Self-emulsifying cationic silicone wax as well as preparation method and application thereof

Abstract

The invention belongs to the field of organic silicon, and particularly provides self-emulsifying cationic silicone wax as well as a preparation method and application thereof. The self-emulsifying cationic silicone wax is represented by the following average composition formula (I): R < 1 > aR < 2 > bR < 3 > cSiO < 4-a-b-c > / 2 (I), in the formula, R1 is represented by a general formula (II), and R2 is represented by a general formula (III); r3 is an organic group; * represents a connection position; a ranges from 0.01 to 0.5, b ranges from 0.05 to 0.5, and c ranges from 1.4 to 2.5. The preparation method of the self-emulsifying cationic silicone wax comprises the following steps. The self-emulsifying cationic silicone wax provided by the invention is soft hydrophobic silicone wax, not only can provide excellent waterproofness and soft hand feeling, but also can improve the durability of the effect, and can be widely applied to the fields of daily chemicals, textiles, coatings and the like.

Description

A self-emulsifying cationic silicone wax, its preparation method and application Technical Field

[0001] This invention belongs to the field of organosilicon technology, specifically relating to a self-emulsifying cationic silicone wax, its preparation method, and its application. Background Technology

[0002] Silicone wax is a polysiloxane product with long-chain substituents. The film it forms is smooth and hydrophobic, providing excellent and durable waterproof and water-resistant properties. It is also chemically stable and not easily oxidized or degraded. However, when used in aqueous systems, it requires the addition of a relatively large amount of suitable emulsifier to emulsify into a stable emulsion. If the chosen emulsifier is unsuitable, problems such as demulsification, precipitation, and layering of the silicone wax emulsion can easily occur during storage, and electrolytes in the formulation can also easily disrupt the emulsion system. Self-emulsifying silicone wax, by introducing hydrophilic groups into its molecular chain segments, allows it to self-emulsify into a silicone wax emulsion, effectively solving the above problems.

[0003] CN120737350A discloses a silicone wax that can self-emulsify into a blue light emulsion and its preparation method. This silicone wax, capable of self-emulsifying into a blue light emulsion, has the following general molecular formula: (CH3)3SiO[(CH3)2SiO] a [(CH3)(C 18~30 H 37 - 61 )SiO] b [(CH3)(R)SiO]CSi(CH3)3, where R is a polyether group with the structural formula "-C3H6O-(C3H6O)m-(C2H4O)nH" or "-C3H6O-(C3H6O)m-(C2H4O)n-CH3"; This silicone wax, which can self-emulsify into a blue light emulsion, solves the problem of instability or layering when mixed with other wax emulsions, which are common in conventional silicone wax emulsions containing emulsifiers, thus avoiding defects and risks in downstream applications.

[0004] However, this self-emulsifying silicone wax is a polyether-type silicone wax, which has poor film adhesion and durability on substrates such as textiles or hair products. Summary of the Invention

[0005] Against this backdrop, the present invention aims to provide a self-emulsifying cationic silicone wax, its preparation method, and its applications. The core of this material design lies in its unique self-emulsifying ability, allowing for stable dispersion in water without the need for external emulsifiers, thus fundamentally eliminating the performance and stability degradation problems caused by added emulsifiers. This self-emulsifying cationic silicone wax, by simultaneously introducing long-chain quaternary ammonium salts and long-chain ester groups with hydroxyl groups, exhibits superior film-forming adhesion and durability, especially in textiles and hair products. Introducing it into fluorine-free waterproofing agent formulations not only effectively maintains or even enhances waterproof durability but also significantly improves the soft and smooth feel of fabrics, enhancing the overall quality and added value of end products. This provides a new technical path for developing high-performance, multi-functional integrated fluorine-free waterproofing finishing solutions.

[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a self-emulsifying cationic silicone wax, wherein the self-emulsifying cationic silicone wax is represented by the following average compositional formula (Ⅰ): R 1 a R 2 b R 3 c SiO （4-a-b-c） / 2 (I); where R 1 It is represented by the following general formula (II): (II); where R 4 Selected from substituted or unsubstituted alkyl, aryl, and polyether groups, wherein the alkyl group is optionally interrupted by one or more oxygen atoms; each R 5 They may be the same or different, selected from straight-chain or branched alkyl groups, and have at least one R. 5 Selected from C8-C45 alkyl groups (e.g., alkyl groups with 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 8, 39, 40, 42, 44, etc.); more preferably, C8-C30 alkyl groups; R 2 It is represented by the following general formula (Ⅲ): (Ⅲ); R 8 Selected from substituted or unsubstituted hydrocarbon groups; preferably hydrocarbon groups containing 8 or more carbon atoms; more preferably substituted or unsubstituted C8-45 alkyl groups (e.g., alkyl groups with 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 8, 39, 40, 42, 44, etc.); further preferably substituted or unsubstituted C12-35 alkyl groups; R 3* indicates an organic group; * indicates a connection position; a is 0.01~0.5 (e.g., 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, ...). 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, etc.), where b is 0.05~0.5 (e.g., 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16). , 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, etc.), c The values ​​range from 1.4 to 2.5 (e.g., 1.5, 1.53, 1.55, 1.56, 1.58, 1.6, 1.62, 1.65, 1.68, 1.7, 1.71, 1.72, 1.75, 1.77, 1.78, 1.8, 1.82, 1.85, 1.88, 1.9, 1.92, 1.95, 1.97, 2, 2.04, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, etc.).

[0007] From the perspective of improving the emulsifiability of the polymer, a is preferably 0.03~0.5, more preferably 0.05~0.5, and even more preferably 0.08~0.5; b is preferably 0.05~0.45, more preferably 0.05~0.4, and even more preferably 0.05~0.35.

[0008] From the perspective of improving the emulsifiability of the polymer, a is preferably 0.03~0.5, more preferably 0.05~0.5, and even more preferably 0.08~0.5; b is preferably 0.05~0.45, more preferably 0.05~0.4, and even more preferably 0.05~0.35.

[0009] From the perspective of not affecting the hydrophobicity of the polymer, a is preferably 0.01~0.4, more preferably 0.01~0.35, and even more preferably 0.01~0.3; b is preferably 0.08~0.5, and more preferably 0.1~0.5.

[0010] More preferably, c is 1.5 to 2. More preferably, c is 1.5 to 1.8.

[0011] Specifically, R 3 It can be selected from any one of alkyl, aryl, aralkyl, siloxane, hydroxyl, and alkoxy, and is more preferably alkyl.

[0012] Preferably, the raw materials for preparing the self-emulsifying cationic silicone wax include: epoxy-modified polysiloxane, long-chain alkyl fatty acid, long-chain alkyl tertiary amine, organic acid, and optionally an esterification catalyst; the long-chain alkyl fatty acid has a C8-C45 long carbon chain; the long-chain alkyl tertiary amine has a C8-C45 long carbon chain.

[0013] Preferably, the long-chain alkyl fatty acids include one or more of the following: lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, erucic acid, palmitoleic acid, ricinoleic acid, α-linolenic acid, γ-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid.

[0014] More preferably, in step S2, the long alkyl chain fatty acid is one or a combination of two or more of palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, erucic acid, palmitoleic acid, ricinoleic acid, α-linolenic acid, γ-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid.

[0015] Preferably, the long-chain alkyl tertiary amine includes one or more of the following: trioctylamine, tridecylamine, tri(dodecyl)amine, di(dodecyl)methylamine, docosyldimethylamine, di(tetradecyl)methylamine, di(hexadecyl)methylamine, di(octadecyl)methylamine, decyldimethylamine, dodecyldimethylamine, and tetradecyldimethylamine.

[0016] More preferably, the long alkyl chain tertiary amine includes one or more of the following: tridecylamine, tri(dodecyl)amine, di(dodecyl)methylamine, di(tetradecyl)methylamine, di(hexadecyl)methylamine, di(octadecyl)methylamine, decyl dimethylamine, dodecyl dimethylamine, and tetradecyl dimethylamine.

[0017] Preferably, the organic acid is one or more of acetic acid, lactic acid, citric acid, formic acid, malic acid, and tartaric acid.

[0018] Preferably, the esterification catalyst is one or more of tetrabutylammonium bromide, tetraethylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, triethylamine, and triphenylphosphine.

[0019] Preferably, epoxy-modified polysiloxanes are obtained by reacting hydrogen-containing polysiloxanes and alkenyl-containing epoxy compounds in the presence of a hydrosilylation catalyst.

[0020] More preferably, in step S1, the molar ratio between the hydrogen-containing siloxane and the alkenyl epoxy compound is 1:(2.1~45), and the amount of catalyst used is 1~30 ppm.

[0021] More preferably, the hydrogen-containing siloxane has a molecular weight of 500~18000 g / mol and a hydrogen content of 0.05~2.0%.

[0022] More preferably, the hydrogen-containing siloxane has a molecular weight of 500-16000 g / mol and a hydrogen content of 0.1-1.5%; for example, it can be 500 (0.6% hydrogen content), 600 (0.55% hydrogen content), 980 (0.45% hydrogen content), 1350 (0.53% hydrogen content), 1450 (0.65% hydrogen content), 1500 (0.68% hydrogen content), 2000 (0.75% hydrogen content), 3500 (0.36% hydrogen content), 4000 (0.49% hydrogen content), 6000 (0.36% hydrogen content), 6000 (0.75% hydrogen content), 9000 (1.28% hydrogen content), or 10000 (1.05% hydrogen content). 13000 (0.45% hydrogen content), 15000 (0.75% hydrogen content), etc.

[0023] Preferably, the alkenyl epoxy compound includes one or more combinations of allyl glycidyl ether, allyl functionalized bisphenol A type epoxy resin, allyl phenyl glycidyl ether, eugenol glycidyl ether, trimethylolpropane diallyl ether glycidyl ether, allyl cyclohexyl glycidyl ester, glycidyl methacrylate, and allyl furfuryl glycidyl ether.

[0024] More preferably, the epoxy derivative includes one or more of allyl glycidyl ether, allyl phenyl glycidyl ether, eugenol glycidyl ether, trimethylolpropane diallyl ether glycidyl ether, allyl cyclohexyl glycidyl ester, glycidyl methacrylate, and allyl furfuryl glycidyl ether.

[0025] Preferably, the hydrosilylation catalyst is one or a combination of two or more of the following: Karstedt catalyst, Speier catalyst, and modified catalyst.

[0026] Preferably, the molar ratio between the epoxy-modified polysiloxane and the long-chain alkyl fatty acid is 1:(1.1~30).

[0027] Preferably, the molar ratio between the long-chain alkyl fatty acid and the long-chain alkyl tertiary amine is 1:(0.5~1.3).

[0028] Preferably, the molar ratio between the total number of moles of the long-chain alkyl fatty acid and the long-chain alkyl tertiary amine and the number of epoxy groups contained in the epoxy-modified polysiloxane is 1:(0.9~1.1); the molar ratio between the long-chain alkyl fatty acid and the long-chain alkyl tertiary amine is 1:(0.5~1.3).

[0029] Secondly, the present invention provides a method for preparing the above-mentioned self-emulsifying cationic silicone wax, the method comprising the following steps: S1. Obtaining an epoxy-modified polysiloxane by reacting a hydrogen-containing polysiloxane and an alkenyl epoxy compound under the action of a hydrosilylation catalyst; S2. Reacting the epoxy-modified polysiloxane, a long-chain alkyl fatty acid, and optionally a polycondensation catalyst to obtain an epoxy-containing silicone wax; S3. Reacting the epoxy-containing silicone wax obtained in step S2, a long-chain alkyl tertiary amine, and an organic acid to obtain a soft, hydrophobic, self-emulsifying cationic silicone wax.

[0030] Preferably, in step S1, the reaction temperature is 60~140 ℃, the reaction time is 1~30 h, and the reaction atmosphere is nitrogen.

[0031] Preferably, in step S1, the molar ratio between the hydrogen-containing polysiloxane and the alkenyl epoxy compound is 1:(2.1~45).

[0032] Preferably, the molar ratio between the long-chain alkyl fatty acid and the alkenyl epoxy compound is 1:(1.4~2.6).

[0033] Preferably, in step S3, the molar ratio between the epoxy-containing silicone wax, the long alkyl chain tertiary amine, and the organic acid is 1:(1.1~30):(1.1~32).

[0034] Preferably, in step S2, the reaction temperature is 70~150 ℃ and the reaction time is 5~24 h.

[0035] Preferably, in step S3, the reaction temperature is 40~100 ℃ and the reaction time is 1~16 h.

[0036] Thirdly, the present invention provides the application of a self-emulsifying cationic silicone wax as described in the first aspect or a self-emulsifying cationic silicone wax fluorine-free waterproofing agent prepared according to the preparation method described in the second aspect in daily chemicals, textiles, leather or coatings.

[0037] Fourthly, the present invention provides a silicone wax emulsion comprising a self-emulsifying silicone wax, a co-solvent, and water; wherein the self-emulsifying silicone wax comprises the aforementioned self-emulsifying cationic silicone wax or a self-emulsifying cationic silicone wax obtained according to the aforementioned preparation method.

[0038] The mass ratio of the self-emulsifying silicone wax to the cosolvent and water is (15~30):(15~50):(1~5).

[0039] The above-mentioned silicone wax emulsion can be prepared by the following method: mix self-emulsifying silicone wax and co-solvent and heat to 70-90℃ until completely dissolved. Then, add water at 70-90℃ under high-speed stirring. After the addition is complete, continue high-speed shearing for 20-60 minutes to obtain the silicone wax emulsion.

[0040] Compared with the prior art, the present invention has at least the following beneficial effects: (1) The self-emulsifying cationic silicone wax designed and synthesized by the present invention can spontaneously disperse in the aqueous phase to form a stable emulsion without relying on external emulsifiers, based on its molecular structure design, fundamentally avoiding the many drawbacks of traditional non-self-emulsifying silicone wax or silicone oil that must rely on surfactants to achieve emulsification.

[0041] (2) By introducing long alkyl chain cationic functional groups and long chain ester groups, and simultaneously introducing hydroxyl groups, the present invention significantly improves film-forming density, as well as adhesion and durability on substrates such as textiles and hair products.

[0042] (3) The self-emulsifying cationic silicone wax provided by the present invention can impart excellent self-emulsifying ability to the system, while having good compatibility with different types of polymer resins. It can form films in synergy with other resins, significantly improving the feel, hydrophobicity and durability. Attached Figure Description

[0043] Figure 1 is a synthesis pathway diagram of the self-emulsifying cationic silicone wax provided in Example 1 of the present invention.

[0044] Figure 2 is the infrared spectrum of the self-emulsifying cationic silicone wax provided in Example 1 of the present invention. Detailed Implementation

[0045] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be considered as specific limitations thereof. Embodiment 1

[0046] This embodiment provides a self-emulsifying cationic silicone wax with the following average composition: R 1 0.18 R 2 0.18 R 31.72 SiO 0.96 (Ⅰ-1), where R 1 ;R 2 = ;R 3 It is a methyl group.

[0047] The self-emulsifying cationic silicone wax comprises the following raw materials: 0.5 mol of hydrogen-containing silicone oil (Sloco Polymer, Mn=1500 g / mol, hydrogen content 0.6%), 2 mol of allyl glycidyl ether, 5 ppm of chloroplatinic acid catalyst, 1 mol of stearic acid, 0.05 mol of tetrabutylammonium bromide, 1 mol of docosyldimethyl tertiary amine (CAS: 21542-96-1), and 1.1 mol of glacial acetic acid.

[0048] The preparation method of the above-mentioned self-emulsifying cationic silicone wax includes the following steps, and its synthesis route is shown in Figure 1: After the hydrogen-containing silicone oil and chloroplatinic acid catalyst are mixed evenly, the temperature is raised while stirring. After the system reaches 75 °C, allyl glycidyl ether is slowly added dropwise. The addition is completed in 2 h. The reaction is continued at the temperature for 3 h, and then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Then, a measured amount of stearic acid and tetrabutylammonium bromide are added to the obtained epoxy polysiloxane intermediate. The temperature is slowly raised to 85 °C. After the reaction is kept at the temperature for 4 h, the temperature is lowered to 60 °C, and a measured amount of docosyl tertiary amine and glacial acetic acid are added. The reaction is stirred for 6 h, and then naturally cooled to room temperature to obtain self-emulsifying cationic silicone wax (ZG1).

[0049] As can be seen from the infrared spectrum in Figure 2, the product prepared in this embodiment has CN, C=O, Si-C, Si-O, and -OH groups, proving that the product obtained in this embodiment has the structure shown in structural formula (Ⅰ). Example 2

[0050] This embodiment provides a self-emulsifying cationic silicone wax, the raw materials of which include: 0.5 moles of hydrogen-containing silicone oil (Sloco Polymer, Mn=2000 g / mol, hydrogen content 0.75%), 7.8 moles of allyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 3 moles of behenic acid, 0.2 moles of tetrabutylammonium bromide, 4 moles of di(octadecyl)methylamine (CAS: 4088-22-6) and 4.2 moles of glacial acetic acid.

[0051] The preparation method of the above-mentioned self-emulsifying cationic silicone wax includes the following steps: Hydrogen-containing silicone oil and chloroplatinic acid catalyst are mixed evenly, then heated while stirring. Once the system reaches 110 °C, allyl glycidyl ether is slowly added dropwise over 2 hours. The reaction is continued at this temperature for 5 hours, then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide are added to the obtained epoxy polysiloxane intermediate. The temperature is slowly raised to 95 °C, and the reaction is maintained for 5 hours. The temperature is then lowered to 60 °C, and a measured amount of di(octadecyl)methylamine and glacial acetic acid are added. The reaction is stirred for 6 hours, and then naturally cooled to room temperature to obtain self-emulsifying cationic silicone wax (ZG2). Example 3

[0052] This embodiment provides a self-emulsifying cationic silicone wax, the raw materials of which include: 0.5 moles of hydrogen-containing silicone oil (Sloco Polymer, Mn=2000 g / mol, hydrogen content 0.75%), 7.8 moles of allyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 5 moles of behenic acid, 0.2 moles of tetrabutylammonium bromide, 3 moles of docosyldimethyl tertiary amine, and 3.2 moles of glacial acetic acid.

[0053] The preparation method of the above-mentioned self-emulsifying cationic silicone wax includes the following steps: Hydrogen-containing silicone oil and chloroplatinic acid catalyst are mixed evenly, then heated while stirring. Once the system reaches 110 °C, allyl glycidyl ether is slowly added dropwise over 2 hours. The reaction is continued at this temperature for 5 hours, then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide are added to the obtained epoxy intermediate. The temperature is slowly raised to 95 °C, and the reaction is maintained for 5 hours. The temperature is then lowered to 60 °C, and a measured amount of docosyldimethylamine and glacial acetic acid are added. The reaction is stirred for 6 hours, and then naturally cooled to room temperature to obtain self-emulsifying cationic silicone wax (ZG3). Example 4

[0054] This embodiment provides a self-emulsifying cationic silicone wax, the raw materials of which include: 0.5 moles of hydrogen-containing silicone oil (Sloco Polymer, Mn=6000 g / mol, hydrogen content 0.36%), 11 moles of allyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 6 moles of behenic acid, 0.2 moles of tetrabutylammonium bromide, 5.5 moles of tridecylamine (CAS: 1070-01-5) and 6 moles of glacial acetic acid.

[0055] The preparation method of the above-mentioned self-emulsifying cationic silicone wax includes the following steps: Hydrogen-containing silicone oil and chloroplatinic acid catalyst are mixed evenly, then heated while stirring. Once the system reaches 120 °C, allyl glycidyl ether is slowly added dropwise over 2 hours. The reaction is continued at this temperature for 6 hours, then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide are added to the obtained epoxy polysiloxane intermediate. The temperature is slowly raised to 110 °C, and the reaction is maintained for 4 hours. The temperature is then lowered to 60 °C, and a measured amount of tridecylamine and glacial acetic acid are added. The reaction is stirred for 6 hours, and then naturally cooled to room temperature to obtain self-emulsifying cationic silicone wax (ZG4). Example 5

[0056] This embodiment provides a self-emulsifying cationic silicone wax, the raw materials of which include: 0.5 moles of hydrogen-containing silicone oil (Sloco Polymer, Mn=6000 g / mol, hydrogen content 0.36%), 11 moles of allyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 8 moles of behenic acid, 0.2 moles of tetrabutylammonium bromide, 4 moles of tetradecyl dimethylamine (CAS: 112-75-4) and 4.4 moles of glacial acetic acid.

[0057] The preparation method of the above-mentioned self-emulsifying cationic silicone wax includes the following steps: Hydrogen-containing silicone oil and chloroplatinic acid catalyst are mixed evenly, then heated while stirring. Once the system reaches 120 °C, allyl glycidyl ether is slowly added dropwise over 2 hours. The reaction is continued at this temperature for 6 hours, then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide are added to the obtained epoxy polysiloxane intermediate. The temperature is slowly raised to 105 °C, and the reaction is maintained for 4 hours. The temperature is then lowered to 60 °C, and a measured amount of tetradecyl dimethylamine, docosyl tertiary amine, and glacial acetic acid are added. The reaction is stirred for 6 hours, and then naturally cooled to room temperature to obtain the self-emulsifying cationic silicone wax (ZG5). Example 6

[0058] This embodiment provides a self-emulsifying cationic silicone wax, the raw materials of which include: 0.5 moles of hydrogen-containing silicone oil (Sloco Polymer, Mn=6000 g / mol, hydrogen content 0.36%), 11 moles of allyl phenyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 6 moles of behenic acid, 0.2 moles of tetrabutylammonium bromide, 5.5 moles of docosyl dimethyl tertiary amine, and 6 moles of glacial acetic acid.

[0059] The preparation method of the above-mentioned self-emulsifying cationic silicone wax includes the following steps: Hydrogen-containing silicone oil and chloroplatinic acid catalyst are mixed evenly, then heated while stirring. Once the system reaches 120 °C, allyl phenyl glycidyl ether is slowly added dropwise over 2 hours. The reaction is continued at this temperature for 4 hours, then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide are added to the obtained epoxy intermediate. The temperature is slowly raised to 115 °C, and the reaction is maintained for 3 hours. The temperature is then lowered to 60 °C, and a measured amount of docosyl dimethyl tertiary amine and glacial acetic acid are added. The reaction is stirred for 6 hours, and then naturally cooled to room temperature to obtain self-emulsifying cationic silicone wax (ZG6). Example 7

[0060] This embodiment provides a self-emulsifying cationic silicone wax, the raw materials of which include: 0.5 moles of hydrogen-containing silicone oil (Sloco Polymer, Mn=6000 g / mol, hydrogen content 0.45%), 14 moles of allyl phenyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 7 moles of behenic acid, 0.3 moles of tetrabutylammonium bromide, 7 moles of docosyl tertiary amine, and 7.5 moles of glacial acetic acid.

[0061] The preparation method of the above-mentioned self-emulsifying cationic silicone wax includes the following steps: After mixing the hydrogen-containing silicone oil and chloroplatinic acid catalyst evenly, the mixture is heated while stirring. When the system reaches 135 °C, allyl phenyl glycidyl ether is slowly added dropwise. The addition is completed in 2 hours. The reaction is continued at the same temperature for 5 hours. Then, the mixture is naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, the system is cooled to 115 °C, and a measured amount of behenic acid and tetrabutylammonium bromide are added sequentially. The reaction is continued at the same temperature for 5 hours. Then, the temperature is cooled to 60 °C, and a measured amount of docosyl tertiary amine and glacial acetic acid are added. The reaction is stirred for 8 hours. Then, the mixture is naturally cooled to room temperature to obtain self-emulsifying cationic silicone wax (ZG7).

[0062] Comparative Example 1: This comparative example provides an octadecyl silicone wax, which is prepared as follows: 0.5 moles of hydrogen-containing silicone oil (Sloco Polymer, Mn=1500 g / mol, hydrogen content 0.6%) and chloroplatinic acid catalyst are mixed evenly, and then the temperature is increased while stirring. After the system reaches 75 °C, 2 moles of octadecene are slowly added dropwise. The addition is completed in 2 h. The reaction is continued at the temperature for 3 h, and then naturally cooled to room temperature to obtain octadecyl silicone wax.

[0063] Comparative Example 2 differs from Example 1 only in that the molar ratio of stearic acid to allyl glycidyl ether is changed to 1:1, and docosyl tertiary amine and glacial acetic acid are not added for reaction, thus obtaining hydroxyl-containing silicone wax ZG9.

[0064] The only difference between Comparative Example 3 and Example 1 is that stearic acid was not added for the reaction, and the amount of docosyl tertiary amine added was modified to 2 moles, resulting in a self-emulsifying silicone wax containing only long-chain tertiary amine groups.

[0065] Comparative Example 4 provides a cationic silicone wax with the following average composition: R 1 0.01 R 2 0.55 R 3 1.72 SiO 0.86 (Ⅰ-2); where R 1 for ;R 2 for ;R 3 It is a methyl group.

[0066] Comparative Example 5 provides a cationic silicone wax with the following average composition: R 1 0.55 R 2 0.04 R 3 1.72 SiO 0.85 (Ⅰ-2); where R 1 for ;R 2 for ;R 3 It is a methyl group.

[0067] Application Example 1 This application example provides a cationic silicone wax emulsion, the preparation method of which includes the following steps: 20g of self-emulsifying cationic silicone wax (ZG1) obtained in Example 1 and 3g of dipropylene glycol methyl ether are mixed and heated to 80°C until completely dissolved. Then, 25g of deionized water at 80°C is added under high-speed stirring. After the addition is complete, high-speed shearing is continued for 30min to obtain the silicone wax emulsion.

[0068] Application Examples 2-7 differ from Application Example 1 only in that the self-emulsifying silicone wax used in Application Examples 2-7 is the self-emulsifying silicone wax (ZG2-ZG7) prepared in Examples 2-7 respectively.

[0069] The only difference between Comparative Examples 1-5 and Application Example 1 is that Comparative Examples 1-5 replace the self-emulsifying silicone wax with the silicone wax obtained in Application Examples 1-5.

[0070] Performance testing was conducted on the self-emulsifying cationic silicone waxes obtained in Examples 1-7 and Comparative Examples 1-5 according to the following method: 1. Self-emulsification: 20g of the self-emulsifying cationic silicone waxes obtained in Examples 1-7 and Comparative Examples 1-5 were mixed with 3g of dipropylene glycol methyl ether and heated to 80°C until completely dissolved. Then, 25g of deionized water at 80°C was added under high-speed stirring. After the addition was complete, high-speed shearing was continued for 30min to obtain a silicone wax emulsion. The obtained silicone wax emulsion was left at room temperature for 1h, and its state was observed. The self-emulsification was rated as 1-5 based on its state, with 5 being the best, indicating that the silicone wax emulsion was a homogeneous and stable emulsion without stratification; 1 being the worst, indicating that the silicone wax emulsion had obvious stratification and could not form a stable silicone wax emulsion.

[0071] 2. The silicone wax emulsions obtained in Application Examples 1-7 and Comparative Examples 3-5 were mixed with 25g of cationic acrylate emulsion (CAE), 3g of butanetetracarboxylic acid and 24g of deionized water to obtain a cationic waterproofing agent. 6g of the cationic waterproofing agent was dissolved in 94g of deionized water to prepare a homogeneous finishing solution. Then, Application Example 2 was mixed with 25g of cationic acrylate emulsion (CAE), 3g of butanetetracarboxylic acid, 5g of fatty alcohol polyoxyethylene ether emulsifier and 19g of deionized water to obtain a cationic waterproofing agent. 6g of the cationic waterproofing agent was dissolved in 94g of deionized water to prepare a homogeneous finishing solution. The above finishing solutions were used to treat cotton fabrics according to the following process: soaping → two dips and two nips (80% of the residue) → baking (170℃×2 min). The treated fabrics were subjected to the following performance tests, and the test methods are as follows: (1) Softness test: The treated fabric was cut into 10×10 cm pieces and measured using a computer softness meter. The lower the required testing force, the better the fabric's softness. Test the softness before washing and after 10 washes. The less the softness decreases after washing, the better the softness is retained.

[0072] (2) Surface contact angle test: The surface hydrophobicity and hydrophobicity properties of the finished fabric before and after washing were tested according to GB / T 42694-2023 "Detection and evaluation of the surface anti-wetting properties of textiles - contact angle and roll-off angle method". The surface contact angle was tested before washing and after 10 washes. The smaller the change in surface contact angle after washing, the better the hydrophobicity is maintained. The change in surface contact angle was calculated according to the following formula: △Surface contact angle = (contact angle after washing - contact angle before washing) / contact angle before washing.

[0073] The specific test results are shown in Table 1. The fabric sample that was not treated with fluorine-free waterproofing emulsion was used as a blank example and compared with the fabric sample treated with cationic acrylate emulsion (CAE).

[0074] Table 1

[0075] As shown in Table 1, the self-emulsifying cationic silicone wax provided by this invention exhibits excellent self-emulsifying properties. It can be stably dispersed in water without the addition of any emulsifier, and simultaneously provides good softness and hydrophobicity, maintaining these properties even after washing. In contrast, the octadecyl silicone wax provided in Comparative Example 1 and the silicone wax provided in Comparative Example 2, lacking long-chain tertiary amine groups, do not possess self-emulsifying properties and cannot spontaneously form silicone wax emulsions in water.

[0076] Among them, self-emulsifying cationic silicone wax ZG5 exhibits the best softness. Fabrics treated with finishing solutions containing self-emulsifying cationic silicone wax ZG5 have the highest softness, more than twice that of fabrics treated with pure cationic acrylate emulsion (CAE). This phenomenon can be attributed to the high molecular weight of the silicone wax component in ZG5 and the high proportion of siloxane segments in its molecular structure, thus giving the fabric a superior soft hand feel.

[0077] After washing, the treated fabric showed only a slight decrease in softness and hydrophobicity. This is mainly because the hydroxyl groups in the silicone wax molecules provided by this invention cross-link with the fibers under the action of polycarboxylic acids, enhancing the adhesion strength. In addition, the electrostatic adsorption between the cationic groups and the fibers also improved the bonding strength. The synergistic effect of these two factors significantly enhanced the durability of the waterproofing agent. In contrast, the waterproofing performance of fabrics treated with finishing solutions containing ZG9 decreased significantly. This is because their molecules lack cationic groups, and the emulsifier introduced during the preparation process weakened the cross-linking density between the silicone wax and the fibers to some extent, resulting in a reduction in hand feel and waterproofing performance after washing. This result further demonstrates that the self-emulsifying cationic silicone wax prepared using this invention can effectively avoid the problems of decreased waterproofing and deteriorated hand feel caused by added emulsifiers, and has high practical application value.

[0078] Meanwhile, as can be seen from Comparative Example 3, when long-chain fatty acid ester segments and hydroxyl groups are not introduced, both softness and hydrophobic durability decrease.

[0079] As can be seen from Comparative Examples 4 and 5, when there are too many or too few long-chain tertiary amine segments or long-chain fatty acid ester segments, it is not possible to obtain good self-emulsifying and hydrophobic properties at the same time.

[0080] The above results demonstrate that the self-emulsifying cationic silicone wax-based fluorine-free waterproofing agent synthesized in this invention can effectively improve the waterproofness and washability of fabrics.

[0081] The applicant declares that the present invention has provided a detailed description of a self-emulsifying cationic silicone wax, its preparation method, and its application through the above embodiments. However, it should be understood that the described embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Any modifications, alterations, or equivalent substitutions made to the technical solution within the spirit and principles of the present invention, including but not limited to equivalent substitutions of raw material components, reasonable introduction of auxiliary components, and adjustments to specific process parameters, should be included within the protection scope of the present invention.

Claims

1. A self-emulsifying cationic silicone wax, characterized in that, The self-emulsifying cationic silicone wax is represented by the following average composition formula (Ⅰ): R 1 a R 2 b R 3 c SiO （4-a-b-c） / 2 (I); where R 1 It is represented by the following general formula (II): (II); where R 4 Selected from substituted or unsubstituted alkyl, aryl, and polyether groups, wherein the alkyl group is optionally interrupted by one or more oxygen atoms; each R 5 They may be the same or different, selected from straight-chain or branched alkyl groups, and have at least one R. 5 Selected from C8~C45 alkyl groups, R 2 It is represented by the following general formula (Ⅲ): (Ⅲ); where R 8 Selected from substituted or unsubstituted hydrocarbon groups; R 3 * indicates an organic group; * indicates the connection position; a is 0.01~0.5, b is 0.05~0.5, and c is 1.4~2.

5.

2. The self-emulsifying cationic silicone wax according to claim 1, characterized in that, The raw materials for preparing the self-emulsifying cationic silicone wax include: epoxy-modified polysiloxane, long-chain alkyl fatty acids, long-chain alkyl tertiary amines, organic acids, and optionally an esterification catalyst; the long-chain alkyl fatty acids have a C8-C45 long carbon chain; preferably, the long-chain alkyl fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, creosotenic acid, oleic acid, linoleic acid, erucic acid, palmitoleic acid, ricinoleic acid, α-linolenic acid, γ-linolenic acid, and eicosapentaene. The long-chain alkyl tertiary amine comprises one or more of the following: acid and docosahexaenoic acid; the long-chain alkyl tertiary amine has a C8-C45 long carbon chain; preferably, the long-chain alkyl tertiary amine comprises one or more of the following: trioctylamine, tridecylamine, tri(dodecyl)amine, dodecyldimethylamine, di(dodecyl)methylamine, di(tetradecyl)methylamine, di(hexadecyl)methylamine, di(octadecyl)methylamine, decyldimethylamine, dodecyldimethylamine, and tetradecyldimethylamine.

3. The self-emulsifying cationic silicone wax according to claim 1, characterized in that, The molar ratio between the epoxy-modified polysiloxane and the long-chain alkyl fatty acid is 1:(1.1~30).

4. The self-emulsifying cationic silicone wax according to claim 1, characterized in that, The molar ratio between the total number of moles of the long-chain alkyl fatty acid and the long-chain alkyl tertiary amine and the number of epoxy groups contained in the epoxy-modified polysiloxane is 1:(0.9~1.1); preferably, the molar ratio between the long-chain alkyl fatty acid and the long-chain alkyl tertiary amine is 1:(0.5~1.3).

5. A method for preparing a self-emulsifying cationic silicone wax according to any one of claims 1 to 4, characterized in that, The preparation method includes the following steps: S1. Obtaining epoxy-modified polysiloxane by reacting hydrogen-containing polysiloxane and alkenyl epoxy compound under the action of hydrosilylation catalyst; S2. Reacting the epoxy-modified polysiloxane, long-chain alkyl fatty acid and optionally esterification catalyst to obtain epoxy-containing silicone wax; S3. Reacting the epoxy-containing silicone wax obtained in step S2, long-chain tertiary alkyl amine and organic acid to obtain soft hydrophobic self-emulsifying cationic silicone wax.

6. The preparation method according to claim 5, characterized in that, In step S1, the molar ratio between the hydrogen-containing polysiloxane and the alkenyl epoxy compound is 1:(2.1~45); preferably, the molar ratio between the long-chain alkyl fatty acid and the alkenyl epoxy compound is 1:(1.2~3); preferably, the molar ratio between the long-chain alkyl fatty acid and the alkenyl epoxy compound is 1:(1.4~2.6).

7. The preparation method according to claim 5, characterized in that, In step S3, the molar ratio between the epoxy-containing silicone wax, the long alkyl chain tertiary amine, and the organic acid is 1:(1.1~30):(1.1~32).

8. The preparation method according to claim 5, characterized in that, In step S2, the reaction temperature is 70~150℃ and the reaction time is 5~24 h; preferably, in step S3, the reaction temperature is 40~100℃ and the reaction time is 1~16 h.

9. The application of a self-emulsifying cationic silicone wax as described in any one of claims 1-5 or a self-emulsifying cationic silicone wax fluorine-free waterproofing agent prepared according to the preparation method described in any one of claims 6-8 in the fields of daily chemicals, textiles, leather, or coatings.

10. A silicone wax emulsion, characterized in that, It includes self-emulsifying silicone wax, co-solvent, and water; the self-emulsifying silicone wax includes the self-emulsifying cationic silicone wax according to any one of claims 1-5 or the self-emulsifying cationic silicone wax obtained by the preparation method according to any one of claims 6-8; preferably, the mass ratio between the self-emulsifying silicone wax and the co-solvent and water is (15~30):(15~50):(1~5).

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