shampoo products.

[0134]

[0135] Table 2 is a comparative example of the application of traditional silicone oil

[0136]

[0137] The shampoo preparation methods of application examples 1-5 and application comparative examples 1-5 of the present invention include the following steps:

[0138] S1. Add the water and cationic guar gum of phase A into the emulsifier, homogenize until completely dispersed, start stirring, heat to 75-85°C, and keep warm for 10-30 minutes;

[0139] S2. Add lauryl hydroxysultaine and sodium cocoyl isethionate of phase B into the emulsifier in sequence, and stir at 75°C for 20-30 minutes;

[0140] S3, cool the material prepared in step S2 to below 40°C, add the raw materials of phase C in sequence, and stir and disperse for 10-20 minutes;

[0141] S4. Add phase D to the material prepared in step S3, and stir for 5-20 minutes until the material is evenly dispersed to obtain a finished shampoo.

[0142] Efficacy test example

[0143] 1. Combing smoothness test method:

[0144] The wet hair combing test is a test of the combing force or combing work of isolated human hair bundles using a hair bundle comber. It is used to evaluate the effect of personal care products on improving damaged hair bundles.

[0145] The specific steps of the combing test of the product of the present invention are as follows:

[0146] 1. Hair bundle selection: select hair bundles that have not been tested and conduct combing test on them. Select hair bundles with no obvious difference in combing force or combing work for testing of application examples. The hair bundles used for application testing are divided into control group and test group, with 3 hair bundles in each group for each application test.

[0147] 2. Hair bundle pretreatment: Wash the hair bundle with clean water at a temperature of 38±1°C. After washing, dry it in a constant temperature and humidity chamber for use. The conditions of the constant temperature and humidity chamber are set at: 23±0.5°C, 60±5%RH.

[0148] 3. Baseline wet hair combing test (W0): The test group hair bundles are fully wetted with running constant temperature clean water, and 0.2 grams of cleaning liquid is used per gram of hair bundles, and the cleaning liquid is evenly applied on the surface of the hair bundles for about 30 seconds, left to stand for about 1 minute, and then rinsed for about 30 seconds. The treated hair bundles are fixed in the test position and the combing cycle test is carried out.

[0149] 4. Baseline dry hair combing test (D0): The hair bundle after the wet hair test is placed in a constant temperature and humidity chamber for more than 4 hours, taken out and fixed in the test position, and the combing cycle test is performed. The hair bundle after the test is placed in a constant temperature and humidity chamber for use.

[0150] 5. Sample wet hair combing test (W): Wet the hair bundle that has completed the baseline combing test with running constant temperature clean water, and evenly apply 0.2 grams of sample per gram of hair bundle or the amount in accordance with the sample usage method on the surface of the hair bundle for about 30 seconds, let it stand for about 1 minute, and then rinse for about 30 seconds or skip rinsing. Fix the treated hair bundle in the test position and perform the combing cycle test.

[0151] 6. Sample dry hair combing test (D): After the wet hair test, the hair bundle is placed in a constant temperature and humidity chamber for more than 4 hours, taken out and fixed in the test position, and the combing cycle test is carried out.

[0152] 7. Calculation of combing improvement effect: Wet hair combing improvement = (W0-W) / W0*100%; Dry hair combing improvement = (D0-D) / D0*100%.

[0153] 2. Fluffy performance test method:

[0154] In order to reduce the interference of human body in the test result of fluffiness in blowing, combing and living habits, the fluffiness test method of the present invention uses hair bundles for testing. The specific operation method is as follows:

[0155] 1. Pre-cleaning: Wash the hair with 5% SLES solution once, and hang it in a constant temperature and humidity environment to dry overnight for later use;

[0156] 2. Pre-treat the hair with 1% artificial sebum ethanol solution, dry it, and do not comb it. Take photos of the hair under this condition in a homemade light box in the laboratory. Steam each hair at 120 degrees and take three photos.

[0157] 3. Import the photos into Image Pro image analysis software, calculate the area of ​​each hair strand, and calculate the average initial area A0 based on the areas of the same hair strand at three different angles;

[0158] 4. Wash the hair with the shampoo to be tested, using 0.2g per gram of hair, rubbing for 30s, and rinsing for 30s;

[0159] 5. Hang the washed hair bundle in a constant temperature and humidity room (Rh55%, 22°C) to dry overnight;

[0160] 6. Keep the hair in the state of drying without combing it, and take photos of the hair in this condition in a homemade light box in the laboratory. Steam each hair at 120 degrees and take three photos;

[0161] 7. Import the photo into Image Pro image analysis software, calculate the area of ​​each hair strand, and calculate the average area A based on the area of ​​the same hair strand at three different angles. x .

[0162] 8. Calculate the bulkiness using the following formula:

[0163]

[0164] 3. Test of silicone oil deposition:

[0165] The method refers to the extraction-weighing method in the literature "Deposition of silicone oil in shampoo on hair" by Jiangnan University. The specific steps are as follows:

[0166] 1. Wash the hair bundles with 30% K12 solution 3 times, then rinse with plenty of water and dry at room temperature for later use;

[0167] 2. Weigh 2.0g of hair bundle, add 2.0g of pure water to moisten it, weigh 0.4g of the prepared shampoo sample and add it to the hair, put on disposable PE gloves, apply the shampoo evenly on the hair, rub and foam for 1min, let it stand for 0.5min, rinse with running water for 1min, and dry the washed hair bundle at room temperature for 12h;

[0168] 3. For the hair strands that need to be washed 3 and 5 times, repeat step 2 3 and 5 times respectively;

[0169] 4. Weigh 50g of n-hexane and extract the washed and dried hair in a 40℃ water bath for 24h, filter, put the filtrate in a weighed flask, evaporate the n-hexane with a rotary evaporator, cool and weigh;

[0170] 5. Add 10g of n-hexane to the flask and continue rotary evaporation. After the n-hexane is evaporated, cool and weigh it down. Repeat this process until the weight reaches a constant value. Then stop rotary evaporation and calculate the unit deposition amount of silicone oil.

[0171] Table 3 Combing and smoothing performance of application examples and comparative examples

[0172]

[0173]

[0174] It can be seen from the application examples and application comparison examples in Table 3 that the quaternary ammonium modified comb-shaped water-soluble block polysiloxane prepared by the present invention has better combing improvement performance than traditional polydimethylsiloxane and amino silicone oil when used in shampoo.

[0175] Table 4 Fluffiness test results of application examples and comparative examples

[0176] Application Examples A0 before cleaning (cm2) Ax (cm2) used 5 times <![CDATA[I washed 5 times X > Application Example 1 65.317 132.716 103.19％ Application Example 2 64.258 135.214 110.42％ Application Example 3 64.376 131.427 104.16％ Application Example 4 65.217 132.542 103.23％ Application Example 5 64.382 140.375 118.03％ Application Comparative Example 1 65.224 105.234 61.34％ Application Comparative Example 2 65.378 107.256 64.06％ Application Comparative Example 3 64.312 100.435 56.17％ Application Comparative Example 4 64.465 98.457 52.73％ Application Comparative Example 5 64.327 105.462 63.95％

[0177] It can be seen from the application examples and application comparison examples in Table 4 that, in terms of fluffy performance, the quaternary ammonium modified comb-shaped water-soluble block polysiloxane prepared by the present invention has better fluffy performance than traditional polydimethylsiloxane and amino silicone oil when used in shampoo.

[0178] Table 5 Deposition amount of deposited silicone oil in application examples and comparative examples (mg / g)

[0179]

[0180]

[0181] It can be seen from the application examples and application comparison examples in Table 5 that when the quaternary ammonium modified comb-shaped water-soluble block polysiloxane prepared by the present invention is used in shampoo, the amount of silicone oil deposited on the surface is smaller than that of traditional polydimethylsiloxane and amino silicone oil.

[0182] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

Claims

1. A quaternary ammonium modified comb-shaped water-soluble block polysiloxane, characterized in that: Its structure satisfies the general structural formula (1): wherein a is independently an integer selected from 20 to 200; b is independently an integer selected from 1 to 10; c is independently an integer selected from 1 to 10; d is independently an integer selected from 1 to 20; e is an integer from 1 to 20; and R is a C1 to C20 alkyl group.

2. The quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to claim 1, characterized in that: In the general structural formula (1), a is independently an integer selected from 20 to 100; b is independently an integer selected from 1 to 5; c is independently an integer selected from 1 to 5; d is independently an integer selected from 8 to 20; e is an integer from 8 to 20; and R is a C1 to C20 alkyl group.

3. The method for preparing the quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to claim 1, characterized in that: The specific steps include: Step 1: Preparation of epoxy-modified polysiloxane prepolymer A: Add hydrogen-terminated silicone with hydrogen groups on the side chain and epoxy compounds containing double bonds into a reaction vessel, stir and preheat at 40-60° C. for 10-30 min under nitrogen protection, add chloroplatinic acid-isopropanol catalyst, heat to 70-90° C., stir and react for 5-7 hours, remove the solvent isopropanol by rotary evaporation, and obtain epoxy group-modified silicone prepolymer A; Step 2: Preparation of alkyl tertiary amine modified polysiloxane prepolymer B: The epoxy-modified silicone oil reacts with the long alkyl tertiary amine under the action of isopropanol and glacial acetic acid, the reaction temperature is 60-120°C, the reaction time is 1-7 hours, and after the reaction is completed, the solvent is removed by extraction and concentration to obtain a silicone oil prepolymer B whose side chain is modified by a polyether alkyl tertiary amine; Step 3: Preparation of polyether-modified block polysiloxane prepolymer C: The hydrogen-terminated polydimethylsiloxane and the alkenyl-terminated polyether are subjected to addition reaction at 80-160° C. to obtain a polyether-modified block silicone oil prepolymer C; Step 4: Preparation of quaternary ammonium modified comb-shaped water-soluble block polysiloxane: The prepolymer B and prepolymer C prepared in step 2 and step 3 are reacted with the side chain amino silicone polymer at 60 to 90° C. for 5 to 10 hours to obtain the final quaternary ammonium modified comb-shaped water-soluble block silicone oil.

4. The method for preparing the quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to claim 3, characterized in that: In step 1), the stirring preheating temperature is 45°C and the time is 30 minutes; the chloroplatinic acid-isopropanol catalyst is added, the temperature is raised to 80°C, and the stirring reaction is for 7 hours; In step 2), the reaction temperature is 80°C and the reaction time is 4 to 6 hours; In step 3), the addition reaction temperature is 120°C; In step 4), the reaction temperature is 80° C. and the reaction time is 6 hours.

5. The method for preparing the quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to claim 3, characterized in that: In step 3), the mass fraction of the hydrogen-terminated polydimethylsiloxane is 1 to 5 times that of the alkenyl-terminated polyether.

6. The method for preparing the quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to claim 3, characterized in that: In step 4), the added mass ratio of the prepolymer B, prepolymer C, and amino silicone oil is: (0.5-3): (0.5-3): (1-4).

7. Use of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to any one of claims 1 to 6 in the preparation of daily chemicals.

8. The use of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to claim 7 in the preparation of daily chemicals, characterized in that: The daily chemicals include but are not limited to shampoo, conditioner, hair lotion, and hair essential oil.

9. The use of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to claim 7 in the preparation of daily chemicals, characterized in that: The prepared quaternary ammonium modified comb-shaped water-soluble block polysiloxane can be used in daily chemicals by directly adding it into the product and stirring and dispersing it evenly; the added amount is 0.3% to 30%.

10. The use of the quaternary ammonium modified comb-shaped water-soluble block polysiloxane according to claim 8 in the preparation of daily chemicals, characterized in that: The daily chemical product is shampoo; The formula of the shampoo is the following components in percentage by weight: Phase A: balance water, cationic guar gum 0.2%; Phase B: Lauryl Hydroxysultaine 30%, Sodium Cocoyl Isethionate 5%; Phase C: citric acid 0.08%, phenoxyethanol 0.5%, sodium benzoate 0.4%, fragrance 0.6%; Phase D: 0.5-0.8% of quaternary ammonium modified comb-shaped water-soluble block polysiloxane; The preparation method of the shampoo comprises the following steps: S1. Add the water and cationic guar gum of phase A into the emulsifier, homogenize until completely dispersed, start stirring, heat to 75-85°C, and keep warm for 10-30 minutes; S2. Add lauryl hydroxysultaine and sodium cocoyl isethionate of phase B into the emulsifier in sequence, and stir at 75°C for 20-30 minutes; S3, cool the material prepared in step S2 to below 40°C, add the raw materials of phase C in sequence, and stir and disperse for 10-20 minutes; S4. Add phase D to the material prepared in step S3, and stir for 5-20 minutes until the material is evenly dispersed to obtain a finished shampoo.

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