A silicone wax, a silicone wax emulsion, and a method for preparing and using the same

Abstract

The application discloses a kind of organic silicon wax, silicon wax emulsion and its preparation method and application.The preparation raw materials of the organic silicon wax include: hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, alpha-olefin, platinum gold catalyst, bisulfite.The application adopts alkenyl epoxy compound, allyl polyether, alpha-olefin and hydrogen-containing polysiloxane to carry out silicon hydrogen addition reaction, further through the ring-opening sulfonation reaction of bisulfite and epoxy group, introduce hydroxyl sulfonate structure side chain, polyether side chain and long alkyl side chain on polysiloxane main chain, synergistic effect of three, obtain the organic silicon wax with excellent self-emulsifying performance, can be effectively dispersed in aqueous system, and when being used for fabric waterproof finishing, can give consideration to high waterproof grade, excellent washability and soft hand feeling.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon material technology, specifically relating to an organosilicon wax, a silicone wax emulsion, its preparation method, and its application. Background Technology

[0002] In the field of waterproof finishing of textiles, as environmental regulations impose increasingly stringent restrictions on perfluorinated compounds (PFCs), the market demand for fluorine-free waterproofing agents continues to grow. Among them, silicone waxes have become an important research direction for achieving fluorine-free waterproof finishing due to their low surface tension, excellent film-forming properties, and good hand feel.

[0003] Existing silicone waxes, when applied to fluorine-free waterproofing technologies, still have certain shortcomings in terms of waterproofing, washability, and hand feel balance. Chinese patent application CN106220856A discloses a rosin-modified silicone wax, utilizing the rigidity and crystallinity of rosin's ternary phenanthrene rings to improve waterproofing and adhesion. However, the rigid structure of rosin restricts the mobility of molecular chain segments, making it difficult to fully contact the fiber surface, resulting in limited improvement in washability of cotton and other fiber fabrics. Furthermore, the finished fabric has a stiff hand feel, affecting wearing comfort. Chinese patent application CN114541148A discloses a blocked isocyanate-modified silicone wax. By introducing blocked isocyanate groups, the silicone wax can covalently bond with fibers or crosslinking agents under baking conditions, significantly improving the washability of the waterproofing agent and providing a better soft and smooth hand feel while reducing scratches. However, this silicone wax molecule lacks a hydrophilic structure, making self-emulsification difficult and significantly limiting its application in aqueous systems.

[0004] Therefore, developing a hydrophilic silicone wax with excellent self-emulsifying properties that can also achieve high water resistance, washability, and a soft feel would have greater application advantages in the field of fluorine-free waterproof finishing. Summary of the Invention

[0005] To overcome the shortcomings of the existing technology, the present invention aims to provide an organosilicon wax with excellent self-emulsifying properties, suitable for fluorine-free waterproof finishing, which can balance high waterproof rating, excellent washability and soft hand feel.

[0006] In a first aspect, the present invention provides an organosilicon wax, the raw materials for which are prepared include: (a) Hydrogen-containing polysiloxanes; (b) Alkenyl epoxy compounds; (c) Allyl polyether; (d) α-olefins; (e) Platinum catalyst; (f) Bisulfite.

[0007] Furthermore, the molar ratio of the hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, α-olefin, and platinum catalyst is 1:(3~10):(5~20):(18~35):(10) -7 ~10 -4 ).

[0008] Furthermore, the molar ratio of the bisulfite to the alkenyl epoxy compound is 1:(0.8~1.0).

[0009] Preferably, the number-average molecular weight of the hydrogen-containing polysiloxane is 3000~15000 g / mol (e.g., any value from 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000 or a range between the two), and the hydrogen content is 0.3%~1.2% (e.g., any value from 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2% or a range between the two). More preferably, the number-average molecular weight of the hydrogen-containing polysiloxane is 4500~12000 g / mol, and the hydrogen content is 0.5%~0.8%.

[0010] The alkenyl epoxy compound is a compound whose molecular structure contains both an alkenyl group and a terminal epoxy group. Its alkenyl group can undergo a hydrosilylation reaction with the silane-hydrogen bond of a hydrogen-containing polysiloxane, introducing an epoxy-containing side chain into the siloxane backbone and providing an active site for subsequent ring-opening sulfonation reactions. Preferably, the alkenyl epoxy compound is selected from any one of allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, glycidyl methacrylate, and glycidyl acrylate; more preferably, the alkenyl epoxy compound is selected from any one of allyl glycidyl ether, 2-methyl allyl glycidyl ether, and vinyl glycidyl ether.

[0011] The allyl polyether undergoes a hydrosilylation reaction with the alkenyl group and the hydrogen siloxane via silane-hydrogen bonds, introducing polyether side chains into the siloxane backbone. Preferably, the allyl polyether is selected from any one of allyl polyoxyethylene ether, allyl polyoxypropylene ether, and allyl polyoxyethylene-polyoxypropylene copolyether. Further, the number average molecular weight of the allyl polyether is preferably 300-600 g / mol. This invention selects to introduce a certain amount of short-chain polyether, which can form more uniform and stable hydrophilic points, avoid localized excessive hydrophilicity, and reduce physical interference with the hydrophobic crystallization region of the long-chain alkyl groups, thus facilitating the formation of a dense waterproof barrier; moreover, it has less impact on the flexibility of the main chain, better preserving the soft and slippery properties of silicone oil.

[0012] The α-olefin undergoes a hydrosilylation reaction with the alkenyl group and the hydrogen siloxane via a silane-hydrogen bond, introducing a long-chain alkyl side chain into the siloxane backbone. Further, the α-olefin is preferably at least one of straight-chain α-olefins having 22 to 40 carbon atoms; more preferably at least one of straight-chain α-olefins having 26 to 35 carbon atoms.

[0013] This invention introduces sulfonate groups by undergoing a ring-opening sulfonation reaction between bisulfite and epoxy groups. The introduction of an appropriate amount of hydroxysulfonate-containing side chains improves hydrophilicity and, synergistically with polyether side chains, allows the silicone wax to maintain excellent self-emulsifying properties while ensuring water resistance through the introduction of high-carbon-number, long alkyl chains. Furthermore, it forms strong ionic / hydrogen bonds with fabric fibers, further enhancing wash resistance.

[0014] Preferably, the bisulfite is selected from any one of sodium bisulfite, magnesium bisulfite, and potassium bisulfite.

[0015] Preferably, the platinum catalyst can be a conventional platinum-based catalyst such as a Karstedt catalyst, a Speier catalyst, or a MOF-modified Karstedt catalyst.

[0016] Furthermore, depending on the actual application requirements, a small amount of auxiliary components such as antioxidants, anti-yellowing agents, and dispersants can be added. The amount added is 0.01~0.5% of the total mass of the core components, preferably 0.05~0.3%, to further improve the product's resistance to yellowing and storage stability without affecting the product's core performance and reactivity.

[0017] Furthermore, the melting point of the silicone wax of the present invention is 45~70℃, preferably 50~65℃; the number-average molecular weight of the silicone wax is 10000~30000 g / mol. The melting point is determined with reference to standard GB / T 2539-2023; the number-average molecular weight is determined with reference to standard GB / T 27843-2011.

[0018] Secondly, the present invention provides a method for preparing the aforementioned organosilicon wax, comprising the following steps: S1. Under inert gas protection, hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, α-olefin and platinum catalyst are mixed and subjected to hydrosilylation reaction at 70~130℃ for 2~10 h to obtain epoxy-polyether-long-chain alkyl modified polysiloxane. S2. The product obtained in step S1 and the bisulfite are added to a mixture of propylene glycol methyl ether and water, and a ring-opening sulfonation reaction is carried out at 60~110℃ for 3~24h. After the reaction is completed, the mixture is filtered while hot, and the filtrate is distilled under reduced pressure to obtain the organosilicon wax.

[0019] Furthermore, the mass ratio of propylene glycol methyl ether to water is (25~35):1.

[0020] Furthermore, the amount of propylene glycol methyl ether and water used is 20% to 50% of the total mass of the reactants.

[0021] Thirdly, the present invention provides a silicone wax emulsion comprising, by weight percentage, the following components: The organosilicon wax mentioned in the first aspect is 15%~35%; Stabilizer 1%~5%; Preservatives: 0.1%~2%; Deionized water balance.

[0022] Preferably, the stabilizer is selected from at least one of stearates. The stearates include at least one of aluminum stearate, calcium stearate, magnesium stearate, and sodium stearate.

[0023] Preferably, the preservative is selected from at least one of phenoxyethanol and 1,2-benzisothiazolin-3-one. More preferably, the preservative is phenoxyethanol and 1,2-benzisothiazolin-3-one in a mass ratio of (1.5-3):1.

[0024] The present invention provides a method for preparing the silicone wax emulsion, comprising the following steps: heating organosilicon wax until completely dissolved, adding deionized water under high-speed stirring, then continuing high-speed shearing, then reducing the speed and adding stabilizer and preservative in sequence, and continuing to stir evenly to obtain silicone wax emulsion.

[0025] Fourthly, the present invention provides the application of the aforementioned organosilicone wax or silicone wax emulsion in the fields of textiles, leather, and coatings.

[0026] Fifthly, the present invention provides a fluorine-free waterproofing agent, comprising the organosilicone wax as described in the first aspect or the silicone wax emulsion as described in the third aspect.

[0027] Furthermore, the fluorine-free waterproofing agent, by weight percentage, comprises the following components: The organosilicon wax mentioned in the first aspect is 15%~30%; Anionic waterborne polyurethane resin 20%~35%; Emulsifier 0~6%; Cosolvent 1%~5%; Crosslinking agent 1%~5%; Deionized water balance.

[0028] In the fluorine-free waterproofing agent of the present invention, the emulsifier, co-solvent, and crosslinking agent can be corresponding additives conventional in the art. Preferably: The emulsifier is selected from at least one of anionic and nonionic emulsifiers. The anionic emulsifier may be selected from sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, etc.; the nonionic emulsifier may be selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. In practical use, it is preferred to use a combination of anionic and nonionic emulsifiers to obtain better emulsion stability.

[0029] The co-solvent may be selected from at least one of alcohol ether solvents and alcohol solvents. The alcohol ether solvents include dipropylene glycol methyl ether, propylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, etc.; the alcohol solvents include isopropanol, n-butanol, ethylene glycol, propylene glycol, etc. The present invention preferably uses dipropylene glycol methyl ether.

[0030] The crosslinking agent can be selected from any one of blocked isocyanate crosslinking agents, aziridine crosslinking agents, carbodiimide crosslinking agents, and epoxy silane coupling agents. The present invention preferably uses blocked isocyanate crosslinking agents.

[0031] This invention provides a method for preparing the fluorine-free waterproofing agent, comprising the following steps: S1. Mix the silicone wax and cosolvent, heat until completely dissolved, then add the emulsifier and stir evenly. Then, under stirring conditions, add water accounting for 30% to 70% of the total weight of water and continue stirring to obtain a silicone wax emulsion. S2. Add the silicone wax emulsion obtained in step S1 to the anionic waterborne polyurethane resin, crosslinking agent and remaining water, mix evenly to prepare the fluorine-free waterproofing agent.

[0032] Compared with the prior art, the present invention has the following beneficial effects: This invention employs an alkenyl epoxy compound, allyl polyether, α-olefin, and hydrogen-containing polysiloxane to undergo a hydrosilylation reaction. Further, a ring-opening sulfonation reaction is carried out between bisulfite and epoxy groups, introducing a certain number of hydroxyl sulfonate side chains, polyether side chains, and long alkyl side chains onto the polysiloxane backbone. These three components synergistically enhance the effect, resulting in an organosilicone wax with excellent self-emulsifying properties. It can be effectively dispersed in aqueous systems and, when used for waterproof finishing of fabrics, can simultaneously achieve high waterproof ratings, excellent washability, and a soft hand feel.

[0033] The organosilicon wax of this invention has anionic properties and good compatibility with anionic or nonionic polymer resins, thus broadening the application range of organosilicon wax in the field of fabric finishing. Moreover, its preparation method is simple and the reaction conditions are mild. It adopts a one-pot hydrosilylation reaction to simultaneously introduce three functional side chains, and then obtains the target product through a ring-opening sulfonation reaction. It is suitable for large-scale industrial production, with controllable costs, and has good economic benefits and market competitiveness. Attached Figure Description

[0034] Figure 1 The infrared spectrum of hydrophilic modified organosilicon wax I in Example 1; Figure 2 The infrared spectrum of hydrophilic modified organosilicon wax II in Example 2; Figure 3 The infrared spectrum of hydrophilic modified silicone wax III in Example 3 is shown. Detailed Implementation

[0035] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0036] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0037] Unless otherwise specified, room temperature or normal temperature in the embodiments of the present invention refers to 25±1°C. Example 1

[0038] This embodiment provides an organosilicon wax, the preparation method of which is as follows: S1. Under nitrogen protection, a methyl-terminated hydrogen-containing polysiloxane (number-average molecular weight approximately 5500 g / mol, hydrogen content 0.76%) was added to a reactor. The temperature was raised to 80°C, and a mixture of allyl glycidyl ether, allyl polyoxyethylene ether (number-average molecular weight 410 g / mol), and 1-triatoene was slowly added dropwise. Simultaneously, a Karstedt catalyst was added and mixed. The temperature was raised to 110°C, and the reaction was maintained at this temperature for 8 hours to obtain epoxy-polyether-long-chain alkyl-modified polysiloxane A1. The molar ratio of the hydrogen-containing polysiloxane, allyl glycidyl ether, allyl polyoxyethylene ether, 1-triatoene, and Karstedt catalyst was 1:5:12:25:10. -6 ; S2. Add sodium bisulfite to the reactor, and add 30% of the total material mass of propylene glycol methyl ether-water mixed solvent (the mass ratio of propylene glycol methyl ether to water is 30:1). Heat to 80℃ and react at this temperature for 12 h. After the reaction is complete, filter while hot to remove a small amount of impurities. Remove the solvent from the filtrate by vacuum distillation to obtain organosilicon wax I, with a melting point of 62℃ and a number-average molecular weight of 23540 g / mol.

[0039] The infrared spectrum of the organosilicon wax I prepared in this embodiment is as follows: Figure 1 As shown. Example 2

[0040] This embodiment provides an organosilicon wax, the preparation method of which is as follows: S1. Under nitrogen protection, hydrogen-containing polysiloxane (number-average molecular weight approximately 8000 g / mol, hydrogen content 0.68%) was added to a reactor, and the temperature was raised to 80°C. A mixture of allyl glycidyl ether, allyl polyoxyethylene-polyoxypropylene block copolymer ether (EO:PO = 2:1; number-average molecular weight 350 g / mol), and 1-hexadecene was slowly added dropwise, along with Karstedt catalyst. The mixture was then heated to 110°C and reacted at this temperature for 8 hours to obtain epoxy-polyether-long-chain alkyl-modified polysiloxane A2. The molar ratio of hydrogen-containing polysiloxane, allyl glycidyl ether, allyl polyoxyethylene ether, 1-hexadecene, and Karstedt catalyst was 1:8:15:32:10. -5 ; S2. Add sodium bisulfite to the reactor, and add 30% of the total material mass of a propylene glycol methyl ether-water mixed solvent (the mass ratio of propylene glycol methyl ether to water is 30:1). Heat to 80℃ and react at this temperature for 14 h. After the reaction is complete, filter while hot to remove a small amount of impurities. Remove the solvent from the filtrate by vacuum distillation to obtain organosilicon wax II, with a melting point of 55℃ and a number-average molecular weight of 26780 g / mol.

[0041] The infrared spectrum of the organosilicon wax II prepared in this embodiment is as follows: Figure 2 As shown. Example 3

[0042] The only difference between this embodiment and Example 1 is that 1-triacontene in the raw materials is replaced by 1-eicosadiene in equal amounts; all other aspects are the same as in Example 1. Organosilicon wax III is obtained with a melting point of 46°C and a number-average molecular weight of 19460 g / mol.

[0043] The infrared spectrum of the organosilicon wax III prepared in this embodiment is as follows: Figure 3 As shown.

[0044] Comparative Example 1 This comparative example provides an organosilicon wax, the preparation method of which is as follows: S1. Under nitrogen protection, a methyl-terminated hydrogen-containing polysiloxane (number-average molecular weight approximately 5500 g / mol, hydrogen content 0.76%) was added to a reaction vessel. The temperature was raised to 80°C, and a mixture of allyl glycidyl ether and 1-triatoene was slowly added dropwise, along with Karstedt catalyst. The mixture was then heated to 110°C and reacted at this temperature for 8 hours to obtain an epoxy-long-chain alkyl-modified polysiloxane. The molar ratio of the hydrogen-containing polysiloxane, allyl glycidyl ether, 1-triatoene, and Karstedt catalyst was 1:17:25:10. -6 ; S2. Add sodium bisulfite to the reactor, and add 30% of the total material mass of propylene glycol methyl ether-water mixed solvent (the mass ratio of propylene glycol methyl ether to water is 30:1). Heat to 80℃ and react at this temperature for 12 h. After the reaction is complete, filter while hot to remove a small amount of impurities. Remove the solvent from the filtrate by vacuum distillation to obtain organosilicon wax IV.

[0045] Comparative Example 2 This comparative example provides an organosilicon wax, the preparation method of which is as follows: S1. Under nitrogen protection, methyl-terminated hydrogen-containing polysiloxane (number average molecular weight approximately 5500 g / mol, hydrogen content 0.76%) was added to a reactor. The temperature was raised to 80°C, and a mixture of allyl polyoxyethylene ether (number average molecular weight 410 g / mol) and 1-triatoene was slowly added dropwise, along with Karstedt catalyst. The mixture was then heated to 110°C and reacted at this temperature for 8 hours. The molar ratio of hydrogen-containing polysiloxane, allyl polyoxyethylene ether, 1-triatoene, and Karstedt catalyst was 1:17:25:10. -6 After the reaction is complete, the temperature is lowered to room temperature, and the mixture is filtered to remove a small amount of impurities, yielding organosilicon wax V.

[0046] Comparative Example 3 This comparative example provides an organosilicon wax, the preparation method of which is as follows: S1. Under nitrogen protection, a methyl-terminated hydrogen-containing polysiloxane (number-average molecular weight approximately 5500 g / mol, hydrogen content 0.76%) was added to a reactor. The temperature was raised to 80°C, and a mixture of allyl-terminated epoxy polyoxyethylene ether (number-average molecular weight 460 g / mol) and 1-triatoene was slowly added dropwise, along with Karstedt catalyst. The mixture was then heated to 110°C and reacted at this temperature for 8 hours to obtain a polyether epoxy-long-chain alkyl-modified polysiloxane. The molar ratio of the hydrogen-containing polysiloxane, allyl-terminated epoxy polyoxyethylene ether, 1-triatoene, and Karstedt catalyst was 1:17:25:10. -6 ; S2. Add sodium bisulfite and 30% by mass of propylene glycol methyl ether-water mixed solvent (mass ratio of propylene glycol methyl ether to water is 30:1) to the reaction vessel, heat to 80℃ and react at a constant temperature for 12 h. After the reaction is complete, filter while hot to remove a small amount of impurities, and remove the solvent by vacuum distillation of the filtrate to obtain organosilicon wax VI.

[0047] The silicone waxes from Examples 1-3 were used to prepare silicone wax emulsions: 25 parts by weight of silicone wax were heated to 80°C until completely dissolved. 70.5 parts by weight of deionized water at 80°C were added under high-speed stirring, followed by high-speed shearing for 30 minutes. Then, the stirring speed was reduced, and 3 parts by weight of aluminum stearate, 1.0 part by weight of phenoxyethanol, and 0.5 parts by weight of 1,2-benzisothiazolin-3-one were added sequentially, with stirring continued for 30 minutes to obtain the silicone wax emulsion. The obtained silicone wax emulsions were left at room temperature for 24 hours, and the emulsion state was observed. The results are shown in Table 1.

[0048] Table 1. State of silicone wax emulsions prepared in Examples 1-3

[0049] Application Example 1 The silicone waxes used in the examples and comparative examples were used to prepare fluorine-free waterproofing agents. The formulations of the fluorine-free waterproofing agents are as follows (by mass percentage): 22% silicone wax; Anionic waterborne polyurethane resin (Dolphin 1352, Guangzhou Dolphin New Materials) 28%; Sodium dodecylbenzenesulfonate 2%; 3% dipropylene glycol methyl ether; Blocked HDI trimer (HTBL-175S, Wanhua Chemical) 2%; Deionized water 43%.

[0050] Preparation steps: According to the formula, mix organosilicon wax and dipropylene glycol methyl ether, heat to 80°C until completely dissolved, then add sodium dodecylbenzene sulfonate and stir evenly. Then, under stirring conditions, add water accounting for 50% of the total weight of water and continue stirring for 30 minutes to obtain silicone wax emulsion. Then add anionic waterborne polyurethane resin, blocked HDI trimer and the remaining water, mix evenly, and prepare fluorine-free waterproofing agent.

[0051] The fluorine-free waterproofing agent obtained from the application example was mixed with deionized water at a mass ratio of 10:90 to prepare a finishing solution, which was then used to treat pure cotton woven fabric (weight 120 g / m²) according to the following process. 2 The treatment process included soaping, two dips and two nips (80% pick-up), and baking (170℃, 2 min). The treated fabric underwent the following performance tests: 1. Water resistance: The water repellency rating of the fabric is tested in accordance with standard GB / T 4745-2012.

[0052] 2. Softness: Cut the treated fabric into 10 cm * 10 cm samples and measure them using a computerized softness meter. The lower the required test force (mN), the better the softness of the fabric.

[0053] 3. Washability: Ten standard washing cycles were performed according to standard ISO105-C04, and the water resistance and softness were tested before and after washing.

[0054] The test results are shown in Table 2.

[0055] Table 2 Performance test results of fluorine-free waterproofing agents in application examples

[0056] As can be seen from the above results, the organosilicon wax of the present invention introduces a certain number of hydroxy sulfonate-containing side chains, polyether side chains and long alkyl side chains on the polysiloxane main chain. The three synergistic effects result in excellent self-emulsifying properties, can be effectively dispersed in aqueous systems, and can take into account high waterproof rating, excellent washability and soft hand feel when used for waterproof finishing of fabrics.

[0057] Compared with the silicone wax IV used in Application Example 1, which lacks polyether side chains, has poor self-emulsification ability and is difficult to disperse evenly in an aqueous system, resulting in discontinuous film formation, poor initial water resistance, poor softness, and poor washability. After washing tests, the water repellency and softness changed significantly.

[0058] Compared to the silicone wax V used in Application Example 2, which does not contain sulfonate side chains, its washability is significantly insufficient, and its water resistance and softness change significantly after washing tests.

[0059] In contrast, the sulfonate structure of silicone wax VI used in application example 3 is located at the end of the polyether chain, and the two affect each other in terms of steric hindrance, resulting in poor water resistance, softness and washability.

Claims

1. An organosilicon wax, characterized in that, The raw materials for preparing the organosilicon wax include: (a) Hydrogen-containing polysiloxanes; (b) Alkenyl epoxy compounds; (c) Allyl polyether; (d) α-olefins; (e) Platinum catalyst; (f) Bisulfite.

2. The organosilicon wax according to claim 1, characterized in that, The hydrogen-containing polysiloxane has a number-average molecular weight of 3000~15000 g / mol and a hydrogen content of 0.3%~1.2%; the alkenyl epoxy compound is selected from any one of allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, glycidyl methacrylate, and glycidyl acrylate; the bisulfite is selected from any one of sodium bisulfite, magnesium bisulfite, and potassium bisulfite; the allyl polyether is selected from any one of allyl polyoxyethylene ether, allyl polyoxypropylene ether, and allyl polyoxyethylene-polyoxypropylene copolyether; the allyl polyether has a number-average molecular weight of 300~600 g / mol.

3. The organosilicon wax according to claim 1, characterized in that, The α-olefin is selected from at least one of straight-chain α-olefins having 22 to 40 carbon atoms; preferably, the α-olefin is selected from at least one of straight-chain α-olefins having 26 to 35 carbon atoms.

4. The organosilicon wax according to claim 1, characterized in that, The molar ratio of the hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, α-olefin, and platinum catalyst is 1:(3~10):(5~20):(18~35):(10) -7 ~10 -4 ); The molar ratio of the bisulfite to the alkenyl epoxy compound is 1:(0.8~1.0).

5. The organosilicon wax according to claim 1, characterized in that, The melting point of the silicone wax is 45~70℃; the number average molecular weight of the silicone wax is 10000~30000g / mol.

6. The method for preparing organosilicon wax according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Under inert gas protection, hydrogen-containing polysiloxane, alkenyl epoxy compound, allyl polyether, α-olefin and platinum catalyst are mixed and subjected to hydrosilylation reaction at 70~130℃ for 2~10 h to obtain epoxy-polyether-long-chain alkyl modified polysiloxane. S2. The product obtained in step S1 and the bisulfite are added to a mixture of propylene glycol methyl ether and water, and a ring-opening sulfonation reaction is carried out at 60~110℃ for 3~24h. After the reaction is completed, the mixture is filtered while hot, and the filtrate is distilled under reduced pressure to obtain the organosilicon wax.

7. A silicone wax emulsion, characterized in that, By mass percentage, it includes the following components: The organosilicon wax according to any one of claims 1 to 5 comprises 15% to 35%; Stabilizer 1%~5%; Preservatives: 0.1%~2%; Deionized water balance.

8. The application of the organosilicone wax according to any one of claims 1 to 5, and the silicone wax emulsion according to claim 7, in the fields of textiles, leather, and coatings.

9. A fluorine-free waterproofing agent, characterized in that, Includes the organosilicone wax as described in any one of claims 1 to 5 or the silicone wax emulsion as described in claim 7.

10. The fluorine-free waterproofing agent according to claim 9, characterized in that, The fluorine-free waterproofing agent comprises the following components by weight percentage: The silicone wax according to any one of claims 1 to 5 comprises 15% to 30%; Anionic waterborne polyurethane resin 20%~35%; Emulsifier 0~6%; Cosolvent 1%~5%; Crosslinking agent 1%~5%; Deionized water balance.

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