Block type quaternary ammonium salt organic silicone oil as well as preparation method and application thereof

Abstract

The invention relates to the technical field of high polymer material synthesis and fine chemical engineering, in particular to block type quaternary ammonium salt organic silicone oil as well as a preparation method and application thereof. The preparation method comprises the following steps: dispersing end hydrogen-containing silicone oil and N-methylallylamine in a solvent to carry out hydrosilylation reaction, and then adding 2, 3-epoxypropyl trimethyl ammonium chloride to carry out epoxy ring-opening reaction to prepare the block type quaternary ammonium salt organic silicone oil. The preparation process is relatively simple and convenient, the preparation conditions are relatively simple, a simple two-step method is adopted for preparation, an inert gas atmosphere is not needed, and reaction preparation can be performed in an air atmosphere, so that the preparation risk is reduced. The prepared block type quaternary ammonium salt organic silicone oil is good in emulsion effect and better in thermal stability, can be effectively applied to after-finishing of fabrics, and enables the fabrics to have excellent softness, yellowing resistance and staphylococcus aureus resistance. The antibacterial softening agent is used for finishing fabrics and has the advantages of being good in softening effect, not prone to yellowing and resistant to staphylococcus aureus.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material synthesis and fine chemical industry, and in particular to a block-type quaternary ammonium salt organic silicone oil, a preparation method thereof and an application thereof. Background Art

[0002] Silicone softeners offer superior performance, outstanding results, and a wide range of applications. These materials are non-toxic, environmentally friendly, and low-cost, making them suitable for finishing a wide range of textiles (natural fibers, synthetic fibers, blends, etc.), and they hold broad application prospects. Silicone softeners originated in the 1950s and have now reached their fourth stage: block-modified silicone oils. These have significantly improved softness, washability, and elasticity, meeting diverse user demands for fabrics and becoming the mainstream direction of silicone softener development. Amino-modified block silicone oils are the most common, but the presence of highly active hydrogen in the amino group can lead to yellowing when applied to light-colored fabrics under high temperatures or UV exposure.

[0003] Staphylococcus aureus is a major pathogen causing common human infections. It is usually transmitted through direct human contact and contact with contaminated objects (such as clothing, telephones, doorknobs, TV remote controls, or elevator buttons). Clothing contact is a major route of infection, and clothing's resistance to Staphylococcus aureus plays an important role in preventing skin infections. Cotton fabric is the textile fabric most frequently touched by humans. Under suitable conditions, the glucose residues on cotton fibers can provide energy for the growth and reproduction of microorganisms, which can potentially lead to the production of pathogens. This is one of the main reasons why people become ill due to bacterial infections through contact with clothing. Therefore, during the fabric finishing process, attention should be paid not only to imparting a pleasant skin feel, whiteness, and smoothness, but also to the fabric's antibacterial properties.

[0004] Current research on antibacterial fabric finishing agents primarily includes natural compounds, inorganic materials (metal ions), nanomaterials, and quaternary ammonium salts. Quaternary ammonium salts are cationic surfactants that utilize their positive charge to electrostatically bind to bacterial surfaces. This binding can disrupt bacterial membrane structure and interfere with cell wall synthesis, ultimately leading to bacterial death. Furthermore, amino-modified long-chain polysiloxanes can impart a smooth and soft feel to cotton fabrics.

[0005] In the prior art, Chinese patent application CN115262212A discloses a method for wrinkle-resistant and antibacterial finishing of cotton fabrics based on an organosilicon resin. This method aims to provide a method for wrinkle-resistant and antibacterial finishing of cotton fabrics based on an organosilicon resin. The finished cotton fabric achieves excellent wrinkle-resistant and antibacterial properties, and is endowed with high tensile strength, wash resistance, and a smooth skin feel. The preparation method comprises first dissolving ethylaminodiethylmercaptan and bromopropane in an ethanol solution, heating and refluxing the solution under magnetic stirring to prepare a bis-mercapto-functionalized quaternary ammonium salt; then dissolving the resulting bis-mercapto-functionalized quaternary ammonium salt in N,N-dimethylformamide, adding a catalyst DMPA and a vinyl-functionalized organosiloxane, and subjecting the resulting quaternary ammonium salt-functionalized double-headed siloxane precursor to a catalytic reaction. The precursor is then dissolved in acetone with a photobase initiator, mixed to form a homogeneous mixed solution, and then evenly impregnated into the interior of cleaned cotton fabric through a dipping process; the resulting mixture is then transferred to ultraviolet light for crosslinking. However, its preparation method is relatively complicated. The preparation process is divided into five steps, using a large number of raw materials and three solvents, and cross-linking with the fabric under specific ultraviolet light. The overall process is not simple enough. Summary of the Invention

[0006] In order to overcome the deficiencies of the prior art, the first object of the present invention is to provide a block type quaternary ammonium salt silicone oil, which has the advantages of good softening effect, not easy to turn yellow and having resistance to Staphylococcus aureus when used to finish fabrics.

[0007] A second object of the present invention is to provide a method for preparing a block-type quaternary ammonium salt silicone oil. The preparation process of the preparation method is relatively simple, the preparation conditions are relatively simple, and the preparation can be carried out by a simple two-step method. No inert gas atmosphere is required, and the reaction preparation can be carried out in an air atmosphere, thereby reducing the risk of its preparation.

[0008] The third object of the present invention is to provide a fabric softening, anti-yellowing and antibacterial finishing emulsion, which, when used for fabric finishing, can greatly improve the softness, anti-yellowing effect and anti-Staphylococcus aureus effect of the fabric.

[0009] The fourth object of the present invention is to provide a method for preparing a fabric softening, anti-yellowing and antibacterial finishing emulsion.

[0010] A fifth object of the present invention is to provide an antibacterial softener, which has the advantages of good softening effect, low yellowing and resistance to Staphylococcus aureus when used for finishing fabrics.

[0011] A sixth object of the present invention is to provide a method for preparing an antibacterial softener.

[0012] In order to achieve the first object of the above invention, the technical solution adopted by the present invention is as follows:

[0013] The present invention provides a block-type quaternary ammonium salt organic silicone oil having a chemical structure as shown in Formula I:

[0014]

[0015] Wherein, n is an integer.

[0016] The block type quaternary ammonium salt organic silicone oil of the present invention can be used for softening, anti-yellowing and antibacterial finishing of fabrics, so that the finished fabrics have the advantages of good softening effect, low yellowing and resistance to Staphylococcus aureus.

[0017] In order to achieve the second purpose of the above invention, the technical solution adopted by the present invention is as follows:

[0018] Provided is a method for preparing a block-type quaternary ammonium salt organic silicone oil, comprising the following steps: S1, dispersing terminal hydrogen-containing silicone oil and N-methylallylamine in a solvent, heating the solvent in an air atmosphere, and then adding a catalyst to carry out a hydrosilylation reaction to obtain a preliminary block-structured organic silicone oil;

[0019] S2. Add 2,3-epoxypropyltrimethylammonium chloride to the system in step S1, and continue heating under air atmosphere to perform epoxy ring-opening reaction, thereby obtaining the block quaternary ammonium salt silicone oil.

[0020] The present invention discloses a method for preparing a block-type quaternary ammonium salt organosilicone oil. The method comprises dispersing a hydrogen-terminated silicone oil and N-methylallylamine in a solvent, performing a hydrosilylation reaction, and then adding 2,3-epoxypropyltrimethylammonium chloride to perform an epoxy ring-opening reaction to prepare the block-type quaternary ammonium salt organosilicone oil. The method has a relatively simple preparation process and conditions, employing a simple two-step process. No inert gas atmosphere is required; the reaction can be performed in an air atmosphere, thereby reducing the risk of the preparation. Furthermore, the prepared block-type quaternary ammonium salt organosilicone oil has a good emulsion effect and excellent thermal stability, and can be effectively used in fabric finishing, whereby the finished fabric has excellent softness, anti-yellowing properties, and anti-Staphylococcus aureus properties.

[0021] Wherein, the terminal hydrogen-containing silicone oil has the chemical structure shown in Formula II:

[0022]

[0023] Wherein, n is an integer; and / or

[0024] Furthermore, the molecular weight of the hydrogen-terminated silicone oil is 6,000 to 12,000.

[0025] Furthermore, the preliminary block structure organic silicone oil has a chemical structure as shown in Formula III:

[0026]

[0027] Wherein, n is an integer.

[0028] Furthermore, in step S1, the molar ratio of the hydrogen-terminated silicone oil to N-methylallylamine is 1:(1.6-2.4); and / or

[0029] The solvent is at least one of toluene, ethanol, isopropanol, n-butanol, or ethylene glycol monobutyl ether; the mass of the solvent accounts for 10% to 20% of the total mass of the hydrogen-terminated silicone oil and N-methylallylamine; wherein the selected solvent is easy to dissolve the reactants of the present invention, and the solvent is readily available and low in cost. The amount of the solvent used can provide a good medium environment for the reaction without wasting materials. And / or

[0030] The catalyst is a Speier catalyst; wherein the Speier catalyst is a mixture of chloroplatinic acid and isopropyl alcohol. The catalyst is added to accelerate the reaction speed, shorten the reaction time and reduce the reaction temperature, which is conducive to the progress of the hydrosilylation reaction. The mass of the catalyst is 10ppm-30ppm of the mass of the terminal hydrogenated silicone oil; the amount of the above materials can reasonably accelerate the synthesis of the preliminary block structure organic silicone oil in step S1 and save costs. And / or

[0031] The temperature of the hydrosilylation reaction is 60°C to 80°C, and the reaction time is 5h to 7h; wherein the temperature and time of the hydrosilylation reaction can make the entire reaction complete and avoid the occurrence of side reactions. And / or

[0032] The heating method of the hydrosilylation reaction is oil bath heating or electric heating; wherein oil bath heating or electric heating has a good heating effect, so that the reaction proceeds smoothly. And / or

[0033] When dispersing the hydrogen-terminated silicone oil and N-methylallylamine in the solvent, stirring is performed at a speed of 250 rpm / min to 300 rpm / min. This stirring speed can promote a uniform reaction without wasting energy.

[0034] Furthermore, in step S2, the molar ratio of the 2,3-epoxypropyltrimethylammonium chloride to the preliminary block structure silicone oil is (1.6-1.8):1; and / or

[0035] The temperature of the epoxy ring-opening reaction is 90° C. to 120° C., and the reaction time is 11 h to 15 h. The temperature and time of the epoxy ring-opening reaction can ensure that the entire reaction is complete.

[0036] After the epoxy ring-opening reaction is complete, the solvent is removed; and / or the solvent removal conditions are -0.01 MPa and 50°C to 90°C for 1 hour. Removing the solvent after the epoxy ring-opening reaction can produce a high-purity silicone oil. Furthermore, the solvent removal conditions ensure that the solvent is fully removed without affecting the structure of the silicone oil.

[0037] In order to achieve the third purpose of the above invention, the technical solution adopted by the present invention is as follows:

[0038] Provided is a fabric softening, anti-yellowing and antibacterial finishing emulsion, comprising the above-mentioned block type quaternary ammonium salt organic silicone oil or the block type quaternary ammonium salt organic silicone oil prepared by the above-mentioned method for preparing the block type quaternary ammonium salt organic silicone oil.

[0039] In order to achieve the fourth object of the above invention, the technical solution adopted by the present invention is as follows:

[0040] Provided is a method for preparing a fabric softening, anti-yellowing, and antibacterial finishing emulsion, wherein the fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following components in parts by weight:

[0041]

[0042] The emulsifier is an AEO series nonionic surfactant, and the solubilizer is ethylene glycol butyl ether. The addition of the emulsifier and solubilizer can make the emulsion used for the softening, anti-yellowing and antibacterial finishing of fabrics more uniformly dispersed and soluble.

[0043] The stabilizer is EDTA or EDTA-2Na. The addition of the stabilizer can make the fabric softening, anti-yellowing and antibacterial finishing emulsion more stable and exert good effects.

[0044] The preparation method of the fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following steps: stirring and mixing a formulated amount of a block quaternary ammonium salt organic silicone oil, an emulsifier, and a solubilizer at a rotation speed of 3000 rpm / min to 10000 rpm / min to obtain an oil phase; adding a formulated amount of a stabilizer and water to the oil phase; and dispersing and homogenizing the mixture at a rotation speed of 5000 rpm / min to 6000 rpm / min for 10 to 20 minutes; and then adjusting the pH of the system to 5 to 6, thereby obtaining the fabric softening, anti-yellowing, and antibacterial finishing emulsion.

[0045] The solid content of the fabric softening, anti-yellowing and antibacterial finishing emulsion is 15% to 30%. When used for fabric finishing, the emulsion with this solid content can well improve the softness of the fabric and the anti-Staphylococcus aureus effect.

[0046] In the method for preparing the antibacterial, anti-yellowing, and softening emulsion for fabrics, the antibacterial, anti-yellowing, and softening emulsion for fabrics is prepared after adjusting the pH of the system to 5-6 and allowing the bubbles to disappear. Furthermore, the prepared antibacterial, anti-yellowing, and softening emulsion for fabrics exhibits a milky white color.

[0047] In order to achieve the fifth purpose of the above invention, the technical solution adopted by the present invention is as follows:

[0048] Provided is an antibacterial softener, comprising the above-mentioned antibacterial finishing emulsion for softening and resisting yellowing of fabrics or the antibacterial finishing emulsion for softening and resisting yellowing of fabrics prepared by the above-mentioned preparation method of the antibacterial finishing emulsion for softening and resisting yellowing of fabrics.

[0049] The solid content of the antibacterial softener is 8g / L-30g / L, and the antibacterial softener can make the finished fabric soft, hydrophilic and anti-yellowing.

[0050] In order to achieve the sixth object of the above invention, the technical solution adopted by the present invention is as follows:

[0051] Provided is a method for preparing an antibacterial softener, the antibacterial softener comprising the following components in parts by weight:

[0052] Applied to fabric softening, anti-yellowing and antibacterial finishing emulsion 1 to 3 parts

[0053] 50 to 250 parts water;

[0054] The preparation method of the antibacterial softener comprises the following steps: diluting a formulated amount of a fabric softening, anti-yellowing, and antibacterial finishing emulsion with a formulated amount of water, and stirring the mixture evenly to obtain the antibacterial softener.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] (1) The present invention discloses a block-type quaternary ammonium salt organic silicone oil having a block structure and good stability. It can be used for soft, anti-yellowing and antibacterial finishing of fabrics, making the finished fabrics have the advantages of good softening effect, low yellowing, and resistance to Staphylococcus aureus. Moreover, when used on light-colored fabrics, it can also resist yellowing under high temperature or ultraviolet light conditions.

[0057] (2) The present invention provides a method for preparing a block-type quaternary ammonium salt organic silicone oil. The method comprises dispersing a terminal hydrogenated silicone oil and N-methylallylamine in a solvent to carry out a silylation reaction, and then adding 2,3-epoxypropyltrimethylammonium chloride to carry out an epoxy ring-opening reaction to prepare the block-type quaternary ammonium salt organic silicone oil. The preparation process of the method is relatively simple, the preparation conditions are relatively simple, and the method can be prepared by a simple two-step method. No inert gas atmosphere is required, and the reaction can be carried out in an air atmosphere, thereby reducing the risk of the preparation. The obtained block-type quaternary ammonium salt organic silicone oil has a good emulsion effect and good thermal stability, and can be effectively used in the finishing of fabrics, and the finished fabrics have excellent softness, anti-yellowing properties and anti-Staphylococcus aureus properties.

[0058] (3) The present invention provides a fabric softening, anti-yellowing, and anti-bacterial finishing emulsion. When used for fabric finishing, the emulsion can greatly improve the softness, anti-yellowing effect, and anti-Staphylococcus aureus effect of the fabric.

[0059] (4) The present invention provides a fabric softening, anti-yellowing and antibacterial finishing emulsion. The preparation conditions are relatively simple. The prepared emulsion does not stratify when left standing for more than three months at room temperature and has good stability.

[0060] (5) The antibacterial softener of the present invention has the advantages of good softening effect, low yellowing and resistance to Staphylococcus aureus when used for finishing fabrics. The polymer dispersibility index of the antibacterial softener is small, and the particle size distribution is basically at 120nm, showing milky white, and having good penetration ability into fabric fibers. In addition, the critical micelle concentration value of the antibacterial softener is low, which can achieve the purpose of reducing the amount of emulsion used and thus saving production costs. In addition, the surface tension of the antibacterial softener is low, which can make the fabric fibers easily expand their surface and stretch their length after finishing the fabric, so that the fabric becomes fluffy and plump, and has a soft feel.

[0061] (6) The preparation method of the antibacterial softener of the present invention has the characteristics of simple preparation method, low production cost, and suitability for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0063] Figure 1This is a synthetic route for a block-type quaternary ammonium salt organic silicone oil of the present invention; in the figure, H-PDMS refers to terminal hydrogen silicone oil, NAMA refers to N-methylallylamine, PASO refers to preliminary block structure organic silicone oil, GTAC refers to 2,3-epoxypropyltrimethylammonium chloride, and GPTAC refers to block-type quaternary ammonium salt organic silicone oil.

[0064] Figure 2 FT-IR analysis curve of the block quaternary ammonium salt silicone oil prepared in Example 1 of the present invention.

[0065] Figure 3 3 is a thermogravimetric analysis curve of the block quaternary ammonium salt silicone oil prepared in Example 1 of the present invention.

[0066] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of the block quaternary ammonium salt silicone oil prepared in Example 1 of the present invention.

[0067] Figure 5 1 is a graph showing the static contact angle test results of the antibacterial softener prepared in Example 9 of the present invention after finishing the fabric.

[0068] Figure 6 This is a graph showing the test data of whiteness, hydrophilicity, softness, stiffness and friction coefficient of fabric before and after finishing with the antibacterial softener prepared in Example 9 of the present invention.

[0069] Figure 7 1 is a graph showing the antibacterial activity of the antibacterial softener prepared in Example 9 of the present invention against Staphylococcus aureus before and after fabric finishing. DETAILED DESCRIPTION

[0070] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0071] The terms used in the embodiments of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. In the present invention, the singular forms "a," "an," "the," and "the" used in the embodiments and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0072] In an embodiment of the present invention, a block-type quaternary ammonium salt organic silicone oil has a chemical structure as shown in Formula I:

[0073]

[0074] Wherein, n is an integer.

[0075] In an embodiment of the present invention, a method for preparing a block-type quaternary ammonium salt organic silicone oil comprises the following steps:

[0076] S1. Dispersing hydrogen-terminated silicone oil and N-methylallylamine in a solvent, heating in an air atmosphere, and then adding a catalyst to carry out a hydrosilylation reaction to obtain a preliminary block structure silicone oil;

[0077] S2. Add 2,3-epoxypropyltrimethylammonium chloride to the system in step S1, and continue heating under air atmosphere to perform epoxy ring-opening reaction, thereby obtaining the block quaternary ammonium salt silicone oil.

[0078] In some embodiments, the hydrogen-terminated silicone oil has a chemical structure as shown in Formula II:

[0079]

[0080] Wherein, n is an integer; and / or

[0081] The molecular weight of the hydrogen-terminated silicone oil is 6,000 to 12,000.

[0082] Wherein, N-methylallylamine has the chemical structure of formula IV:

[0083]

[0084] Wherein, the preliminary block structure organic silicone oil has the chemical structure shown in Formula III:

[0085]

[0086] Wherein, n is an integer.

[0087] Wherein, 2,3-epoxypropyltrimethylammonium chloride has the chemical structure of Formula V:

[0088]

[0089] In some embodiments, in step S1, the molar ratio of the hydrogen-terminated silicone oil to N-methylallylamine is 1:(1.6-2.4); and / or

[0090] The solvent is at least one of toluene, ethanol, isopropanol, n-butanol or ethylene glycol monobutyl ether; the mass of the solvent accounts for 10% to 20% of the total mass of the hydrogen-terminated silicone oil and N-methylallylamine; and / or

[0091] The catalyst is a Speier catalyst; the mass of the catalyst is 10ppm-30ppm of the mass of the end-hydrogenated silicone oil; and / or

[0092] The temperature of the hydrosilylation reaction is 60° C. to 80° C., and the reaction time is 5 h to 7 h; and / or

[0093] The heating method of the hydrosilylation reaction is oil bath heating or electric heating; and / or

[0094] When dispersing the hydrogen-terminated silicone oil and N-methylallylamine in the solvent, stirring is adopted, and the stirring speed is 250 rpm / min to 300 rpm / min.

[0095] In some embodiments, in step S2, the molar ratio of the 2,3-epoxypropyltrimethylammonium chloride to the preliminary block structure silicone oil is (1.6-1.8):1; and / or

[0096] The temperature of the epoxy ring-opening reaction is 90°C to 120°C, and the reaction time is 11h to 15h;

[0097] After the epoxy ring-opening reaction is completed, the solvent is removed; and / or the solvent is removed at -0.01 MPa and 50° C. to 90° C. for 1 hour.

[0098] In an embodiment of the present invention, a fabric softening, anti-yellowing, and antibacterial finishing emulsion is provided, which comprises the aforementioned blocked quaternary ammonium salt organic silicone oil or the blocked quaternary ammonium salt organic silicone oil prepared by the aforementioned method for preparing the blocked quaternary ammonium salt organic silicone oil.

[0099] In an embodiment of the present invention, a method for preparing a fabric softening, anti-yellowing, and antibacterial finishing emulsion is provided. The fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following components in parts by weight:

[0100]

[0101]

[0102] The preparation method of the fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following steps: stirring and mixing a formulated amount of a block quaternary ammonium salt organic silicone oil, an emulsifier, and a solubilizer at a rotation speed of 3000 rpm / min to 10000 rpm / min to obtain an oil phase; adding a formulated amount of a stabilizer and water to the oil phase; and dispersing and homogenizing the mixture at a rotation speed of 5000 rpm / min to 6000 rpm / min for 10 to 20 minutes; and then adjusting the pH of the system to 5 to 6, thereby obtaining the fabric softening, anti-yellowing, and antibacterial finishing emulsion.

[0103] In an embodiment of the present invention, an antibacterial softener includes the above-mentioned antibacterial finishing emulsion for softening and anti-yellowing fabrics or the antibacterial finishing emulsion for softening and anti-yellowing fabrics prepared by the above-mentioned method for preparing the antibacterial finishing emulsion for softening and anti-yellowing fabrics.

[0104] In an embodiment of the present invention, a method for preparing an antibacterial softener is provided, wherein the antibacterial softener comprises the following components in parts by weight:

[0105] Applied to fabric softening, anti-yellowing and antibacterial finishing emulsion 1 to 3 parts

[0106] 50 to 250 parts water;

[0107] The preparation method of the antibacterial softener comprises the following steps: diluting a formulated amount of a fabric softening, anti-yellowing, and antibacterial finishing emulsion with a formulated amount of water, and stirring the emulsion uniformly to obtain the antibacterial softener.

[0108] The following describes the details in conjunction with specific embodiments.

[0109] Example 1

[0110] A method for preparing a block-type quaternary ammonium salt organic silicone oil comprises the following steps:

[0111] S1. Dispersing hydrogen-terminated silicone oil and N-methylallylamine in n-butanol at a speed of 280 rpm / min with stirring, heating to 70° C. in an oil bath in an air atmosphere, and then adding a Speier catalyst for a hydrosilylation reaction for 6 hours to obtain a preliminary block structure organosilicon oil, code-named PASO; in this embodiment, the molecular weight of the hydrogen-terminated silicone oil is 9000; in this embodiment, the molar ratio of the hydrogen-terminated silicone oil to N-methylallylamine is 1:2; the mass of n-butanol accounts for 15% of the total mass of the hydrogen-terminated silicone oil and N-methylallylamine; the mass of the Speier catalyst is 20 ppm of the mass of the hydrogen-terminated silicone oil;

[0112] S2. Add 2,3-epoxypropyltrimethylammonium chloride to the system of step S1, continue heating to 100°C under air atmosphere, and carry out the epoxy ring-opening reaction for 13 hours. Then, remove the solvent at -0.01 MPa and 70°C for 1 hour to obtain a block quaternary ammonium salt silicone oil, a light yellow, transparent, viscous liquid, code-named GPTAC. In this embodiment, the molar ratio of 2,3-epoxypropyltrimethylammonium chloride to the preliminary block structure silicone oil is 1.7:1.

[0113] The synthetic route of the block quaternary ammonium salt organic silicone oil is shown in Figure 1 .

[0114] Among them, the FT-IR analysis curve of a block type quaternary ammonium salt silicone oil prepared in this embodiment is shown in FIG. Figure 2 . Figure 2 In the table, H-PDMS refers to hydrogen-terminated silicone oil, NAMA refers to N-methylallylamine, PASO refers to preliminary block structure silicone oil, and GPTAC refers to block type quaternary ammonium salt silicone oil. Figure 2 Visible in the middle, of which 950cm -1 -1100cm -1 、1260cm -1 The signals are the characteristic stretching vibrations of -Si-O-Si- and -Si-CH3 in polysiloxane. -1 and 2160cm -1 The -Si-H signal in H-PDMS is not present in the PASO infrared curve. -1 The -NH stretching vibration is absent in the infrared signals of GPTAC, indicating the successful synthesis of GPTAC.

[0115] The thermogravimetric analysis curve of the block quaternary ammonium salt organic silicone oil prepared in this embodiment is shown in FIG. Figure 3 ,from Figure 3 As shown in the figure, GPTAC is stable below 400°C, decomposing between 425°C and 650°C. Within the temperature range of 0°C to 425°C, GPTAC experiences a relatively slow mass loss, with a weight loss of 7.5%. This is due to the repetitive Si-O segments in the GPTAC structure, which prevent chemical bonds from breaking at high temperatures. This indicates that GPTAC has good thermal stability. Cotton fabric was treated with GPTAC emulsion and then dried at 130°C. Therefore, GPTAC emulsions can meet the high-temperature requirements of fabric finishing.

[0116] The H NMR spectrum of the block quaternary ammonium salt organic silicone oil prepared in this embodiment is shown in FIG. Figure 4 .from Figure 4 It can be seen that the signals of δ = -0.05 (aH) and δ = 0.04 (bH) are attributed to the methyl and methylene protons connected to silicon in the polydimethylsiloxane main chain. The signals of δ = 0.16 (cH) and δ = 0.91 (dH) represent the methylene protons connected to carbon atoms; the signals of δ = 2.26 (eH), δ = 2.50 (fH) and δ = 3.49 (gH) represent the methyl and methylene protons connected to nitrogen, and δ = 3.63 (hH) is the methine signal connected to the O atom. Figure 2 FT-IR and Figure 4 1 The results of the H NMR spectrum show that the GPTAC product was synthesized in the present invention.

[0117] Example 2

[0118] A method for preparing a block-type quaternary ammonium salt organic silicone oil comprises the following steps:

[0119] S1. Dispersing hydrogen-terminated silicone oil and N-methylallylamine in ethanol at a stirring speed of 250 rpm / min, heating to 60° C. by electric heating in an air atmosphere, and then adding a Speier catalyst for a hydrosilylation reaction for 7 hours to obtain a preliminary block structure organic silicone oil, code-named PASO; in this embodiment, the molecular weight of the hydrogen-terminated silicone oil is 6000; in this embodiment, the molar ratio of the hydrogen-terminated silicone oil to N-methylallylamine is 1:1.6; the mass of ethanol accounts for 10% of the total mass of the hydrogen-terminated silicone oil and N-methylallylamine; the mass of the Speier catalyst is 10 ppm of the mass of the hydrogen-terminated silicone oil;

[0120] S2. Add 2,3-epoxypropyltrimethylammonium chloride to the system in step S1, continue heating to 90°C under air atmosphere, and conduct the epoxy ring-opening reaction for 15 hours. Then, remove the solvent at -0.01 MPa and 50°C for 1 hour to obtain a block quaternary ammonium salt silicone oil, a light yellow, transparent, viscous liquid, code-named GPTAC. In this embodiment, the molar ratio of 2,3-epoxypropyltrimethylammonium chloride to the preliminary block structure silicone oil is 1.6:1.

[0121] Example 3

[0122] A method for preparing a block-type quaternary ammonium salt organic silicone oil comprises the following steps:

[0123] S1. Dispersing hydrogen-terminated silicone oil and N-methylallylamine in toluene with stirring at a speed of 300 rpm / min, heating to 80° C. in an oil bath in an air atmosphere, and then adding a Speier catalyst for hydrosilylation reaction for 5 hours to obtain a preliminary block structure organosilicon oil, code-named PASO; in this embodiment, the molecular weight of the hydrogen-terminated silicone oil is 12,000; in this embodiment, the molar ratio of the hydrogen-terminated silicone oil to N-methylallylamine is 1:2.4; the mass of toluene accounts for 20% of the total mass of the hydrogen-terminated silicone oil and N-methylallylamine; the mass of the Speier catalyst is 30 ppm of the mass of the hydrogen-terminated silicone oil;

[0124] S2. Add 2,3-epoxypropyltrimethylammonium chloride to the system in step S1, continue heating to 120°C under air atmosphere, and carry out the epoxy ring-opening reaction for 11 hours. Then, remove the solvent at -0.01 MPa and 90°C for 1 hour to obtain a block quaternary ammonium salt silicone oil, a light yellow, transparent, viscous liquid, code-named GPTAC. In this embodiment, the molar ratio of 2,3-epoxypropyltrimethylammonium chloride to the preliminary block structure silicone oil is 1.8:1.

[0125] Example 4

[0126] A method for preparing a block-type quaternary ammonium salt organic silicone oil comprises the following steps:

[0127] S1. Dispersing hydrogen-terminated silicone oil and N-methylallylamine in isopropanol at a speed of 260 rpm / min with stirring, heating to 650° C. in an oil bath in an air atmosphere, and then adding a Speier catalyst for a hydrosilylation reaction for 6.5 hours to obtain a preliminary block structure organosilicon oil, code-named PASO. In this embodiment, the molecular weight of the hydrogen-terminated silicone oil is 8000. In this embodiment, the molar ratio of the hydrogen-terminated silicone oil to N-methylallylamine is 1:1.8. The mass of isopropanol accounts for 12% of the total mass of the hydrogen-terminated silicone oil and N-methylallylamine. The mass of the Speier catalyst is 15 ppm of the mass of the hydrogen-terminated silicone oil.

[0128] S2. Add 2,3-epoxypropyltrimethylammonium chloride to the system in step S1, continue heating to 95°C under air atmosphere, and conduct the epoxy ring-opening reaction for 14 hours. Then, remove the solvent at -0.01 MPa and 60°C for 1 hour to obtain a block quaternary ammonium salt silicone oil, a light yellow, transparent, viscous liquid, code-named GPTAC. In this embodiment, the molar ratio of 2,3-epoxypropyltrimethylammonium chloride to the preliminary block structure silicone oil is 1.7:1.

[0129] Example 5

[0130] A method for preparing a block-type quaternary ammonium salt organic silicone oil comprises the following steps:

[0131] S1. Dispersing hydrogen-terminated silicone oil and N-methylallylamine in ethylene glycol monobutyl ether with stirring at a speed of 290 rpm / min, heating to 75° C. by electric heating in an air atmosphere, and then adding a Speier catalyst for hydrosilylation reaction for 5.5 hours to obtain a preliminary block structure organic silicone oil, code-named PASO; in this embodiment, the molecular weight of the hydrogen-terminated silicone oil is 11,000; in this embodiment, the molar ratio of the hydrogen-terminated silicone oil to N-methylallylamine is 1:2.2; the mass of the solvent accounts for 18% of the total mass of the hydrogen-terminated silicone oil and N-methylallylamine; the mass of the Speier catalyst is 25 ppm of the mass of the hydrogen-terminated silicone oil;

[0132] S2. Add 2,3-epoxypropyltrimethylammonium chloride to the system in step S1, continue heating to 110°C under air atmosphere, and conduct the epoxy ring-opening reaction for 12 hours. Then, remove the solvent at -0.01 MPa and 80°C for 1 hour to obtain a block quaternary ammonium salt silicone oil, a light yellow, transparent, viscous liquid, code-named GPTAC. In this embodiment, the molar ratio of 2,3-epoxypropyltrimethylammonium chloride to the preliminary block structure silicone oil is 1.6:1.

[0133] Example 6

[0134] A fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the block quaternary ammonium salt organic silicone oil prepared in Example 1. The fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following components in parts by weight:

[0135]

[0136] In this embodiment, the emulsifier is a nonionic surfactant of the AEO series, the solubilizer is ethylene glycol butyl ether, and the stabilizer is EDTA.

[0137] The preparation method of a fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following steps: stirring and mixing a formulated amount of a block quaternary ammonium salt organic silicone oil, an emulsifier, and a solubilizer at a rotation speed of 6000 rpm / min to obtain an oil phase; adding a formulated amount of a stabilizer and water to the oil phase; and dispersing and homogenizing the mixture at a rotation speed of 5500 rpm / min for 15 minutes; and then adjusting the pH of the system to 5.5, thereby obtaining the fabric softening, anti-yellowing, and antibacterial finishing emulsion.

[0138] Example 7

[0139] A fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the block quaternary ammonium salt organic silicone oil prepared in Example 2. The fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following components in parts by weight:

[0140]

[0141] In this embodiment, the emulsifier is a nonionic surfactant of the AEO series, the solubilizer is ethylene glycol butyl ether, and the stabilizer is EDTA-2Na.

[0142] The preparation method of a fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following steps: stirring and mixing a formulated amount of a block quaternary ammonium salt organic silicone oil, an emulsifier, and a solubilizer at a rotation speed of 3000 rpm / min to obtain an oil phase; adding a formulated amount of a stabilizer and water to the oil phase; and dispersing and homogenizing the mixture at a rotation speed of 5000 rpm / min for 20 minutes; and then adjusting the pH of the system to 5, thereby obtaining the fabric softening, anti-yellowing, and antibacterial finishing emulsion.

[0143] Example 8

[0144] A fabric softening, anti-yellowing, and antibacterial finishing emulsion comprising the block-type quaternary ammonium salt organic silicone oil prepared in Example 3. The fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following components in parts by weight:

[0145]

[0146]

[0147] In this embodiment, the emulsifier is a nonionic surfactant of the AEO series, the solubilizer is ethylene glycol butyl ether, and the stabilizer is EDTA.

[0148] The preparation method of a fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following steps: stirring and mixing a formulated amount of a block quaternary ammonium salt silicone oil, an emulsifier, and a solubilizer at a rotation speed of 10,000 rpm / min to obtain an oil phase; adding a formulated amount of a stabilizer and water to the oil phase; and dispersing and homogenizing the mixture at a rotation speed of 6,000 rpm / min for 10 minutes; and then adjusting the pH of the system to 6, thereby obtaining the fabric softening, anti-yellowing, and antibacterial finishing emulsion.

[0149] Example 9

[0150] An antibacterial softener, comprising the anti-yellowing and antibacterial finishing emulsion for fabric softening of Example 6. The antibacterial softener comprises the following components in parts by weight:

[0151] 3 parts of fabric softening, anti-yellowing and antibacterial finishing emulsion

[0152] 100 parts water.

[0153] The preparation method of the antibacterial softener comprises the following steps: diluting a formulated amount of a fabric softening, anti-yellowing, and antibacterial finishing emulsion with a formulated amount of water, and stirring the emulsion evenly to obtain the antibacterial softener.

[0154] Example 10

[0155] An antibacterial softener, comprising the anti-yellowing and antibacterial finishing emulsion for fabric softening of Example 7. The antibacterial softener comprises the following components in parts by weight:

[0156] 1 part of fabric softening, anti-yellowing and antibacterial finishing emulsion

[0157] 50 parts water.

[0158] The preparation method of the antibacterial softener comprises the following steps: diluting a formulated amount of a fabric softening, anti-yellowing, and antibacterial finishing emulsion with a formulated amount of water, and stirring the emulsion evenly to obtain the antibacterial softener.

[0159] Example 11

[0160] An antibacterial softener, comprising the anti-yellowing and antibacterial finishing emulsion for fabric softening of Example 8. The antibacterial softener comprises the following components in parts by weight:

[0161] 3 parts of fabric softening, anti-yellowing and antibacterial finishing emulsion

[0162] 250 parts water.

[0163] The preparation method of the antibacterial softener comprises the following steps: diluting a formulated amount of a fabric softening, anti-yellowing, and antibacterial finishing emulsion with a formulated amount of water, and stirring the emulsion evenly to obtain the antibacterial softener.

[0164] Fabric finishing experiments:

[0165] The antibacterial softener prepared in Example 9 was used to perform a fabric finishing experiment. The fabric finishing experiment process is as follows:

[0166] A certain area of cotton fabric (woven cotton cloth, weave count 40) was cut and immersed in the antibacterial softener prepared in Example 9. The fabric was then placed in a liquid press to remove excess liquid (squeeze rate > 80%). The fabric was then baked in an oven at 130°C for 3 minutes and then allowed to regain moisture at room temperature for 24 hours. The fabric was then subjected to fabric performance tests, including wettability test, whiteness test, hydrophilicity test, softness test, and antibacterial performance test.

[0167] (1) Wettability test

[0168] The water drop wettability test was conducted on the fabric samples treated with the antibacterial softener of Example 9 and the fabric samples before treatment using the video optical contact angle measuring instrument OCA100 produced by Dataphysics of Germany. The contact angle results were averaged from 5 measurement points. Please refer to the test results. Figure 5 .

[0169] Depend on Figure 5 The results show that the wettability of the fabric treated with the antibacterial softener of the present invention has been improved qualitatively, and the contact angle of the original cotton cloth has dropped to 0° in less than 1 second (see Figure 5 ac), and cotton fabric modified with antibacterial softener, GPTAC, takes 5 seconds to drop to 0° (see Figure 5 This may be largely due to the long polysiloxane chains of GPTAC.

[0170] (2) Whiteness test

[0171] According to the method of GB / T 7973-2003, fabric samples before finishing and after finishing with the antibacterial softener of Example 9 were tested on a colorimeter. The fabric samples were tested five times in parallel. The five measured values were averaged and compared with the whiteness value of the fabric samples before finishing to measure the yellowing resistance of the finished fabric. The test results are shown in Table 1.

[0172] (3) Hydrophilicity test

[0173] According to the AATCC 79-2000 Textile Water Absorption Test Standard, the time it takes for the fabric to completely absorb a drop of water (i.e., the time it takes for the light reflection of the water drop to disappear) is measured under static conditions before and after finishing, and the average value is taken from the five measurements.

[0174] (4) Softness test

[0175] Fabric softness was assessed using three indicators: softness, smoothness, and stiffness. Softness was measured according to GB / T8942-2002 using a RH-R1000 computerized softness meter, with the average value calculated as five measurements. Smoothness was measured according to GB10006-88 using an MXD-02 friction coefficient tester, with the average value calculated as five measurements. Stiffness was measured according to GB / T18318.1-2009 using a YG(B)022d automatic fabric stiffness tester, with the average value calculated as five measurements.

[0176] The results of the whiteness, hydrophilicity and softness tests on the fabric samples before and after finishing are shown in the table below. Figure 6 .

[0177] Depend on Figure 6 The result shows, adopt the fabric after antibacterial softening agent of the present invention to process to compare with the whiteness value of undressed fabric cloth sample, the fabric after antibacterial softening agent is processed, its whiteness does not change substantially, and after the antibacterial softening agent that therefore a kind of block type quaternary ammonium salt organosilicone oil of the present invention makes carries out after-treatment to fabric, fabric has good anti-yellowing property.In addition, fabric only needs 2.15 seconds to have sucked a drop of water before arrangement, and after antibacterial softening agent of the present invention is arranged, and needs 41.05 seconds to have sucked a drop of water, shows that after the antibacterial softening agent that a kind of block type quaternary ammonium salt organosilicone oil of the present invention makes carries out after-treatment to fabric, fabric has hydrophobic property.In addition, after antibacterial softening agent is arranged, the softness and the stiffness of fabric greatly improve, and smoothness also improves simultaneously, shows that a kind of block type quaternary ammonium salt organosilicone oil of the present invention has good softness property.

[0178] Combined with the whiteness test, hydrophilicity test and softness test results of the fabric before and after finishing with the antibacterial softener, it can be shown that the antibacterial softener prepared from the block quaternary ammonium salt silicone oil of the present invention has excellent hydrophilicity, softness and anti-yellowing ability.

[0179] (5) Antibacterial performance test

[0180] The antibacterial performance test was carried out according to GB / T20944.3-2008 standard by the colony count of Staphylococcus aureus provided by the plate count method.

[0181] Among them, the fabric samples before and after finishing were tested for Staphylococcus aureus. The test results can be found in Figure 7 .

[0182] Depend on Figure 7 Results show that cotton fabric treated with higher concentrations of antimicrobial softener exhibits enhanced antimicrobial activity against Staphylococcus aureus. Cotton fabric treated with antimicrobial softener at concentrations of 20 g / L or higher virtually kills Staphylococcus aureus. This is attributed to the amino structures, particularly the quaternary ammonium groups, at both ends of the block quaternary ammonium salt silicone oil produced by the present invention. Overall, this indicates that cotton fabric treated with the antimicrobial softener of the present invention exhibits excellent antimicrobial activity against Staphylococcus aureus.

[0183] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A block type quaternary ammonium salt silicone oil, characterized in that, It has the chemical structure shown in Formula I: Wherein, n is an integer.

2. The method for preparing a block type quaternary ammonium salt organic silicone oil according to claim 1, wherein The following steps are involved: S1. Dispersing hydrogen-terminated silicone oil and N-methylallylamine in a solvent, heating in an air atmosphere, and then adding a catalyst to carry out a hydrosilylation reaction to obtain a preliminary block structure silicone oil; S2. Add 2,3-epoxypropyltrimethylammonium chloride to the system in step S1, and continue heating under air atmosphere to perform epoxy ring-opening reaction, thereby obtaining the block quaternary ammonium salt silicone oil.

3. A method for preparing a block type quaternary ammonium salt organosilicone oil as claimed in claim 2, wherein: The hydrogen-terminated silicone oil has a chemical structure as shown in Formula II: wherein n is an integer; and / or The molecular weight of the hydrogen-terminated silicone oil is 6,000 to 12,000.

4. The method for preparing a block type quaternary ammonium salt organic silicone oil as claimed in claim 2, wherein: The preliminary block structure organic silicone oil has a chemical structure as shown in Formula III: Wherein, n is an integer.

5. A method for preparing a block type quaternary ammonium salt organosilicone oil as claimed in claim 2, wherein: In step S1, the molar ratio of the hydrogen-terminated silicone oil to N-methylallylamine is 1:(1.6-2.4); and / or The solvent is at least one of toluene, ethanol, isopropanol, n-butanol or ethylene glycol monobutyl ether; the mass of the solvent accounts for 10% to 20% of the total mass of the hydrogen-terminated silicone oil and N-methylallylamine; and / or The catalyst is a Speier catalyst; the mass of the catalyst is 10ppm-30ppm of the mass of the end-hydrogenated silicone oil; and / or The temperature of the hydrosilylation reaction is 60° C. to 80° C., and the reaction time is 5 h to 7 h; and / or The heating method of the hydrosilylation reaction is oil bath heating or electric heating; and / or When dispersing the hydrogen-terminated silicone oil and N-methylallylamine in the solvent, stirring is adopted, and the stirring speed is 250 rpm / min to 300 rpm / min.

6. A method for preparing a block type quaternary ammonium salt organosilicone oil as claimed in claim 2, characterized in that, In step S2, the molar ratio of the 2,3-epoxypropyltrimethylammonium chloride to the preliminary block structure silicone oil is (1.6-1.8):1; and / or The temperature of the epoxy ring-opening reaction is 90°C to 120°C, and the reaction time is 11h to 15h; After the epoxy ring-opening reaction is completed, the solvent is removed; and / or the solvent is removed at -0.01 MPa and 50° C. to 90° C. for 1 hour.

7. A fabric softening, anti-yellowing and antibacterial finishing emulsion, characterized in that: The invention relates to a block type quaternary ammonium salt organic silicone oil according to claim 1 or a block type quaternary ammonium salt organic silicone oil prepared by the preparation method of the block type quaternary ammonium salt organic silicone oil according to any one of claims 2 to 6.

8. The method for preparing the fabric softening, anti-yellowing and antibacterial finishing emulsion according to claim 7, characterized in that: The fabric softening, anti-yellowing and antibacterial finishing emulsion comprises the following components in parts by weight: The preparation method of the fabric softening, anti-yellowing, and antibacterial finishing emulsion comprises the following steps: stirring and mixing a formulated amount of a block quaternary ammonium salt organic silicone oil, an emulsifier, and a solubilizer at a rotation speed of 3000 rpm / min to 10000 rpm / min to obtain an oil phase; adding a formulated amount of a stabilizer and water to the oil phase; and dispersing and homogenizing the mixture at a rotation speed of 5000 rpm / min to 6000 rpm / min for 10 to 20 minutes; and then adjusting the pH of the system to 5 to 6, thereby obtaining the fabric softening, anti-yellowing, and antibacterial finishing emulsion.

9. An antibacterial softener, characterized in that: The invention comprises the fabric softening, anti-yellowing and antibacterial finishing emulsion as claimed in claim 7 or the fabric softening, anti-yellowing and antibacterial finishing emulsion prepared by the preparation method of the fabric softening, anti-yellowing and antibacterial finishing emulsion as claimed in claim 8.

10. The method for preparing an antibacterial softener according to claim 9, characterized in that: The antibacterial softener comprises the following components in parts by weight: Applied to fabric softening, anti-yellowing and antibacterial finishing emulsion 1 to 3 parts 50 to 250 parts water; The preparation method of the antibacterial softener comprises the following steps: diluting a formulated amount of a fabric softening, anti-yellowing, and antibacterial finishing emulsion with a formulated amount of water, and stirring the emulsion uniformly to obtain the antibacterial softener.

Images