A hard low refractive index polymer nanoparticle stabilized silicone oil emulsion, its preparation method and application

Abstract

The application belongs to the technical field of textile auxiliaries, and specifically discloses a hard low-refractive-index polymer nanoparticle-stabilized silicone oil emulsion as well as a preparation method and application thereof; components of the hard low-refractive-index polymer nanoparticle-stabilized silicone oil emulsion include amino silicone oil, an emulsifier, a hard low-refractive-index polymer nanoparticle emulsion, a pH regulator and deionized water. The application solves the problems of poor stability of silicone oil emulsion, low efficiency of textile finishing and high COD of finishing residual liquid, and the obtained silicone oil emulsion has excellent dispersion stability; the addition of the hard low-refractive-index polymer nanoparticle emulsion does not change the apparent color depth of fabrics, effectively balances the hand feeling and slippage of textiles, reduces the amount of emulsifier, better reduces the COD value in padding waste liquid, and is not prone to sticking to rollers, and has good production continuity, thereby improving the practicality and comfort.

Description

Technical Field

[0001] This invention relates to the field of textile auxiliaries, specifically to a silicone oil emulsion stabilized by rigid, low-refractive-index polymer nanoparticles, its preparation method, and its application. Background Technology

[0002] Silicone oils possess characteristics such as low interfacial tension, high molecular chain flexibility, and good film-forming properties, which can impart softness, smoothness, and fluffiness to finished fabrics. Therefore, they are widely used as finishing agents in textiles to improve the fabric's feel. In textile processing, silicone oils are usually pre-emulsified into an "oil / water" emulsion. For example, patent CN113185710A discloses an amino silicone oil emulsion and its preparation method. This involves first mixing an emulsifier and a stabilizer (amino silicone oil), and then adding a co-emulsifier and water to obtain an emulsion with a bicontinuous phase structure between O / W and W / O. This amino silicone oil emulsion exhibits high stability. Patent CN112048067B provides a method for preparing polyurethane-modified amino polyether silicone oil. This method features high reaction efficiency, multiple active groups with side chains and end chains, forming a multi-dimensional network cross-linked structure that effectively enhances the permeability to fabrics, improves fabric softness, and simultaneously enhances hydrophilicity.

[0003] However, taking silicone oils with smoothing properties as an example, their high molecular weight and high viscosity often result in poor dispersion stability of their emulsions. To prevent demulsification and roller sticking in such silicone oil emulsions, the amount of emulsifier added during silicone oil emulsification is often very high, sometimes even reaching 50% of the silicone oil mass. High doses of emulsifier not only increase the processing cost of silicone oil emulsions, but also form a thick hydrophilic layer on the surface of silicone oil droplets, hindering the adsorption of silicone oil droplets onto the fabric. This reduces the efficiency of silicone oil finishing and significantly increases the COD of the residual liquid. Therefore, developing new and efficient silicone oil emulsification or dispersion systems is crucial.

[0004] In Pickering emulsions using solid particles as stabilizers, the emulsion is stabilized by solid particles adsorbed at the oil / water interface. During emulsification, by altering the particle size and the hydrophilic-lipophilic balance of the particle surface, the solid particles irreversibly adsorb at the oil / water interface, forming a mechanical barrier that inhibits the aggregation of dispersed droplets. Because the adsorption is irreversible, the stabilization efficiency of the solid particles for droplets is significantly higher than that of emulsifier molecules in dynamic equilibrium. Furthermore, the solid particles do not form a hydrophilic layer on the surface of dispersed phase droplets such as silicone oil, thus not reducing the efficiency of the dispersed phase droplets adsorbing onto the fabric.

[0005] Recently, patent application CN113698626A published "A Soft Nanoparticle-Stabilized Silicone Oil Emulsion and Its Preparation Method": The patent reports a method for preparing a silicone oil emulsion stabilized by an emulsifier and soft polymer particles such as PEHA, PBA, or PPA. This technology can obtain a stable and dispersed silicone oil emulsion with the help of soft polymer particles, using an emulsifier dosage of 7.7% by mass of silicone oil. The amount of emulsifier used in this silicone oil emulsion is only 1 / 7 of that used without soft nanoparticles. The characteristic of this technology is that it reduces the amount of emulsifier used, but with the softening and film formation of soft particles and the efficient adsorption of silicone oil, the fiber surface becomes very smooth, and the degree of fabric splitting is aggravated.

[0006] Papers (such as Colloids and Surfaces A: Physicochemical and Engineering Aspects 132 (1998) 257-265; Journal of Colloid and Interface Science 2010, 351, 348–356) reported a scheme using modified silica as pickering particles to stabilize silicone oil emulsions. However, this scheme is not suitable for textile finishing because, when testing the rubbing fastness of silicone oil-finished fabrics using this scheme, the high hardness of silica particles causes severe fiber wear, and the exposed dye contaminates the rubbing head, easily leading to problems such as substandard rubbing fastness. The same reason also appears in the paper by Masami Kawaguchi et al. using titanium dioxide as a stabilizer (Colloids and Surfaces A: Physicochemical.Eng.Aspects 2011, 392, 283–287).

[0007] Papers (Langmuir 2004, 20, 3492-3494;), (Journal of Colloid and Interface Science 2011, 363, 307–313), and (doi:10.1080 / 01932691.2015.1007377) report a scheme for stabilizing silicone oil emulsions using polystyrene particles or modified large-particle-size (>300 nm) polystyrene (PSt) particles as Pickering particles. While large-sized PST particles help stabilize silicone oil emulsions and have lower hardness than silica particles, thus not causing a decrease in fabric rubbing fastness, PST has a high refractive index (approximately 1.60). Especially when the particle size is greater than 160 nm (=800 / 1.6 / 3.14, Nano letters, 2008, 8(9):2638-2642), PST applied to the fabric can cause light scattering, making the fabric appear white and altering the fabric's color depth and other properties. Summary of the Invention

[0008] To address the problems in existing technologies, this invention provides a silicone oil emulsion stabilized by rigid low-refractive-index polymer nanoparticles, its preparation method, and its application. This solves the problems of poor stability of silicone oil emulsions and poor finishing effects on textiles. The silicone oil emulsion exhibits excellent emulsion stability. The addition of rigid low-refractive-index polymer nanoparticle emulsion effectively balances the hand feel and cracking of textiles, reduces the amount of emulsifier used, significantly reduces the COD value in padding wastewater, and is less prone to sticking to rollers, resulting in good production continuity. This improves its practicality and comfort.

[0009] To achieve the above technical objectives, the technical solution of the present invention is as follows:

[0010] A silicone oil emulsion stabilized by hard, low-refractive-index polymer nanoparticles comprises the following components in parts by weight: 20-30 parts amino silicone oil, 2-10 parts emulsifier, 2-30 parts hard, low-refractive-index polymer nanoparticle emulsion, 0.8-1.5 parts pH adjuster, and 50-60 parts deionized water.

[0011] The emulsifier is one or more of isotridecyl alcohol polyoxyethylene ether, isodecanol polyoxyethylene ether, and octadecyl alcohol polyoxyethylene ether.

[0012] The rigid nanoparticle emulsion is one or more of polymethyl methacrylate copolymer emulsion (PMMA) and polymethyl methacrylate isobornyl acrylate copolymer emulsion (PIBoMA). The polymer constituting the nanoparticles has a low refractive index, wherein the refractive index of polymethyl methacrylate is 1.49 and the refractive index of polymethyl methacrylate is 1.50.

[0013] The pH adjuster is acetic acid.

[0014] The method for preparing the silicone oil emulsion includes:

[0015] Amino silicone oil and emulsifier are added to a mixing vessel and mixed until homogeneous. At room temperature (10-35℃), the silicone oil is stirred at a speed of 1000-1200 rpm, while water containing hard low-refractive-index polymer nanoparticles and pH adjuster is slowly added to the mixing vessel. After the addition is completed, stirring is continued for 30-50 minutes to obtain a milky white and uniformly dispersed silicone oil emulsion.

[0016] Application of the aforementioned silicone oil emulsion stabilized by rigid, low-refractive-index polymer nanoparticles in textile finishing.

[0017] This invention employs a hard, low-refractive-index polymer nanoparticle-stabilized silicone oil emulsion, which has the following advantages:

[0018] 1. Compared with inorganic nanoparticles such as silica, polymer nanoparticles have lower hardness and are less likely to cause a decrease in the color fastness of fabrics due to rubbing.

[0019] 2. Hard nanoparticles adhere to the surface of the finished fabric, giving it a nanoscale roughness, which can improve the problem of easy cracking in silicone oil-finished fabrics to a certain extent; moreover, hard particles are less likely to stick to the rollers, improving the continuity of the finishing process.

[0020] 3. The use of low-refractive-index polymer particles, combined with particle size screening, ensures that the particles attached to the fabric do not cause scattering, but instead reduce reflection, giving the finished fabric a deeper visual effect.

[0021] 4. The addition of particles can effectively improve the stability of silicone oil emulsions, especially under conditions of low emulsifier dosage, silicone oil emulsions can still achieve good long-term stability, reducing the amount of emulsifier used.

[0022] 5. When applied to textile post-processing, this invention effectively reduces the COD value in padding wastewater, prevents sticking to rollers, ensures good production continuity, and effectively balances the hand feel and tear resistance of textiles, thereby meeting modern people's demand for textile comfort. The emulsification process provided by this invention is simple and low-cost, easy to implement and control, and conducive to widespread production. It also has strong designability, facilitating process adjustments, and the obtained materials have broad application prospects in textiles, cosmetics, and other fields. Attached Figure Description

[0023] Figure 1 This is a particle size distribution diagram of the hard, low-refractive-index polymer nanoparticles prepared in Example 3;

[0024] Figure 2This demonstrates the durable stability of the silicone oil emulsion stabilized by hard, low-refractive-index polymer nanoparticles prepared in Comparative Example 3 and Examples 2, 3, and 5.

[0025] Figure 3 The changes in COD before and after finishing of the rigid low-refractive-index polymer nanoparticle-stabilized silicone oil emulsion polyester prepared in Comparative Example 3 and Examples 2, 3, and 5 are shown.

[0026] Figure 4 The surface whiteness of the silicone oil emulsion-treated fabrics stabilized by hard, low-refractive-index polymer nanoparticles prepared in Comparative Example 1 and Example 2 is shown. Detailed Implementation

[0027] The present invention will be further described below with reference to specific embodiments, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions, or modifications made based on the present invention to solve essentially the same technical problems and achieve essentially the same technical effects are all covered within the protection scope of the present invention.

[0028] A silicone oil emulsion stabilized by hard, low-refractive-index polymer nanoparticles, its preparation method, and its application, comprising the following steps:

[0029] 1) Preparation of silicone oil emulsion stabilized by hard, low-refractive-index polymer nanoparticles:

[0030] Amino silicone oil and isomeric tridecyl alcohol polyoxyethylene ether are added to a reaction vessel and mixed until homogeneous. At room temperature, the silicone oil is stirred at a speed of 1000-1200 rpm, while water containing hard low refractive index polymer nanoparticles and acetic acid is slowly added to the reaction vessel. After the addition is completed, stirring is continued for 30-50 minutes to obtain a milky white and uniformly dispersed silicone oil emulsion.

[0031] 2) Finishing applications of polyester fabrics

[0032] According to the designed dosage, dilute the silicone oil emulsion with water to the target concentration, stir evenly and set aside; use a one-dip-one-puff process to finish the fabric, and bake at 180℃ for 90s to obtain the finished fabric.

[0033] Examples 1-6 and Comparative Examples 1-4:

[0034] Prepare according to the formula in Table 1 below.

[0035] The formula consists of the following components:

[0036] Amino silicone oil: 20%-30%

[0037] Emulsifier: 2%-10%

[0038] Hard, low-refractive-index polymer nanoparticle emulsion: 2%-30%

[0039] pH adjuster: 0.8%-1.5%

[0040] Deionized water: 50%-60%

[0041] Table 1 Formula (Kg)

[0042]

[0043] Note: 1. The remaining substances are deionized water, with a total mass of 100 kg.

[0044] 2. PMMA and PIBoMA are hard, low-refractive-index polymer nanoparticles with refractive indices of 1.49 and 1.50, respectively; PSt is a hard, high-refractive-index polymer nanoparticle with a refractive index of 1.60; and modified silica nanoparticles are hard, low-refractive-index inorganic nanoparticles with a refractive index of 1.46.

[0045] 3. The preparation methods of the particles are shown in Table 2.

[0046] Table 2 Formulations for preparing polymer nanoparticles

[0047]

[0048] Note: Prepared using a fine emulsion polymerization method: hexadecane is added to the monomer and stirred until homogeneous (oil phase); hexadecyltrimethylammonium bromide is dissolved in deionized water (aqueous phase); the oil phase is added to the aqueous phase and ultrasonically refined for 60 minutes; the refined emulsion is transferred to a reactor, heated to the temperature specified in the "Note", and an initiator is added to initiate the polymerization reaction. After the reaction time is reached, the product is discharged.

[0049] Table 3. Test results of silicone oil emulsion

[0050]

[0051] Table 4 Test Results of Fabrics Finished with Silicone Oil Emulsion

[0052]

[0053] Note: The original fabric has a K / S value of 23.5, which corresponds to a wavelength of 580nm.

[0054] Description of the characterization methods involved in the examples and comparative examples:

[0055] The rubbing fastness test was conducted in accordance with GB / T 3920-2008 "Textiles - Tests for color fastness - Color fastness to rubbing".

[0056] The yarn slippage test was conducted in accordance with GB / T 13772.2:2008 "Determination of anti-slippage of yarn at seams of woven fabrics - Part II: Constant load method";

[0057] The tactile test was conducted with reference to patents CN 112048067 B "A polyurethane modified amino polyether silicone oil and its preparation method and application" and CN 114702680 A "An ultra-high stability block silicone oil and its preparation method". Specifically, 10 professionals were grouped to rate the tactile feel on a scale of 1 to 5. The higher the rating number, the better the softness.

[0058] The COD value was tested in accordance with HJ828-2017 "Determination of Chemical Oxygen Demand in Water - Dichromate Method";

[0059] The K / S value is measured for each fabric using a Datacolor spectrophotometer. A higher K / S value indicates a darker surface color, while a lower K / S value indicates a lighter surface color.

[0060] Standing stability: Pour the amino silicone oil emulsion into a standard test tube, let it stand for 24 hours, and observe the layering of the emulsion;

[0061] Centrifugation stability: Place the emulsion in a 50 mL centrifuge tube, centrifuge at 3000 r / min for 45 min, then remove it to observe and record its appearance;

[0062] Durability test: Pour the amino silicone oil emulsion into a standard test tube, let it stand for 3 months, and observe the layering of the emulsion.

[0063] Figure 1 This is a particle size distribution diagram of the rigid low-refractive-index polymer nanoparticles prepared in Example 3. As shown in the figure, the particle size of the rigid low-refractive-index polymer nanoparticles is 150 nm. Since the particle size of the nanoparticles is small (less than 160 nm), the PMMA treated on the fabric will not cause light scattering, which is beneficial to giving the treated fabric a deeper visual effect.

[0064] Figure 2 This figure shows the long-term stability of the silicone oil emulsions stabilized by hard low-refractive-index polymer nanoparticles prepared in Comparative Example 3 and Examples 2, 3, and 5. As can be seen from the figure, after standing for 3 months, Comparative Example 3 without hard low-refractive-index polymer nanoparticles showed stratification, indicating decreased emulsion stability. Examples 2, 3, and 5, with the addition of hard low-refractive-index polymer nanoparticles, maintained a homogeneous and stable state. This demonstrates that the addition of hard low-refractive-index polymer nanoparticles can effectively improve the stability of silicone oil emulsions, achieving good long-term stability even under low emulsifier dosage conditions.

[0065] Figure 3This section describes the changes in COD values ​​of fabrics treated with silicone oil emulsions stabilized by rigid low-refractive-index polymer nanoparticles before and after Comparative Example 3 and Examples 2, 3, and 5. While increasing the emulsifier concentration improves the stability of the silicone oil emulsion, it also increases the COD value in the waste liquid. The COD reduction rate of the fabric in Comparative Example 3 (without rigid low-refractive-index polymer nanoparticles) before and after padding was 57.4%, while the COD reduction rates of the fabrics in Examples 2, 3, and 5 (with rigid low-refractive-index polymer nanoparticles) before and after padding were 63.3%, 61.0%, and 62.0%, respectively. This indicates that the addition of rigid low-refractive-index polymer nanoparticles effectively reduced the COD value in the padding waste liquid.

[0066] Figure 4 The comparison shows the surface whiteness of fabrics treated with silicone oil emulsion stabilized by rigid low-refractive-index polymer nanoparticles, as described in Comparative Example 1 and Example 2. The fabric treated with polystyrene copolymer emulsion in Comparative Example 1 exhibits a completely white visual effect, while the fabric treated with rigid low-refractive-index polymer nanoparticles in Example 2, due to the use of low-refractive-index polymer particles and particle size sieving, does not cause scattering by the particles adhering to the fabric; instead, it achieves anti-reflection, giving the treated fabric a deeper visual effect.

[0067] The above are merely preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be considered as limitations on the present invention, and the scope of protection of the present invention should be determined by the scope defined in the claims. For those skilled in the art, several improvements and modifications can be made without departing from the spirit and scope of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A process for the preparation of a hard, low refractive index, polymer nanoparticle stabilized silicone oil emulsion, characterized in that, The following components are used in the following weight parts: Amino silicone oil 20-30 parts; Emulsifier 2-10 parts; Hard low refractive polymer nanoparticle emulsion 2-30 parts; pH adjuster 0.8-1.5 parts; Deionized water 50-60 parts; The emulsifier is one or several of isomeric tridecanol polyoxyethylene ether, isodecanol polyoxyethylene ether, octadecanol polyoxyethylene ether; The hard low refractive polymer nanoparticle emulsion is one or both of polymethyl methacrylate copolymer emulsion, polyisobornyl methacrylate copolymer emulsion; The preparation method comprises the following steps: The amino silicone oil and the emulsifier are added into a reactor and mixed until uniform, stirred at a speed of 1000-1200 rpm at 10-35℃, while water containing hard low refractive polymer nanoparticles and pH adjuster is added into the reactor, after the addition is completed, continue to stir for 30-50 min, to obtain a milky white and uniformly dispersed silicone oil emulsion.

2. The method for preparing a hard, low refractive index polymer nanoparticle stabilized silicone oil emulsion according to claim 1, characterized in that, The pH adjuster is acetic acid.

3. Application of the hard low refractive polymer nanoparticle stabilized silicone oil emulsion prepared by the preparation method of claim 1 or 2 in textile finishing.

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